Biomass Gasification Search

What is Gasification ?
B. Tech ( APEG ) Semester V

UPES, Dehradun, 6-9-2017
L4&5
G.S.Dang
gurbax49@gmail.com
What is Gasification?
• Gasification is a process in which combustible materials
are partially oxidized or partially combusted
• The product of gasification is a combustible synthesis

gas, or syngas
• Gasification processes operate in an oxygen-lean

environment
What is Gasification?
Oxygep/- I i Extreme Conditions:
1,000 psig or more , 70Kg/cm2
2,600 °F ≈ 1430 o C
f Corrosive slag and H2S gas
%
i
Products (syngas)
CO (Carbon Monoxide)
H2 (Hydrogen)
Gas
Clean-Up
[CO/H2 ratio can be adjusted]
! . W\ Before
4
f
By-products Product
j
H2S (Hydrogen Sulfide) Use

M CO2 (Carbon Dioxide)
mm
Slag (Minerals from Coal)
Water
Gasification History
• First practical use of “town gas” (coal gas) was for
street lighting
• The first public street lighting with gas took place in

Pall Mall, London on January 28, 1807
• Baltimore in Maryland (USA) began the first

commercial gas lighting of residences, streets, and
businesses in 1816
• Used during World War II to convert coal into transportation
fuels (Fischer - Tropsch)
• Used extensively for the last 60+ years to convert coal and
heavy oil into hydrogen - for the production of ammonia /
urea-based fertilizer
• Chemical industry (1960’s)
• Refinery industry (1980’s)
• Global power industry (2000’s)

• Current interest is to generate syngas as an

intermediate in producing chemicals, synthetic fuels,
and clean coal power technologies
• Raw syngas from gasifier must be cleaned (removing

all gases except CO & H2) to produce different
products including for its use in power generation
Gasification
• The stoichiometric oxygen-to-coal ratio for
combustion is almost four times the
stoichiometric oxygen-to-coal ratio for
gasification ( As figure indicates)
Products of Reaction as a function of
Oxygen-to-Coal ratio
100%
CH4 H2S ratio
Gasification Zone so2 T
complete
Combustion
90% - o2
80% -
70% -
H2
e 60%
o
CD
O 50%
40% co2
30% -
CO
20% -
10% -
0%
0,1 0.7 1 .3 1,9 2.5 3.1
02/MAF Coal Feed Coal: Illinois #6
MAF coal - moisture & ash free coal

Coal combustion Vs Gasification
• Products of reaction change significantly as the oxygen-to-fuel
ratio changes from combustion to gasification
• Under gasifying conditions there is not enough oxygen available

to fully react with the feed
• Consequently, instead of producing CO2, the carbon in the feed

is converted primarily to CO, and the hydrogen in the fuel is
converted mostly to H2 rather than H2O
• Both CO and H2 are excellent fuels for use in a combustion

turbine; their combustion characteristics are however quite
different from natural gas
Gasification is similar to combustion but less oxygen is
used:
• Combustion : Excess air

• Gasification : Excess Fuel
Gasification Chemistry - Reaction of Fuel with oxygen
& Steam
• Similar to combustion but less oxygen is needed
• Combustion : Excess air
• Gasification : Excess Fuel
Gasification Chemistry
Gasification with Oxygen

c+l/2o2 CO Gasifier Gas
Composition
(VoI %)
—* Combustion with Oxygen
C + Oj *-*co2
25-30
Gasification with Carbon Dioxide CO 30-60
c + co2 2CO co2 5-15
H2O 2-30
Gasification with Steam CH4 0-5
Oxygen C + H20 * - + H*
H2S 0.2-1
Gasification with Hydrogen COS 0-0.1
C + 2Hj «*—
CH4 NI 0.5-4
Ar 0.2-
Water-Gas Shift IS Rj + HCN 0 -0.3
' CO + H2O HJ + C02
Ash/Slag/PM
Methanation
CO + 3Hj CH4 + H2O
Gasification of coal using steam and oxygen

Combustion Chemistry
Combustion Gas
Combustion with Oxygen Composition
(VoI %)
c + o2 CO*
C02 13.5
tco
2 9.8
Air S02 0.4
v2 o2 + H2 H2O Na 73.2
o2 3.2
Ash/Slag/PM
Coal combustion using excess air ; Products CO2 , H2O , SOx etc
What happens when Coal burns ?
•Carbon => C02 (carbon dioxide)

* Ash => flyash
•Sulfur => S02, S03 (SOx)
•Nitrogen => N2 and NOx
•Hydrogen => H20
•Mercury => Hg, HgCI2
•Water => water vapor (H20)
Combustion Vs Gasification
Comparative Evaluation
Parameters Combustion Gasification
Chemical Process Full Oxidation Partial Oxidation
Chemical Excess oxygen (air) oxidizing Oxygen-starved - reducing
Environment
Primary Product Heat(e.g.Steam) Producer gas(CO & H2)
Downstream Electric power Electric power, pure H2, liquid
Products fuels, chemicals
Current Dominates coal-fired power Mostly for power generation and
application generation worldwide thermal applications
Efficiency 35-37%(HHV) 39-42%(HHV)
Emissions ~NSPS ~1/10 NSPS
Capital cost Rs 5 Crores/MW Rs 5.5 Crores/MW
Maturity/Risk High experience, low risk Reliability needs improved
NSPS – New Service performance Standards ( CO2 Emissions from power plants after Aug 2015 in US)
Primary Products in
Combustion & Gasification
Combustion Gasification
Carbon co2 CO
Hydrogen H2O H2
Nitrogen NO, N()2 HCN, NH3 or N2
Sulfur S02 or S03 H2S or COS
Water H20 H2
•S02 & S03 is scrubbed out of •H2S & COS are easily removed
stack gas - reacted with lime from syngas and converted to
to form gypsum solid sulfur or sulfuric acid
•NOx controlled with low NOx •NH3 washes out of gas with water,
burners and catalytic thermal NOx controlled by diluent
conversion (SCR) injection in GT
•Large volume of flyash & •Ash is converted to glassy slag

sludge which is inert and usable
•Hg can be removed by •>90% of Hg removed by passing

contacting flue gas with high pressure syngas thru
activated carbon activated carbon bed
• Another major difference is the amount of heat released by

the chemical reaction in two processes
 In combustion all the fuel’s chemical energy is released as

heat ( assuming complete fuel combustion) but
 In gasification most of the fuel’s chemical energy is not

released as heat rather a fraction of chemical energy of
fuel remains in the product syngas
 This is termed as cold gas efficiency

• Fate of Fuel’s Nitrogen and Sulphur
 Fuel bound nitrogen is predominantly converted in NOX

in combustion
 In gasification it is converted into N2, NH3 and HCN
 which are removed from syngas during gas clean up to

a very low level
• Fate of Fuel’s Nitrogen and Sulphur
 Sulphur in the fuel produces SOx in combustion but it is

converted to H2S & COS in gasification
 These compounds are removed efficiently in gas clean up

to a level of about 20ppm
 Thus 99% of sulphur is removed from fuel and hence no

problem of SOX emissions
Environmental Contrasts
sulfur converted to... S02 H2S
flue gas scrubbers, boiler absorbed in physical or
sulfur capture
limestone injection chemical solvents
sulfur disposal gypsum sold for wallboard sold as H2S04 or elemental S
traces of NH3 in syngas
nitrogen converted
NOx (syngas combustion produces
to...
low levels of NOx)
required currently not needed for IGCC
NOx control {e.g.p low-NOx burners, staged (but tighter regs could require
combustion, SCR/SNCR) SCR)
C is converted to... C02 mostly CO in syngas
post-combustion removal from pre-combustion removal from
C02 control
diluted stream concentrated stream
much more steam cycle some water needed for slurry,

water requirements
cooling water needed steam cycle and process needs
Gasification Feedstocks
In addition to coal, gasification processes can use
other feedstocks like:
• Petroleum coke,
• Petroleum Residues /Heavy oils, or
• Biomass,
• Natural gas
The Gasifier / Reactor choice is very much linked to the

type of feedstock
Coal
• Buried biomass turned into peat under the influence
of time, pressure and temperature
• Conversion into browncoal or lignite
• Lignite in prolonged periods turns into sub-bituminous ,
bituminous and finally into anthracite coal
• Coal is classified in terms of its rank ; browncoal to
anthracite
D
0
n •• %
1
o
•*v %
’ A>
Carbbffÿ
£
•
5®
Cs
Ash (rdck)
Sulfur v•
Nitrogen
*
Hydrogen
Mercury
Water
Coal Formation and Types
-
© 2002 Brooks/Cole Thomson Learning
I Increasing heat and carbon content
Increasing moisture content
Peat Lignite Bituminous Coal Anthracite

(not a coal) (brown coal) (soft coal) (hard coal)
tgm
Heat Heat Heat
Pressure Pressure
ij Pressure
Partially decayed Low heat content; Extensively used Highly desirable fuel
plant matter in swamps low sulfur content; as a fuel because because of its high
and bogs; low heat limited supplies in of its high heat content heat content and
content most areas and large supplies; low sulfur content;
normally has a supplies are limited
high sulfur content in most areas
Gasification Feedstocks-Coal
Classification of Coal (ash & moisture free) by rank
Class Volatile matter Fixed carbon Heating value
Wt% Wt% MJ/Kg
Anthracite <8 >92 36-37
Bituminous 8-22 78-92 32-36
Sub-bituminous 22-27 73-78 28-32
Brown coal 27-35 65-73 26-28

( Lignite)
Coal Vs Petroleum- Elemental Composition
Anthracite Bituminous Lignite Peat Crude Oil

Element wt%
C
93 I SO 3 72.7 50-70 83-87
24 5.0 4.2 5.0-61
H 11-14
24
O 4.1 213 2.5-4.5 03-0.9
0.9 up to0.2
N 17 1.2 0.5-1.9
S 06 OS 0.6 0.1-0.5 up to 5
Coal - Proximate Analysis
It determines
• Moisture
• Volatile matter
• Fixed carbon &
• Ash
It provides coal quality and type
Coal-Ultimate Analysis
It provides elemental composition ( %) of the coal

• Carbon
• Hydrogen
• Oxygen
• Sulphur &
• Nitrogen
Sulphur (mostly as pyrite) may range from 0.5 to 6.0 wt
%, nitrogen ranges from 0.5 to 2.5 wt%
Coal Heating Value
• Heating value is obtained by combustion of the sample
in a calorimeter. It can also be calculated by following
formula
HHV in MJ/Kg = 33.86*C+144.4*(H-O/8)+9.428*S

C , H ,O & S values from Ultimate analysis
HHV in MJ/Kg = 34.91*C+117.83*H-10.34*O -

1.51*N+10.05*S-2.11*Ash
C, N,H O and ash from Proximate analysis
Coal as Feedstock
• Coal ( ≈49 %) is largely used feedstock for gasification

followed by petcoke ( ≈40 %), remaining 11% feedstock
include natural gas, biomass/ MSW etc
• Coal has volatile matter( ≈20%) except in anthracite

coal and so has medium reactivity; can be gasified at
medium temperatures ( 900-1000 oC)
• High ash containing coal creates various operation

problems
Petroleum Coke/ petcoke
• Petcoke is a product of refineries from delayed coking

process
• High sulphur material
• An attractive feedstock for gasification

• Petcoke has high carbon content but volatile matter is

less
• It is less reactive feedstock and requires high

temperature for gasification ( 1400-1500 oC)
• High sulphur content in petcoke ( >5%) requires

arrangement of removing it from syngas
• Heavy petroleum residues including petcoke are

preferred feedstocks owing to their low cost/ being
negative value streams
• Gasification is rarely applied to heavy oil feedstocks

whose value exceeds $ 10 / bbl
Indian Coal / Petcoke Characteristics
Indian Coals in general :

• Have high ash content up to 40 %
• Are highly reactive
High ash content limits it suitability for gasification
Petcoke on the contrary:

• Have very low ash content
• Are not highly reactive
Combination of Coal with Petcoke forms a balanced feed

for Gasifier
Change of Feed Property with the
Mixing of Coal and Petcoke
Coal Pet coke Mixed feed
Moisture 11.8 7.00 9.40
Ash(%w) 41.10 0.26 20.68
C (%w) 36.27 82.21 59.21
H (%w) 2.48 3.11 2.80
N (%w) 0.81 1.90 1.36
O (%w) 6.62 0.02 3.32
S (%w) 0.93 5.50 3.21
LHV (MJ/kg) 13.10 31.99 22.55
Liquid & Gaseous Feedstocks
• Refinery residues like distillation bottoms , visbreaker
vacuum bottoms, asphalt /pitch from deasphalting
• Orimulsion or emulsified bitumen-water mixture produced

from bitumen fields
• Over 95% of liquid material gasified consists of refinery

residues
• Gaseous feedstocks-natural gas ; suitable for units for

production of oxo-alcohols and synfuels using Fischer-
Tropsch Technology
Biomass
• All agricultural and forestry wastes as well as purpose
grown material as biomass
• Wastes from paper and sugar industries
• Animal biomass from poultry , Pigs & Cattle farms

Biomass Feedstock
• Biomass is term used for all organic materials obtained from
plants, trees, crops, algae - such as wood, woody crops,
wood wastes, bagasse, waste paper, sawdust , grass, food
processing waste etc
• Biomass contains considerable amts of C & H and large amt

of volatile matter(>70%); high moisture and low carbon
content-lower heating values
• Highly reactive and their gasification takes place at lower

temps, 800-900 oC
• MSW can also treated as biomass

Products From Syngas
• Syngas produced from various feedstocks after clean

up is processed into ammonia (for fertilizer
production) and methanol
• In both cases gasification based applications amount to

10% global production
• Other chemical applications include production of pure

hydrogen, or carbon monoxide , Synfuels , acetic acid
manufacture and syngas for oxo-alcohol synthesis
Products From Syngas
• Another application gaining increasing attention is

integrated gasification combined cycle (IGCC)
 In IGCC the syngas produced/ cleaned is used to fuel

gas turbine combined cycle power plant
 Electric Power is generated at high efficiencies and

much reduced emissions
Product (Syngas) Composition as a function of
Feedstock & Process of Production (Typical)
Raw material Syngas Composition

(process) CO H2/CO co2 CH4
H2 N2+ Ar
Methane
(steam 75.7 15.5 5 8.1 0.2 0.5
reforming)
Gas Oil (partial
46.7 47.3 1 4.3 1.4 0.3
oxidation)
Coal
31 68 0.5 1.0
(gasification)
what can you do with CO and H2 ?
Syngas
i
>* \
w I //
u
Building Blocks for
L \
/
Clean
\
Chemical Industry Electricity

Transportation Fuels
(Hydrogen)
Polygeneration Potential of Gasification
_ _. I Naphtha I l Coal
T Ammonia
| Waxes |.Lÿ Gasification & Urea
Coal To
| Car Fuel |*~ Liquids Synthesis Gas |—
—&
H2 |
| FT Diesel Fuel Cells
Chemicals
Power & Steam
4 1 Refinery
Applications
Clean Electricity
w w&
Gasification - Benefits
• Gasification
 Stable, affordable, high-efficiency energy supply with a

minimal environmental impact
 Feedstock Flexibility/Product Flexibility
 Flexible applications for new power generation, as well

as for repowering older coal-fired plants
Gasification - Benefits
• Big Picture
 Energy Security - - Maintain coal as a significant

component in the energy mix
 A Cleaner Environment (…reduced emissions of
pollutants) -- The most economical technology for CO2
capture
 Ultra-clean Liquids from Coal -- Early Source of
Hydrogen
Gas Cleanup- Hg Removal
• Hg is removed by adsorption in carbon beds
• 90 to 100% Hg is removed from the syngas depending

upon the efficiency of the carbon bed adsorption
process
• Addition of system for Hg removal from syngas causes

incremental increase in plant capital cost and also cost
of electricity generation goes up marginally
( Hg removal essential from environmental angle)
IGCC with Mercury Removal

CONDENSE
ACID GAS
COAL SLURRY REMOVAL
*ÿ
OXYGEN
COS yg
HYDROLYSI — jH
BFW I T
WATER
MERCURY
SYNGAS
noni FF? i
J REMOVAL
L
CmD -( O
AIR
GAS
<D )
m
STEAM | PARTICULATE
REMOVAL
TUBINE
r BFW
HRSG
FINES
SI AO STEAM TURBINE
( HD
48
Energy Sources & Challenges

L2&3
G.S.Dang
gurbax49@gmail.com
Presentation Outline
• Introduction
• Energy sources
• Clean Energy / Clean Technologies
• Renewable Sources of Energy
• Summary
50
Importance of Energy
• Energy use is directly related to the development
• Development is important for all countries and hence

energy needs are ever increasing – a big challenge
• Most widely used energy sources include: Coal, oil,

natural gas, hydropower, nuclear, solar, wind and fast
developing source – Biomass
• Energy use is strongly related to environment pollution

51
Coal, Petroleum and Natural Gas
J
• Coal, petroleum, and natural gas are

m
being widely used

Ik
%
 Can not be replenished in a short

period of time (non-renewables)
ii* V
 These are called fossil fuels

.ÿ
J
s
A -
x
j
J
52
Non Renewable & Renewable
Energy Sources - Usage
• Non renewables source Oil 37% Coal 25% Gas 23%
- Available only in finite

amounts
• Fossil fuels for Energy, Nuclear 6% Biomass 4% Hydro 3%
Coal, Oil & Gas – usage

85% Solar heat 0.5% Wir'd 0.3%
• Balance by renewables
Approximate world usage

of fossil fuels + Renewables
Growing Energy Demand
Global Energy Demand Growth by Sector (1971-2030)
130
120
110
100
-
o
-Q
90
sz
30
T3
sz 70
03
E 60
-
Q 50
E5 40
1
SZ
LU 30
20
10
0
1971 2002 2030
Key: (-transport -power -industry | - other sectors
Notes: 1. Power includesheatgen erated at p ower pI ants Source: IEAWE0 20X

2. Other sectors includes residential, agricultural and service
bnboe – billion bbls oil equivalent

Global Fossil Reserves
£-.000
i
Yet to Find
E,000 -
*
3
4,000
L Unconventional
£2
3
4 Unconventional
u
M 3,000
£ Ri'P Ratio
Proven 164 yrs.
2,000 -
£
L Yet to Find
£ 1.000 -
Proven R/P Ratio RVP Ratio
Proven
41 yrs. 67 yrs.
0
Oil Gas Coal
Source: World Energy Assess merit 2OT1. HIS. Wood Mackenzie, BP Sla1 Review 2)005. BP eslimales
Primary Energy – Reserves , Production /
Consumption
Reserves Production Availability

per year for next *
Crude oil 1.5 trillion 88.77 45 years

bbls (mb/day)
Natural Gas 208.4 TCM 3.066 TCM 64 years
Coal 860938 mmt 7678 mmt 112 years
* estimates
56
Unconventional Oil production
Million Barrels Oil Equivalent per Day
12
IGas-to-Uquids
10-
8 -
ICoal-to-Liquids
Oil __
Coal-to-Liquids
Sands/Bitumen H in 2030
uim
approx
960,000 b d
2005 2010 2015 2020 2025 2030
Source: EIA International Energy Outlook 2008. Reference Case

World Energy – Current Use
• Current energy trends are unsustainable – socially ,
environmentally and economically
• Oil will remain the leading energy source but:
- The era of cheap oil is over, price volatility will remain

- Oil field decline is the key determinant of investment needs
• To avoid “abrupt & irregular” climate change we need a major

decarbonisation of world energy system
58
Energy use - Protective Measures
• Use of fossil fuels leads to continued release of harmful
emissions / toxic gases to the atmosphere
• These emissions ( CO2 , CO , CH4 , SOX , NOX, Particulate Matter

etc) have potential to cause global warming and health
problems to general masses
• Since energy use is to continue hence certain measures are

essential
 Use of Clean Energy Technologies; less harmful emissions
 Efficient use of energy - Reduced Energy needs
 Use of alternate / renewable energy sources
59
Mitigation - Challenges before Us
• Zero Emissions / Minimizing Emissions
– Using Renewable sources
– Nuclear Energy ?
• Reducing fuel related specific CO2 emissions in energy

generation
– Coal Conversion
– Clean Coal Technology
• Promoting Cleaner Technologies – Participating in CDM
• Developing Carbon Capture and Storage Technology –

Programme on CO2 Sequestration
60
Fossil Fuel Use - Impacts
• Continued use of conventional energy sources has

caused and is causing environment degradation
• The environment degradation is strongly affecting

health of all of us
• To mitigate the adverse effects of use of fossil fuels

many measures are being adopted in the world to
protect environment and health to a greater extent
61
Climate Change Impacts – Concerns
• Effect on Agriculture sector and endangering crop
productivity
• Extreme weather events causing more storms, floods

etc.
• Impact on water causing Scarcity and food

contamination
• Surface temperature rise
• Changing geographical distribution of vector borne diseases

Planning for Climate Change
Mission mode
• Increasing share of Renewables (solar, wind etc)
• Implementing Energy Efficiency
• Cleaner Technology adoption
• Managing Water resources effectively
• Safeguarding Himalayan Glaciers and eco-system
• Making Agriculture to response to climate change
Clean Technologies ?
• Clean technologies means innovative technologies

designed to optimize the use of natural resources and
reduce environmental impact
or
• Promoting the productive and balanced use of natural
resources at affordable costs while conserving the
natural environment
64
Clean Technologies for Energy Production
Drivers for Adoption of Clean Technologies for fossil

fuels and for Renewable sources of Energy include :
• Global Warming
• Depletion of Natural Resources
• Rapid Industrialization
• Energy Security
65
Clean Use of Fossil Fuels
• The existing fossil fuel sources being finite need to be

used more efficiently
• Alternate sources mainly renewables are developing

but can not replace those completely
• Future energy needs of the world shall be met by

combination of non renewables and renewable
sources
66
Clean Use of Fossil Fuels
• Clean technologies need to be adopted for Gas , Oil &

Coal for reducing pollution due to GHG emissions etc
 Gasification route instead of Combustion
67
Natural Gas (NG) – Utilization
• Relatively a cleaner fuel compared to oil

• Longer availability
• Need to be produced more through newer
sources
• Converted to liquid fuels ( GTL technology &
products)
68
Drivers for Conversion of NG to Liquid fuel
• Need for economic utilization of Natural Gas including
the stranded NG through GTL ( Gas to Liquid )
• Reduction in cost of transportation of NG from
producing to consuming regions (same principle as
with LNG)
• Environmental concerns
- Development of clean fuels throughout the world
( gasoline etc)
69
Benefits of NG Use
• Cleaner Environment
• Lower Greenhouse Gas Emissions
• Stronger, More Competitive Energy Industry
• More Jobs
70
Cleaner Technologies for
Utilizing
Petroleum Residues / Petcoke
from Refineries
71
Simple Block Flow Diagram of a Refinery
> Desulphurised
Fuel Gas
Fuel Gas
i1 > ATU > SRU > Sulphur
LPG *ÿ LPG
>•
>• >ÿ Naphtha
SR Naph C5 – 90 C
> CRU T MS(Petrol)
90 – 140 C
HGU MTO
C C Kero Cut RTF/ATF
D D
*• *• KHDS H2 *•
Kerosene
> U U St.Run G.O
Crude > DHDS O.035% S HSD
E
iL
JBO O.005% S HSD

1 2 *ÿ
JBO
MERICHEM
ik 1k >• FCCU MERICAT
GO
SO > CBFS
>
Ext. 100 N
V V LO / IO / HO
RCO
D D > > FEU *ÿ
SDU > HFU T
150 N
* U U NMP
500 N
DAO S.Wax 850 N
1 2
150 BS
PDA •4 >
v_x_y CIDW
Asp. >
SR > > Slack Wax
LO > MCW *ÿ MCW
VBU
ir ir
> >ÿ FO
> Bitumen
BTU
ir
*ÿ >
>ÿ Bit Eml.
*ÿ 72
IFO
Petroleum / Crude Oil Refining
> Gases
Naphtha / Gasoline (Petrol) (C5 – 140 °C)

DISTILLATION
ASMOSPHERIC
>
Kerosene / Jet Fuel (140 - 250 °C)

>
Gas oil / diesel (250 – 370 °C)
Crude >ÿ
Oil
DISTILLATION * Lube oil fractions

VACUUM
* (370 – 540 °C)

Atmospheric
*
Residue >
(370 ° C+) Heavy Lube Oils/
'ÿ
I Bitumen
I
Further Gasification
Vacuum Residue >
Processing (CO + H2, Syn Gas)
(540 °C+)
I
I Petcoke/ /73
Fuel oil
Gasification in Petroleum Refinery
• With increasing % age of heavy crudes in the crude blend of
refineries, higher amount of residues or more of heavy products
like deasphalter pitch or petcoke are produced
• These are low value streams and difficult to upgrade
• Gasification of such residues / streams or petcoke etc is an ideal

route to make zero residue / zero fuel oil refineries
• More and more world refineries are in a process of adopting it

( Reliance Refinery in India is one such Example)
74
• The gasification process converts any

carbon-containing material into a V fc
synthesis gas composed primarily of
carbon monoxide and hydrogen (CO + H2).
• Syngas can be used as a fuel to generate

electricity or steam or used as a basic
chemical building block
>
V for a large
number of uses in :the petrochemical and
refining industries. w
!
• Gasification adds value to low- or
negative-value feedstocks by converting
them to marketable fuels and products.
75
Gasification
Refinery Application
Air emissions
Crude oil >
> Gasoline / Diesel
Steam >
Power
>
>
REFINERY Distillates
HSFO
>
Hydrogen >
A
Gasification
O2/N2
H2 Power Steam
Syngas generated is cleaned , used for production of power , steam and H2 76

Poly-generation with Gasification
Power
Electricity
Steam
Fuels
Fischer-Tropsch Diesel
Syngas Naphtha
>ÿ
Methanol/Ethanol
Dimethyl Ether and
Hydrogen
Coke/Coal
Chemicals
Waxes
Olefins
Acetates and many
Others
77
Clean Coal Technologies
78
Use of Coal for Energy Security
• Electricity demand is ever increasing (demand growth
forecast to exceed supply growth)
• Coal is the main fuel used in power generation (coal
combustion- large scale )
• Immediate need to develop technologies to utilize
coal cleanly
 Carbon capture / Carbon sequestration
 Coal transformation technologies including
gasification and liquefaction
79
Coal
• Coal represents the cheapest and most convenient
fuel to meet expected surge in electricity demand
ft
• Coal is undisputed leader in dirty fuel '' BE ImrS
• Burning coal releases more CO2 per unit of energy

than Oil or Natural Gas
• In terms of it lifecycle, the mining, transportation

and burning of coal leads to major environmental
and health hazards- from smog, acid rain,
m
*
mercury pollution in rivers to asthma and other
respiratory problems
80
IGCC with and without CO2 Removal V
rS
*
i
IGCC no CO2 capture Sulfur *
Coal 1 $
Gas CC
Clean POWER
Air > ASU Gasifier >ÿ >ÿ
Power *
O2 Up Block
i
Slag
H2 & CO2
Sulfur CO2
Coal
Li CC
ASU Gas
Air Gasifier Shift >
Clean
— Power POWER
O2
1 Up 1 Block
Slag
H2
IGCC- Integrated Gasification Combine Cycle

Energy from Fossil Fuels- Summing up
• Energy contribution from nonrewable fossil fuels shall

continue at least for next two decades
• Emphasis is on reducing emissions in the form of toxic

gases and GHGs ( adopting cleaner technologies)
• Use of these sources is also changing from energy to

non energy applications
82
Non Fossil Fuel Energy Sources
83
Nuclear Energy
• Nuclear fission uses uranium to
W m1
create energy
P
<•
r
-A M • Nuclear energy is a nonrenewable
'
resource because once the uranium
!ÿ- ml
is used, it is gone!
ML"
.-
• Nuclear fuels -limited amounts of
uranium for nuclear fission reactors
*
ya
;.‘ S RNtf
but reprocessing of fuel possible
s?r/-
• Difficult to estimate how long these

gnjj
ii £v
iLT rl
- rrzsy “
.1
L4V \
fuels will last - but is it sustainable
P3‘&
-V
,v
- <*
economically or environmentally?
84
Nuclear Energy?
• With nuclear power huge amounts of power can be
produced from a small amount of uranium but
• Produced radioactive waste is dangerous to health and

life for hundreds of years
• There is no secure place for storage
• Public confidence - shattered by the explosion at

Chernobyl in 1986 and disaster at Fukushima Japan
March 2011
85
Nuclear Power Plant - Concerns
• Fire , Earthquake etc. at the plant

• Cost & Lead time for construction of nuclear power plants
• Shortage of skilled labour
• Disposal of radioactive nuclear waste
Source: The International Institute for Strategic Studies (http ww >ig : ySi'eW' n Gati ink n ;:ÿ Gilo •. -1-H )
86
Renewable Energy Resources
Renewable resources are natural
resources that can be replenished in a
short period of time
Hence they will last indefinitely \l

i
-
I
fri;'
. rant
● Solar ● Geothermal * I
m
i
● Wind ● Biomass TV'

i; r. ,/
● Water .1 K ; IV
'I i»
:i< ii •• V
'f.*
/
Ml \/v
1 jWJfl 'A! /
A
87
Sustainable Situation
• Renewable energy sources are being replaced /

generated at the same rate that they are being utilised
• Hence they will last indefinitely
88
Clean Technologies
• Clean Technologies or clean-tech include solar
wind, geothermal, biofuels, and water ( geothermal &
tidal)
• Cleantech also includes energy efficient products
 It is a means to create electricity and fuels, with a

smaller environmental footprints and
minimize pollution
89
Renewables for Electricity Generation
& <£>
• Wind, Solar, Geothermal etc can
play a supplementary useful role
but
• Will not replace fossil fuels in next

two decades
\ jQ
90
Solar Power
• Solar energy is the energy from the sun in the form of

solar radiation for heating or to generate electricity
• Solar powered electricity generation uses either

photovoltaic or heat engines
(Solar heating panels , Solar power generation &

Solar cells / photovoltaic cells)
91
Solar Cells
• Convert light into a small electrical output -milliwatts
output
• Need a bank / array of cells for useful output
• Cost of cells is high but reducing
• Efficiency of cells is up to 23%/ improving
92
Solar Panels
• Are placed on roof of building
• Absorb heat in the form of radiation from sun
• Basically system is like a domestic central heating,

radiator painted black / insulated
• Provides “topping up” of domestic hot water
93
Solar Roof tiles
__ ;« *ÿ Roof mounted solar

panels (Solar century)
/
.*
y
7
-Z 7
z - /
2
7
7
T
I
7
/
iam : £
5773 ft .ÿr '
rjif'if
&ÿ 1 ‘ j
'T '*:
>4
*ÿ
W ••s'
Integrated solar tiles installed by Solar Century X

/
I',
Innovative Sun Slates installation by

Solar century
94
Solar Power Generation
• Located in desert/high intensity/long sunlight hours
• Parabolic mirrors reflect/focus sun’s rays onto metal

water pipe located along focal axis of mirrors
• High temperature produced - steam - electrical power

generated
• Largest Capacity – 354 MW power plant in Mojave

Desert Spain
95
Wind Turbines
V f
1
t
f
I
96
Wind Turbine- Parts
Gearbox
Electrical
generator
Power cable
I
Wind Energy
• Energy from wind
• Ancient application: sailing
• Used since Middle Ages: windmill
• Electricity generation:
wind  turbine  electricity
(reverse of electric fan operation)
Propeller blades
Wind Gearbox & generator in housing

which can be rotated to face the
wind
Tower
98
http://home.clara.net/darvill/altenerg/index.htm
Wind Power
• Wind turbines produce electric power between 1/4
and 2 MW / turbine
• Wind farm needs to be located where there is a

relatively high average wind speed
• Widely used in Europe, Asia , and the US
• Total cumulative installations stand at about 450,000

MW at the end of 2016 (Annual Growth – 15% over
last two years)
99
Offshore Wind Turbines
fi -ÿf
iT-
_
=¥=
LiL
Mi*
Sr
:;--S
:jT
-i
ViAN
h# 7&k
'
FT
- - rrr z, . >>-;
rÿs—-
— -r
100
Hydroelectric Power
• Currently largest source of electricity from renewables
• Needs guaranteed supply of water
• Kinetic energy of water rotates turbines which

generate electricity
• At present it is accounting for 16 % of global electricity

generation
101
Tidal Power
• Located at some coastal sites with large tidal range
• Shape of coastal site above and below sea level

determines range
• At high tide reservoir of water is created which is

allowed to pass through turbines located in dam
• Expensive construction
102
Geothermal
• Geothermal energy is from thermal energy generated

and stored in the Earth
• The heat that is used for geothermal energy can be

from deep within the Earth, all the way down to Earth’s
core – 4,000 miles (6,400 km) down
• The world's largest geothermal power installation is

the Geysers in California, with a rated capacity of 750
MW
103
Biomass
• Cycle of Sunlight - Photosynthesis - Plant growth -
absorption of CO2 - emission of O2
• Combustion of wood – Heat
• Decomposition - Methane/landfill gas (fuel for heating)
104
Why Biomass Energy ?
• Can deliver energy in all forms
- Solid, Gas & Liquid for application
• Gasifier produces fuel at lower cost
• Energy Security
• Poverty Reduction
• Positive Environment effects
- Carbon dioxide neutral
- Restoration of degraded land, water retention etc
105
Biomass Sources
Biomass sources include:

• Wood chips
• Agricultural wastes / residues,
• Animal waste / residues, and
• Organic component of municipal solid waste (MSW)
106
Biomass Gasification
DRYING r\
wrttxxnM ‘(dry h*omo»l»rHO i Hfl
V
biomass
PYROLYSIS
1
H Tar
CH*
HEAT
COMBUSTION
ooÿpo;
4H Q, » 2H,0
(rv?*tiV4i 0,4 rCOj
- co;
HO
6
H
V
REDUCTION
C*00, 2 CO
*
C M,0 ft CO H,
CO
H,
CH nHO j nCO (m/2*n> M,
CH. •nCOk % 2rCO •nV2 H,
107
Environmental Advantages
• Renewable Source
• Reduces landfills
• Protects clean water supplies
• Reduces greenhouse gases
 Carbon dioxide
 Methane
108
Non Renewable & Renewables- Summing up
• Non Renewable Energy sources / Fossil Fuels are being made
cleaner through technology advancement
 Gasification / GTL route
• Renewable energy sources / cleaner energy comes from sources

which are being continually replenished such as sun light, wind,
tides, waves and geothermal heat
• About 16% of global energy consumption comes from renewable

sources
• Future Energy needs will be met by use of both the above

sources , with more and more adoption of clean technologies
109
110
Gasification Reactors
(Fixed bed, Fluidized bed & Entrained bed)
B. Tech APE Course

UPES, Dehradun, 7th Sept’ 2017
G.S.Dang
gurbax49@gmail.com
111
Coal Gasification
• For surface coal gasification coal has to be mined;
transported to the site and gasified for generation of
Synthesis Gas ( CO +H2) using a gasifier / reactor
• Various types of reactors are in use depending upon

the feedstock & its quality
• The gasifier / reactor is integrated with other piece of

equipment i.e. gas cooling & clean up, power generating
turbines, and /or reactors for producing liquid fuels etc
Gasifiers / Gasification Reactors
• Gasifiers (gasification reactors) are of various types /
designs and have different operation characteristics
• Gasifiers are in general classified into following three

categories
 Fixed bed gasifiers ,
 Fluidized bed gasifiers and
 Entrained bed gasifiers / entrained flow gasifiers

Fixed bed Gasifiers
• Fixed bed gasification process involves:
 A bed of fuel ; maintained at a constant-depth by

the addition of fuel from the top of the gasifier &
 It has a stationary reaction zone supported by a

grate
• Fixed bed gasifiers are commercialized as
 Lurgi dry ash gasifier

 British Gas Lurgi (BGL) slagging type and
• In a fixed bed gasifier, feedstock is fed from the top and is

preheated, dried, devolatilized / pyrolysed, gasified and
combusted while moving towards the bottom of the gasifier
Fuel / Coal
li
illl:
Gas
i Drying
ri r H : H'i
m Pyrolysis
r® Reduction
li
Oxidation
Grate
-
Steam
* ®
Ash
Oxygen
or Air
• These gasifiers can carbonize coal containing ash up to
around 35%
• Particle size range of feedstocks is normally 2-50 mm
• The gasifying medium, air / oxygen and steam is

introduced at the bottom of the gasifier
• Around 85 % of coal is gasified by fixed bed gasifiers in

the world
• Since the fuel moves downward continuously under gravity
while reacting, the process is also called Moving bed
gasification
• Moisture is driven off in the drying zone, feedstock (coal

etc.) is further heated and devolatilized/ pyrolysed by a
hotter product gas while moving down to the gasification /
reduction zone, where it is gasified by reacting with steam
and carbon dioxide
• The remaining portion of the char is finally burnt completely

in the combustion/oxidation zone where the bed reaches its
highest temperature
• Maximum temperature in the combustion zone is in

the range of 1500-1800 °C for slagging gasifiers and
1300 °C for dry ash gasifiers
• Operating pressure range is 0.15-2.45 MPa and the

residence time is in the order of 15-30 minutes
• Ash or slag leaves the bottom and produced syngas

exits at the top
• Syngas leaving the gasifier is cooled against in coming

feed and gas exit temperature is range of 400-500 °C,
• Main difference between dry ash and slagging gasifiers

is that the dry ash gasifier uses a much higher ratio of
steam to oxygen than a slagging gasifier
Fixed / Moving bed Gasifier
Coal
t Gasifier
Top I rÿll I
\Gas
0
:v. Coal \
Moving-Bed •*o> \
Gasifier ;*• \
(Dry Ash) \
•
• \
Steam, /
Oxygen
or Airÿ
. i vv..v
f Msh
Steam,
Oxygen
Gasifier
Bottom
1 \ 1 1 I_I
or Air 0 250 500 750 1000 1250 1500
Ash Temperature - °C
Fig. 2. Diagram of a generic moving bed gasifier
Fixed / Moving bed Gasifiers
• Moving bed reactor
(Lurgi – dry ash and BGL -
Slagging) BGL gasifier (fixed
bed, Slagging)
– Counter-current flow of ir
coal and oxidizing blast
coal lock
– Blast composed of air and
hot syngas, so low oxygen gas offtake ,0.
consumption
– Operates on reactive
stirrer
9as quench
carbon sources
– Good heat transfer, heats 3
crude gas !£)
the carbon source creating '
m
methane and tar ;am, oiygen
d tar
. tuyere
w-
ir
– Post production cleaning
and scrubbing requires slag quench
!
greater energy use slag lock
S>
slag
Figure 1: BGL Gasifier
Fixed bed Gasifiers
Gasifiers have the following characteristics:
• Low oxidant requirements;
• Relatively high methane content in the produced gas;
• Production of hydrocarbon liquids, such as tars and oils;
• High “cold gas” thermal efficiency when the heating value of

the hydrocarbon liquids are included;
• Limited ability to handle fines

Fluidized bed Gasifiers
• In a fluidized bed gasifier, feedstock and air/ oxygen are

injected at the bottom of the gasifier
Gasification processes such as
 U-Gas, HTW (High Temperature Winkler),

 IDGCC (Integrated Drying and Gasification Combined Cycle),
 Babcock ABGC (Air Blown Gasification Cycle) and
 KRW (Kellogg-Rust-Westinghouse)
use fluidized bed Gasifiers
Ml*
t llVMOTtZZON
IKltW
NOUrJ»«Vtj
rry
mm1! •ff
4 •••
1CMTVJ5
n JvY •
jJKJ ! &r$' ’v/V%iVv;
VMOrtlS
1* &3ffl
gsgi
•:Vy*v«.
rfov</*. *A vr-vJ *.8
4 VO,s,R
INOlDAO * v . m v1 i
s£ art*:- 1
I
vronmt
Fluidized bed Gasifier

Fluidized Bed Gasifier
Gas
Gasifier
T
Coal
Top
Ml
f
|Gas '
Fluidized-Bed
L I
Gasifier
1
r
Steam
0M n
or Arÿ_ __
5
%
l
Steam Gasifier [_ I jAan,
vr
i
On
or 1
**”*0 250 500 750 1000 1250 1500
Ash -
Temperature *C
Fig. 3. Diagram of a generic fluidized bed gasifier

Fluidized Bed Gasifier
• Required particle size is as 0.5–5mm and residence time of

feedstock in the gasifier is in range of 10-100 s
• Temperature in a fluidized bed gasifier reaches 1200 °C ;

gasification medium - oxygen
• High level of back mixing ensures a uniform temperature

distribution in the gasifier ; operated at temperatures well
below the ash fusion temperature (900–1050 °C) to avoid ash
melting (avoiding clinker formation /loss of fluidity of the bed)
• This device offers the advantage of promoting excellent
mass and heat transfer due to the intensive mixing
• Unreacted carbon particles remain present & are removed

from the bed along with fully reacted particles (ash)
• The best existing fluidized bed devices offer a carbon

conversion of 97%. (moving-beds and entrained-flow
processes offer carbon conversions of 99%)
• Main advantage - this gasifier can be operated at variable

loads resulting in a high turn down ratio / flexibility
• Fluid-bed reactor (Winkler,
HTW, CFB – dry ash; KRW, U-
Gas – Agglomerating) Winkler Gasifier (Fluid bed, dry
ash)
Fuel and Inert
– Air fluidizes a bed and carbon Gas Lines
Gas to Dust
Collector &
containing particles added To Stack
Waste Heat
Boiler
– Proper mixing of fuel and t

oxidant provide good mass /
transfer and heat transfer /
Fuel Bunker o
– Fine particles may escape 2

/
o
<D
cz
/ Refractory
— Lining
with syngas and need to be > CD
e?
Steel Shell
cleaned
– Very good heat/mass transfer — Starting
Generator
; partially reacted carbon may X °L1Z°Z = 0
settle with ash f

If Scraper for
Ratchet Drive
Ash Removal
– Slagging will reduce Water Cooled
-
— Grate
fluidization, so temp remains
Shaft
Steam 30 ifn r-Ratchet Drive
below softening point for ash x"

Water Cooled
Shaft
Oxygen or
Oxygen -air t
Drive
Water-jacketed
o-V Ash Receiver
M ixture Screw Conveyor
The Winkler gasifier.
Figure 2: Winkler Gasifier

• Generic characteristics of Fluidized bed gasifiers

include:
 Extensive solids recycling
 Uniform and moderate temperature; and
 Moderate oxygen and steam requirements

Entrained bed / flow Gasifier
• Majority of coal gasification processes, developed after 1950,
are based on entrained-flow, slagging gasifiers operating at
pressures of 20 to 70 bar and at high temperature (≥1400°C)
• These gasifiers are more versatile as both solid & liquid fuels
can be processed under high operating temperatures ( above
ash slagging) to ensure high carbon conversion
• Entrained-flow gasifiers have become the technology of choice

for hard coals, and have been selected for the many of
commercial-sized IGCC plants as well as for production
ammonia, methanol, acetic acid and other chemicals
Entrained bed /flow Gasifier
• Entrained flow gasifiers have the ability to handle any
solid or liquid feedstock and produce a clean, tar-free
Syngas
• Ash is produced in the form of inert slag or frit
• This is achieved through coal preparation and high

oxygen consumption
Entrained bed Gasifier
Steam.
“irsr Gasifier
Top
U. 1 I T
- QHMM
or Ar
Entra«ned-How
Gasifier V*.
r°“
j Gas
Gasifier I i w I
Booom 0 ?50 500 750 1000 1?50 1500
Slag -
TerrperaH/e *C
Fig. 4. Diagram of a generic entrained flow gasifier
Entrained bed / flow gasifiers
• Entrained flow reactors (Shell,
Texaco, E-gas, Noell, KT - Slagging)
Texaco Gasifier (entrained
– Carbon source is made of very flow, Slagging)
fine particles in a liquid or slurry Coni Slurry
for very good mass transfer Oxygen from Air
I
– Very little residence time
Sepnraiion Pliinl
– Co-current flow with oxygen

where high temperatures can be
reached Texaco
Gasifier
– Low heat transfer means hot
exiting gas with no methane or
/
tar, but more oxygen required
– High temperature and very small Food
Water
carbon particles make it an ideal

process for coal gasification.
• High temperatures without
charring Radiant HU
Prossuro
Syngas Steam
• No agglomeration because of Cooler
fine particle size preparation Syngas
Slag to
Disposal •Black Water*
Recycled
Figure 1: Texaco Gasifier

Entrained bed / flow gasifier –Two Stage
• Recent development in entrained bed gasifier is two

stage gasification reactors of Conoco Philips ( known as E
Gas Technology)
• The slurry feedstock reacts with Oxygen is first stage to
form hydrogen, CO , CO2, and methane at high
temperature
• The first stage ( horizontal) traps inorganic materials like
ash and metals as slag
• In second stage hot syngas enters from first stage along
with additional slurry to increase syngas quantity
Current Commercial Technology
Shell GE (Chevron Texaco) ConocoPhillips (E-Gas)

£4# t
Sjnimm
Ir - I W.n r
1 )'<, LHJ*I ,
— u
CMI S-
*— -Tjÿ
1 u
fifty
yL > > I
Q*rr>" f
S
* Lock hopper feed * Slurry feed * Slurry feed
* Water cooled * Refectory lined * Refectory lined
* Syngas cooler * Quench available * 2 Stage
* PRB capable * Not PRB capable * 999
at cost A
Salient Characteristics of Major Gasification
Technologies
Technology GE Energy E-Gas Shell
Name/ Design (ConocoPhillips)
Feature
Feed System Coal in Water Coal in Water Dry Coal. Lock
Slurry Slurry Hopper &
Pneumatic
Conveying
Gasifier Single Stage Two Stage Upflow Single Stage
Configuration Downflow Upflow
Gasifier Wall Refractory Refractory Membrane Wall
Pressure (psig) 500-1000 Up to 600 Up to 600
Notes Offered as Currently only Currently only

Quench or with offered with Heat offered with Heat
Heat Recovery Recovery Recovery
Entrained bed / flow gasifiers
Generic characteristics
• High-temperature slagging operation;
• Entrainment of some molten slag in the raw syngas;
• Relatively large oxidant requirements;
• Large amount of sensible heat in the raw syngas; and
• Ability to gasify all types of coal regardless of rank,
caking characteristics or amount of fines
Hybrid & Novel Gasifiers
• These gasifiers are based on either hybrid

combinations of the three types or novel processes
such as a molten metal bath
• The transport reactor-based gasifier developed by

Kellogg Brown & Root (KBR) is an example of a hybrid
gasifier
• It has characteristics of both a fluidized bed and an

entrained bed gasifier – limited commercialization
so far
KBR Reactor
Disengager To Primary
Gas Cooler
Riser ) t
Cyclone
Mixing
Zone
Fuel / Coal >

Sorbent Loopseal
T
Oxygen / Air -ÿ
Steam J-leg
Startup « Standpipe
Burner V
(propane)
KBR Gasifier
C
DL
I Hi
Standp4,
w
•ÿ1
r
i
’l
M
KBR Gasifier
• In this gasifier, feedstock is introduced into an upward flow of gas

(either air or oxygen/steam) that fluidizes the bed of fuel while
reaction takes place
• The premixed coal and limestone etc., is fed to the transport
reactor through three nozzles located at various elevations on
the riser
• During operation, feed is admitted through only a single nozzle at
a time. Oxidant is also fed to the riser by three pairs of nozzles at
differing elevations within the mixing zone.
• For combustion mode of operation, two additional Nozzles are
provided in the riser to introduce secondary air.
KBR Gasifier
• High level of back mixing ensures a uniform temperature
distribution in the gasifier, which
 Operates at a temperature well below the ash fusion
temperature (900–1050 °C) &
 Avoids ash melting / avoiding clinker formation and loss of
fluidity of bed
• In the gasifier (hybrid system), coal is first devolatilized/ gasified

in the fluidized bed (mixer) followed by char combustion in a
fluidized bed combustor riser) thus increasing carbon
conversion leading to higher cold gas efficiency
Salient features of various types of gasifiers.
Gasifier Technology Typical process condirions Remarks
CD (2) £3) £4)
Fixed bed BGL Combustion temp.: 1300 T (slurry feed) -Car carbonize coal containing -35% ash.
Lurgy and 150GMSO0 *C (dry feed) -Carnot use liquid fuels
Liry ash Gas outlet temp,: 400-500 °C -Steam requirement is high
Pressure: 0.15-2.45 Mra -Syngas contains tar and phenolic compounds
R.T.: 15-30 min -More loss oF fine particles of feed produced
Feed particle size: 2-50 nmn during feed preparation
Oj/Feed: 0.64 Nm*/kg
Gas heat value (MJ/Nm3); 10.04
Cold gas efficiency: high
Fluidized bed HTW. IDGCC KKW, Combustion temp.: 900-1200 °C -In situ sulfur capture when 5 content •ÿ2 wt.%
Mitsui Babcock Gas outlet temp.: 700-900 "C -Preferred for high reactive feedstocks Jike waste fuels.
Pressure: 0.1-2.94 MPa biomass and low rank coal
R.T: 10-100 s -Char particles need to be recycled for high conversion
Particle size: 0.5- 5.0 mm -Moderate steam requirement
fVFeed: 0.37 Nmÿ/ltg -Syngas does not contain tar or phenolic compounds
Gas heat value(ÿNmJ):10.71 -Reduced loss of fines
Cold gas efficiency: medium
Entrained bed BBP, Hitachi, MHI, Combustion temp.: 1500 "C Syngas does not contain any tar or phenolic compounds
PRENFLQ, SCCP. Gas out let temp.: 900-1400 °C -Preferred for low reactivity fuels like pet coke
E-Gas, Texaco Pressure :2.04-3.43 MPa -Suitable for co-gasification of petcoke and high ash coal
R.T: 1-10 s
Particle size: -:20Q mesh (90%)
-
mixture having 22% ash.
-Steam requirement is moderate
Oz/Fecd: 1,17 Niriÿ/kg -In-situ sulfur removal and no fine loss
Gas heat value (MJ/Nm3): 9.5S
Transport reactor KRR Combustion temp.; 900-1050 "C -Prevents exposure of raw coal to the oxidant pieventing
Gas out lei lemp.: 590-980 “C combustion of the volatile matters released
Pressure: 0.29-1.47 MPa -Only char combustion and improved process efficiency
R.T; 1-10 s -High throughput and conversion
Particle size: ---50 pin -Not well proven
Oj/Feed: 1 .06 Nma/kg
Gas lieat value (MJ/Nm3); -
R.T = residence time. Temp. = temperature.
Source : Review -Syngas production through gasification and cleanup for downstream applications— Recent
developments P. Mondal , G.S. Dang, M.O. Garg , Fuel Processing Technology 92 (2011) 1395–1410
Performance of A Gasifier
• For comparing gasifier performance we focus on

characteristics of the syngas generated
• The main points are carbon conversion ( % of carbon from

the solid fuel converted to carbon in the syngas) and the
syngas temperature, composition, higher heating value
(HHV, BTU and BTU/SCF) and
• Cold gas efficiency (CGE) which is defined as:
m syngas  HHVsyngas
CGE 
m coal  HHVcoal
Operation of Gasifiers
Atmospheric v/s Pressurized
• Gasifiers operate at atmospheric pressure or at
pressures as high as 70 bar
• Pressurized gasifiers are better suited for IGCC operation

since the pressure of product syngas is high enough to
be fed directly into the GT fuel control system
• Low pressure or atmospheric pressure gasifiers require a

fuel gas compressor after the syngas clean-up processes
Dry Feed v/s Slurry Feed
• Coal is fed into a pressurized gasifier either pneumatically

as a dry solid or pumped as coal-water slurry
• Slurry-fed systems have a lower capital cost, but result in

less efficient conversion of coal to syngas (part of syngas is
burnt to vaporize the water in the slurry)
• Syngas produced by a slurry-fed gasifier has more CO2 in it

than a dry-fed gasifier
• More CO2 not detrimental to GT operations ( CO2 acts as an

effective diluent for NOx control); but impacts the design of
the “acid gas removal” section of the IGCC
Air-blown v/s Oxygen-blown
• Oxygen for gasification can be provided by air or by a cryogenic air
separation unit (ASU)
• Air-blown gasifiers have lower capital cost but produce a much lower
calorific value syngas than oxygen blown gasifiers (Nitrogen in air
dilutes the syngas)
• Syngas calorific value for oxygen blown gasifier - 300 Btu/scf;

air-blown gasifier produce syngas with a calorific value of 100 Btu/scf
• Significant impact on the design of the combustion system of the GT

Quench v/s Heat Recovery
• For all type of gasifier the exiting syngas must be cooled down to
about 100oC in order to utilize conventional acid gas removal
technologies
Available Options :
 Using a series of heat exchangers to recover the sensible
heat for use in the steam cycle of the IGCC, or
 By directly contacting the syngas with cool water i.e. quenching

(moisture need to be removed from the syngas )
Vmm
Selection of Gasifier &
Syngas Cooling / Conditioning
B. Tech APE Course

G.S.Dang
gurbax49@gmail.com
152
Salient Characteristics of Major Gasification
Technologies (Entrained bed)
Technology Name/ GE Energy E-Gas Shell
Design Feature (ConocoPhillips)
Feed System Coal in Water Coal in Water Dry Coal. Lock

Slurry Slurry Hopper &
Pneumatic
Conveying
Gasifier Single Stage Two Stage Upflow Single Stage
Configuration Downflow Upflow
Gasifier Wall Refractory Refractory Membrane Wall
Pressure (psig) 500-1000 Up to 600 Up to 600
Notes Offered as Currently only Currently only

Quench or with offered with Heat offered with Heat
Heat Recovery Recovery Recovery
Current Commercial Technology
Shell GE (Chevron Texaco) ConocoPhillips (E-Gas)

£4# t
Sjnimm
Ir - I W.n r
1 )'<, LHJ*I ,
— u
CMI S-
*— -Tjÿ
1 u
fifty
yL > > I
Q*rr>" f
S
* Lock hopper feed * Slurry feed * Slurry feed
* Water cooled * Refectory lined * Refectory lined
* Syngas cooler * Quench available * 2 Stage
* PRB capable * Not PRB capable * 999
at cost A
Gasification of Petcoke
• Suitable gasifiers are entrained bed type
• Very high temperature to provide good carbon conversion for this low
reactivity fuel
• Heavy metals in petcoke can be encapsulated in glass-like slag
• Slurry feed type (GE, E-Gas) and dry feed type (Shell, Prenflow, Noell)
GE gasifier GE gasifier E-Gas Shell/Prenflow/Noell

(WHB) (quench) gasifier gasifier
Oxygen from Air Coal ¥
ir
Separation Plant Slurry
nn
¥
E-Gas™
Fuel Gas HP Steam
t
Texaco
Gasifier <?ÿ RN
Entrained-Flow
Gasifier Raw Gas
©©©©©© Feed Water Section A-B
.
©©©©©-
©©©©©© Preheater
©ffiffi®©
©©©©©©
f
, ©©©©©
©©©©©©
/Ts fT\ /T*\i*TN
Feed .
\X< w w vX1
®©©ffi®
Water Second ®©©ffi©ffi
Stage
Radiant
Syngas
Cooler
l
I M!3 • \ Coal
Slurry
/ First
Stage
Ry Ash
Syngas
Ml
t
\ * Quenching Water
A B
* 4 * : Char
I T
*
High
Pressure
Steam
*ÿ
i*v
IrnB Coal Dust
0
1 t
Oxygen 'S>
Slag
(from Air
•Black Water- Quench
Separation Oxygen Steam
Recycled
Plant)
Slag/Water
Water
cr -S // M
Slag
Slag to Slurry
Disposal
Slag By-product
Gasifiers - Modes of Operation
• Two modes of operation for gasifiers such as quench mode
and boiler mode
• In the case of quench mode operation, hot raw syngas is

injected radially into a quench ring and is shock- cooled
(quenched) by water
• The syngas is cooled almost instantaneously to saturation

steam temperature and leaves the quench separator as as
side stream
• At the bottom of the separator, soot slurry resulting from

quench is drawn off
Gasifiers- Modes of Operation
• Further cooling occurs in a medium pressure steam boiler,
which produces steam at 1.5- 3.0 MPa for use in the
complex
• In the boiler mode of operation, raw hot syngas leaves the

gasifier as a side stream at the bottom to enter directly into
a high pressure steam boiler
• In this mode of operation heat is recovered at the highest

possible temperature. High pressure steam (10 - 15 MPa)
generated in the boiler is the main reason for high
efficiency of a boiler mode IGCC power plant
Texaco (GE) Gasifier
• Texaco gasifier is a cylindrical refractory lined vessel
mounted on the top of the radiant cooler
• It has no movable parts, so its maintenance is simple
• It operates at a temperature ranging from 1200 °C to

almost 1400 °C and a pressure of about 3.00 MPa
• Depending on the final product and extent of heat

recovery from the hot gasifier products different
versions of the Texaco process are available for
commercial use
Full heat recovery design
(Radiant + Convective design)
• In this case, hot gasifier products exit the gasifier at the bottom
and enter radiant cooler that generates high-pressure steam
• At the bottom of the radiant cooler, slag drops into a quench pool
of cooling water prior to its removal, whereas gas flows to a
convection type exchanger, where additional high-pressure steam
is generated
• Cooled gas is further treated to remove particulates and sulphur

to make it suitable for a combustion turbine
• High-pressure steam generated in the radiant and convective

coolers is injected into a steam turbine
Radiant design
• In this case, only a radiant cooler is there and

no convective cooler is provided
• Both slag and syngas are quenched at the

bottom and the cooled gas flows directly to
downstream units
Total Quench design
• In this case, both radiant and convective coolers are

eliminated
• This design offers flexibility for co-production of

hydrogen, chemicals and electricity
• There is a big difference in the cost of these designs,

being the highest for the full heat recovery and the
lowest for the direct quench design
Shell Gasifier
• Shell gasification processes are widely used in both

chemical and power applications
• Are quite flexible with respect to different feedstocks
• Have been successfully used with sizes above 500 t/d

for Shell gasification process (SGP) and 2000 t/d for
Shell coal gasification process (SCGP)
Shell Gasifier
• Gasifiers for large-scale applications for refinery

residues (up to 2000 t/d) and petroleum coke (up to
3700 t/d) have also been developed
• Shell gasifier employs a water-cooled membrane wall

covered with a protective layer of a refractory and
frozen slag
Shell Gasifier
• This arrangement allows recovery of the part of heat generated in the
gasifier in the form of a super heated high-pressure steam
• The molten slag is drained from the gasifier through a slag tap at the
bottom and is collected in a water bath, Part of the slag is entrained
with syngas as a fly slag
• Hot raw syngas is first quenched with recycled product gas to about 930
°C to solidify entrained fly slag
• Syngas and slag then flow to a convective gas cooler where most of the
sensible heat of the syngas is recovered as a super heated high pressure
steam
Shell Gasifier
• Entrained fly slag and ash are then removed from the

partially cooled raw syngas using cyclones and filters
• Syngas is then cooled further and scrubbed of any

residual solids in a wet scrubber system
• Captured solids are recycled to gasifier or mixed with

gasifier slag for disposal
Shell Gasifier
• Solid free raw syngas is then passed over a COS

hydrolysis catalyst and is subsequently treated with a
chemical Solvent to remove all sulphur compounds
• The clean fuel gas is reheated and is saturated with

water before being used in a combustion turbine
Shell Gasifier
• With respect to gasification of petcoke Shell Gasifiers

are perhaps the most widely used gasifiers
• Low ash in petcoke requires addition of a mineral

matter such as limestone, dolomite, etc., to petcoke
for ensuring the formation of protective layer of slag
on membrane wall at the initial stages of operation
Salient features of various types of gasifiers.
Gasifier Technology Typical process condirions Remarks
CD (2) £3) £4)
Fixed bed BGL Combustion temp.: 1300 T (slurry feed) -Car carbonize coal containing -35% ash.
Lurgy and 150GMSO0 *C (dry feed) -Carnot use liquid fuels
Liry ash Gas outlet temp,: 400-500 °C -Steam requirement is high
Pressure: 0.15-2.45 Mra -Syngas contains tar and phenolic compounds
R.T.: 15-30 min -More loss oF fine particles of feed produced
Feed particle size: 2-50 nmn during feed preparation
Oj/Feed: 0.64 Nm*/kg
Gas heat value (MJ/Nm3); 10.04
Cold gas efficiency: high
Fluidized bed HTW. IDGCC KKW, Combustion temp.: 900-1200 °C -In situ sulfur capture when 5 content •ÿ2 wt.%
Mitsui Babcock Gas outlet temp.: 700-900 "C -Preferred for high reactive feedstocks Jike waste fuels.
Pressure: 0.1-2.94 MPa biomass and low rank coal
R.T: 10-100 s -Char particles need to be recycled for high conversion
Particle size: 0.5- 5.0 mm -Moderate steam requirement
fVFeed: 0.37 Nmÿ/ltg -Syngas does not contain tar or phenolic compounds
Gas heat value(ÿNmJ):10.71 -Reduced loss of fines
Entrained bed BBP, Hitachi, MHI, Combustion temp.: 1500 "C Syngas does not contain any tar or phenolic compounds
PRENFLQ, SCCP. Gas out let temp.: 900-1400 °C -Preferred for low reactivity fuels like pet coke
E-Gas, Texaco Pressure :2.04-3.43 MPa -Suitable for co-gasification of petcoke and high ash coal
R.T: 1-10 s
Particle size: -:20Q mesh (90%)
-
mixture having 22% ash.
-Steam requirement is moderate
Oz/Fecd: 1,17 Niriÿ/kg -In-situ sulfur removal and no fine loss
Gas heat value (MJ/Nm3): 9.5S
Transport reactor KRR Combustion temp.; 900-1050 "C -Prevents exposure of raw coal to the oxidant pieventing
Gas out lei lemp.: 590-980 “C combustion of the volatile matters released
Pressure: 0.29-1.47 MPa -Only char combustion and improved process efficiency
R.T; 1-10 s -High throughput and conversion
Particle size: ---50 pin -Not well proven
Oj/Feed: 1 .06 Nma/kg
Gas lieat value (MJ/Nm3); -
R.T = residence time. Temp. = temperature.
Source : Review -Syngas production through gasification and cleanup for downstream applications— Recent
developments P. Mondal , G.S. Dang, M.O. Garg , Fuel Processing Technology 92 (2011) 1395–1410
Selection of Gasifier
• Both quality and quantity of produced syngas depend

upon the type of feedstock and gasifier used
• Salient features of conventional gasifiers along with

transport reactor gasifiers are summarized in Table
( Ref- Prev. presentation)
 The highest residence time gives the least syngas
production rate per unit volume of gasifier under the same feeding rate
 From Table it is evident that the fixed bed gasifier requires

maximum residence time and produces maximum CO2 content in the
Syngas
 Maximum CO2 content in the syngas also makes this gasifier less suitable
for the production of hydrogen and chemicals
 Another drawback associated with the fixed bed gasifier is that it can
handle only solid feedstocks
 However, the highly active feedstocks like wood, low grade coal etc.
containing high ash can be used in this type of gasifier
• There is a slight difference between the compositions of

syngas obtained from fluidized bed and from entrained
bed gasifiers
• Some properties of fluidized bed gasifiers like O 2/feed

ratio, gas heating value, etc., are superior to the
entrained bed gasifier
• However, the residence time is very short for entrained

bed, which gives it more syngas production capacity
• The maximum temperature in the combustion

zone of an entrained bed gasifier also makes it
suitable for the gasification of less active
feedstocks
• Co-gasification i.e. coal and petcoke mix can be

gasified effectively in an entrained bed gasifier
• Based on literature information 75% of the operating

IGCC plants are using Shell and/or Texaco entrained
flow gasifiers
• Also about 70% of the planned gasification projects

will use either the Texaco or Shell entrained bed
designs
Syngas Conditioning and Cleanup
• Raw syngas produced in a gasifier is very hot and

contains impurities like particulates, soot, acid gasses,
etc.
• It also contains high amounts of CO, which is not

desirable for many downstream applications
• Hence, conditioning and cleaning of syngas is required

for its efficient use in various applications
Water gas Shift Reactors
• In commercial gasifiers, the produced syngas contains high
amounts of CO (30-60%) which can be converted to H2 by
water gas shift reaction (WGSR)
• Un-shifted syngas contains 27-50% H2
• This is an important reaction for more H2 production from

syngas coming out from coal gasifiers
• In this catalyzed reaction, steam and CO react to produce H2

and CO2 and the reaction is represented as:
CO +H2O→H2 + CO2; ΔHo298 −41.1kJ/mol

• Shift reactions are carried out either after the

removal of sulphur from syngas (sweet-gas shift
reaction) or is done before sulphur removal (sour-gas
shift reaction)
• Setup for sweet-gas shift reaction has two high

temperature shift (HTS) and one low temperature
shift (LTS) conversion stages with cooling between the
reactors
• Sour-gas shift reaction consists of two to three
conversion stages with heat exchangers and with
steam addition arrangement
• Sweet-gas shift can operate with less steam; desirable

from the economic point of view
• Within two HTS steps, sweet-gas shift can reduce CO

concentration from 45 % to 2.0% at the end of run
(EOR) conditions
• The residual CO can further be converted to 0.5% (EOR)

in LTS step
• Using sour-gas shift, CO can be converted from 45 % to

1.8% (EOR) within two steps using a slightly higher
amount of steam as compared to the sweet-gas shift
concept
• To reach a CO level below 1%, it is necessary to add a

large quantity of steam before running the shift reaction
in a third reactor
• Sweet-gas shift catalysts are usually more expensive

than sour-gas shift catalysts
• Sweet-gas shift catalysts also have more complex

start-up procedure and are more sensitive with
respect to poisons and operational conditions
• Cu/ZnO/Al2O3 is catalyst for the LT shift reaction (200–250 °C),

Fe2O3-Cr2O3 is catalyst for HT shift reaction (320- 450 °C)
• The Cu/ZnO/Al2O3 catalyst has a relatively higher selectivity

than Fe2O3–Cr2O3, its main disadvantage is lower resistance to
sulphur and chloride impurities
• Instead of using Separate catalysts in LT/HT shift rectors,

catalyst like Co–Mo/Al2O3 can also be used over a wide range
of temperatures
• From thermodynamics angle the conversion of CO to

H2 is favoured at higher temperatures allowing
recovery of the heat of reaction at quite high levels
to generate High pressure(HP) steam
• HP steam can be used within the plant
• This consideration may also influence the decision for

using sweet-gas or sour-gas shift reaction
• For power application, sour gas shift reaction is

favourable, where as for chemical use, sweet gas shift
reaction is required
• Pressure swing adsorption (PSA) process to separate

Hydrogen from CO2 (hydrogen recovery - 98%)
Vmm
• Cu/ZnO/Al2O3 is the catalyst for the LT shift reaction (200-250 °C)
whereas Fe2O3–Cr2O3 catalyst is used in the HT shift reaction (320-
450 °C)
• The Cu/ZnO/Al2O3 catalyst has a relatively

higher selectivity than Fe2O3-Cr2O3, but drawback is lower
resistance to sulphur and chloride impurities
• Instead of using Separate catalysts in LT/HT shift rectors, catalyst

like Co-Mo/Al2O3 can also be used over a wide range of
temperatures
IGCC Technology
Production of Electricity & Energy
Efficiency
B. Tech, APEG Course

G.S.Dang
gurbax49@gmail.com
25/26-9-2017
What is IGCC ?
• “Integrated Gasification Combined Cycle” or IGCC
• Chemical conversion of coal to synthesis gas for

combustion in a gas turbine for power generation
• A cleaner process since coal is not combusted and

the produced syngas is relatively easier to clean
up compared to larger volumes of flue gases of a
coal combustion plant
Coal IGCC Process
Process11
Gas End
Feeds Gasification Cleanup Products
o Oxygen
Alternatives:
1
H
Combined Cycle
Power Block
Electricity
Gas & Steam
Coal Turbines Steam
Heavy Oil
Alternatives:
Petroleum Coke Hydrogen
Clean Syngas
SULFUR Ammonia
REMOVAL
Refinery F-T Liquids
Residues
Orimulsion SULFUR Marketable

RECOVERY Byproducts:
Natural Gas
I Solid Sulfur
Slag (ash)
1 Texaco Gasification Power Systems (TGPS)
IGCC Plant- Main parts
IGCC plant is based on highly integrated system
• The plant is divided into three parts;
 The gasification island comprising of feed preparation unit,

gasification unit , gas treatment unit and a sulphur recovery
unit
 The power block comprising of gas turbine , heat recovery

steam generator and steam turbine
 Air separation unit (ASU)

Gasification
• Gasification is a partial oxidation process ; produces syngas
• Carried out in limited supply of Oxygen/ Air
• Oxygen is used as oxidant
• Various types of gasifiers are in use
• Feedstocks
- Coal
- Petroleum residues / petcoke
- Biomass, etc
IGCC
• Gas turbines can be fired with either gaseous fuels or
lighter distillates which can be easily vaporized
• Can not be fired with solid or liquid fuels i.e. coal or fuel oil
• Gasification acts as a bridge between conventional fuels

such as coal or fuel oil and the gas turbines
• A combination of gasification and combine cycle (IGCC) is a

coal based technology almost matching natural gas fired
system - environment performance wise
Syngas Utilization:
Power Production
Downstream Utilization of Syngas
- Power Generation
- Hydrogen production
- FT / Chemicals
Poly-generation with Gasification
Power
Electricity
Steam
Fuels
Fischer-Tropsch Diesel
Naphtha
Syngas Methanol/Ethanol
>ÿ
Dimethyl Ether and

Hydrogen
Coke/Coal
Chemicals
Waxes
Olefins
Acetates and many
Others
Desired Quality of the treated Syngas for
various Downstream Applications
Downstream Sulfur CO2 (Vol.%) CO

use (wppm)
Power 10-15 - -
Hydrogen <1 <0.1 < 50

wppm
Chemical <0.01 0.05 – 2.0 H2/CO

control
Power Generation
Residue/ Raw Gas Combined
Coke/
Gasifier Cleanup Clean Power
* Gas * Cycle
>ÿ >
Gas
Coal
 High efficiency: due to CC (Gas & Steam turbines)

 Potential for even higher efficiency: advanced GT
 GHG reduction: by high efficiency & easy CO2 removal
 Low SOx and NOx : H2S vs SO2, GT has low NOx
 Low water consumption: 2/3 power from GT
:
IGCC Power Plant
Particulate Gas
Removal Cleanup
f- S
Gasifier J
Particulates I
.5
Gaseous Sulfur Byproduct
Constituents
w
Air Separator
T
Oxygen Compressed
Coal, A,r Combustor
Petroleum coke,
Biomass,
1 rr=i
—3-
Air
Waste, etc,
13—Q Generator
Electric
Power
Steam
Air
I
Combustion
Turbine
Hleat Recovery
Steam Generator
+
Steam
1 Generator
Stack
Solid Waste
Steam Turbiiime CHZHZD —3- — Electric
Power
Source: NETL 196

Energy Flow Diagram for an IGCC Unit
(Assumed Efficiency - 44%
upper limit of design)
Particulate Gen
95% Removal Cleanup 75%
Air
Separator 6%
auxUieties
SmH*
c.
* Sulfur
n,
Fly toll
Gaseous By-Product
By-Product 30% ElPCtrtC
Pmr
Constituents 44%
SadAsr I JUr Cnda Combustion | Generator *

100% Soli ns Turtrina l&5% 115%
Hi—rlflflfl
20%
+
r 30%
'stack
r aoQ- XX
CMI,
Potroloum Mb,
i
Hlem&M,
50% 30%
Coating loss
3lag
By*Pn«luct
I5% Sham Turbina
Generator
toss 20%
International coal-based IGCC plants, Buggenum and Puertollano, have been reported as 8,240 (41.4%) and
8,230 (41.5%) Btu/kWh, respectively.
IGCC Efficiency
• Higher efficiencies mean that
 Less fuel is used to generate the rated power,

resulting in better economics
 Lower cost of power production
 Formation of less greenhouse gases

IGCC Efficiency
• IGCC plants operate at efficiencies of about 40% but have the
potential to be as high as 45%
• Coal-fired, subcritical power plants indicate an average efficiency

of 30.9% with a range of 17.6% to 37.8%
• The efficiency of coal-fired PC boilers installed in the power

plants since 1991 ranges from 33% (sub-bituminous coal) to
36.7% (bituminous coal)
• Supercritical pulverized coal (SCPC) performance as 38.3% and

the upper end of ultra-supercritical (USCPC) performance as 42%
to 43% for bituminous and sub-bituminous coals
Supercritical & Ultra-supercritical
Operations
• Supercritical steam cycles means operating above
critical conditions of steam i.e. temperature above 374
o C & pressure more than 221 bar
• Modern supercritical units are pulverized coal fired

units with typical conditions as 285 bar/ 580 o C and
above
• Next step - going to 300 bar/ 600 o C , 620 o C

IGCC Efficiency – Influencing Factors
•Coal type
 High rank coals can be gasified more efficiently than coals of low rank
 The higher moisture and ash content of low rank coals require a higher degree
of oxidation (more oxygen) to achieve slagging temperatures ( energy needed to
vaporize the moisture and melt the ash)
•Gasification technology
 Gasifiers with a dry feed are more efficient than gasifiers with a slurry feed
because less water need to be vaporized
 Gasifier technologies that include syngas coolers for heat recovery of the
thermal energy of the hot syngas, are more efficient than those with a water
quench
IGCC Efficiency – Influencing Factors
• Degree of Air Separation Unit (ASU) Integration

 Integration of ASU with the gas turbine increases the electrical efficiency but
can also result in operational difficulties ( In integration all or part of the ASU
air is supplied from the gas turbine)
 To avoid operational problems, new designs compromise at 25% to 50% of
ASU air supply extracted from the gas turbine compressor ( the remaining air
provided by the ASU’s dedicated compressor)
• Technology level
 Gas turbine technology and turbine inlet temperature, together with the
choice of steam cycle, have the most significant impact on electrical efficiency
IGCC/CCS System
Shift A CO,
Particulate CM Capture
Removal Cleanup
CO,
I T
C
0*pMad OillOat
\ mob Oil R*«ov*r»

Coal IWOi
Raaarvolrt
0**p Salrno *aultor
—
Oaaaoua Sulfur Byproduct
Conatituanta
Air Saparator
45 T<Combuator
Oaygon A,f
Coal,
HMiWvm CO**
BiomoM. Air
Waal*, ate Etactnc
a
Gaoarator
Compilation
Air Turbina Greenhouse Gas
Haat Recovery Sequestration
Steam
I
Steam
r 91 Steam Oanarator
Stack
Staam Turtun* Eiactnc

Solid Waal*
Coal-fired power generation,
Thermal Efficiency
country Technology Efficiency Projected efficiency with CCS
Australia Black ultra-supercritical WC 43% 33%
Black supercritical WC 41%
Black supercritical AC 39%
own ultra-supercritical WC 35% 27%
own supercritical WC 33%
own supercritical AC 31%
Belgium Black supercritical 45%
China Black supercritical 46%
Czech Republic own PCC 43% 38%
own ICGG 45% 43%
Germany Black PCC 46% 38%
own PCC 45% 37%
Japan. Korea Black PCC 41%
Russia Black ultra-supercritical PCC 47% 37%
Black supercritical PCC 42%
South Africa Black supercritical PCC 39%
USA Black PCC &IGCC 39% 39%
USA(EPRI) Black supercritical PCC 41%
Coal-fired power generation,
Thermal Efficiency
• The energy penalty of CCS is generally put at 20-30%
of electrical output,
• Since no full commercial systems are yet in operation,

this is yet to be confirmed
• US and European figures below suggest a small or

even negligible proportion
IGCC Environmental Impacts - Air Pollution
• Commercially available IGCC power plant technologies have

much lower air pollution / emissions than conventional coal plants
• Actual air emissions performance depends on control technology

& performance levels required by the regulators
• Mercury capture at IGCC plants is quite feasible and less costly

than at conventional coal plants and
• Potential exists to indefinitely sequester mercury captured at

IGCC facilities
IGCC Environmental Impacts - Air Pollution
• IGCC technologies for power produce much smaller

volumes (about one half) of solid wastes than do
conventional coal plants using the same coal
• IGCC solid wastes cause less environmental damage

than
fly ash from conventional coal plants
• Ash melts in the gasification process, resulting in an ash

(slag) which is much less subject to leaching pollutants
than is conventional coal combustion fly ash
Mercury Management
• Proven, low cost mercury controls can remove

most of the mercury from coal “syngas” produced
• Mercury is captured in a small volume activated

carbon bed ( bed contents are managed as
hazardous wastes due to the toxics captured)
• Currently coal IGCC, with a carbon bed plant

mercury control, is the only technology that can
convert coal to power and capture much of the
mercury in a form and volume suitable for
permanent sequestration
Er8 m
mk m
M I
. fIM
N
k >.
Hi f
Pi _
ij
r * . :n
L*
iGKW
HI
IT- IIWT *T
Hill
|J|F~
k
«
aw* y
—
!ÿ
fi HUM
Hg Adsorption Towers Hg
IGCC Carbon Emissions
• IGCC plants being more efficient in converting coal to
electricity than conventional coal plants ; produce less
CO2 per unit of electricity generated
– Near-term IGCC plants would produce about 20% less CO2 - per unit of
electricity produced - as would the “average” existing coal plant
– In the longer term IGCC plants may produce about one-third less CO2 -
per unit of electricity produced - as would the “average” existing coal
plant
• IGCC plants have potential to capture and geologically

sequester up to 90% (or more) of coal fuel carbon content
Geologic Carbon Sequestration
• CO2 is currently injected into the oil field operations
to enhance oil field recovery
• CO2 is also removed at some production fields
(along with hydrogen sulfide gas) from natural gas
prior to its transportation through pipelines
• The removed CO2 and hydrogen sulfide gases are
often injected into geologic formations for permanent
disposal
• These technologies (geologic injection and
containment) are now in commercial practice for
CO2 capture at an IGCC plant
Geologic Carbon Sequestration
• Statoil’s Sleipner gas field project, off Norway coast, is
one example of a CO2 sequestration project that injects
captured CO2 into a saline aquifer
• Domestic carbon sequestration would focus initially on

sites where
 CO2 injection would enhance oil recovery or
 Possibility of recovering methane form deep coal
beds
• Longer term sequestration options being explored

include:
 Binding captured CO2 into a mineral which would be

environmentally stable and could readily be disposed
Sleipner Carbon Sequestration Project
Sletpner A
Steipner T
-4
Gas from
S4eipoer West
CO? Injection Wen

V
nun
ormation
Sterner East
Producbon and Injection Wefts
Capital cost Of IGCC vs other Technologies
Total capital requirement ($/kw)
CAPITAL COST: IGCC *£ COMPETITION
1
NGCC ,fG,f 1
SCPC
PFBC
IGCC "H" L
I I I I I I I
IGCC lhF"
400 500 000 700 000 SCO 1000 1100 1200 1300
3
1400 1500
Total Capital Re quire me nt, S/k W
Source: NETL, “Process Engineering Division,” PED-IGCC-1998, Revised June

2000. Fuel price data updated in 2005. (IGCC without & with CO2 capture )
(SCPC –supercritical pulverized coal, PFBC-Pressurized Fluidized bed combustion)
IGCC
Power Production in India

Indian Power Sector
Capacity, MW
185172.88
200000
180000
160000
140000
120000
100000
80000
42783.42
60000 38821.52
40000 24508.63
20000
5780
993.53
T T T T T T
Hydro Coal Gas Diesel Nuclear Renewable

Maximum Coal based generation – greater contributor to pollution
Total capacity 298060MW, Share of coal- 62%
Selected countries emission
standards for coal fired power plants
Country Time NOx ,mg/Nm3 S02,mg/Nm3 PM ,mg/Nm3
Period
existing new existing new existing new
Australia S00 200 80
China hourly 100 50 200/50 35 30/20 10
Germany daily 200 150 200 150 20 10
600/300 600/200 100/50
* India
Indonesia
Cont.
850
100
750 750
100
750 150
30
100
Japan 410 200 200 100 50
South Cont. 1100 750 3500 500 100 50
Africa
Thailand 820 410 2002 515 180 80
USA daily 135 95.3 185 136 18.5 12.3
EU Cont 200 150 200 150 20 20
India new – since Dec 2017,*existing – old

In India Newplants
Norms/newer plantsfrom
Effective afterDec
2003
2017
Evolution of Emission Standard for Power Sector
2015 (effective from 2017)

(PM, S02 & NOx)
2003
PM : 50 mg/Nm3
: 100 mg/Nm3
2002 : Use of Stack Height : 220 m
beneficiated coal 275m

1989
Stack Height : H= 14 (Q)0.3
1984 220m
PM : 350 mg/Nm3
: 150 mg/Nm3
Comparative CO2 Emissions
2,000
1897
1,800
1673
1,600
1,400
Emissions in Pounds per MWH
1,200
1,000
842
800
600
400
238
200
0
New Coal Current IGCC IGCC With CO2 Capture and New Natural gas
Sequestration
Tabic 2: Existing ICCC Plants: Design and Operating features and Emissions Levels
Wabash River
Polk Power NUON/Demkolec ELCOGAS
Cc lierating
Station Station (Biiggenurtn The (Puertollano,
(Florida) Netherlands) Spain)
(Indiana)
DESIGN AND OPERATING FEATURES
Gas turbine, MWc 192 192 155 182
Steam turbine, MWe 121 104 m 135
Auxiliary power, MWe 63 34 31 35
Net Power Output MWe 250 262 253 298
Efficiency, % (HHV basis) 37,5 39.7 41.4 4L5
Efficiency, Btu/kWh (Ell IV 9,100 8,600 8,240 8,230
basis)
Coal Usage (tons/dav) 2,500 2,544 2,200 2,400
EMISSIONS
SOj (Ib/MWb) <1.35" L08' 0.441 0. 1 5J
NO, (Ih/MWIi) (152d I 09c 0.71 G.88J
Particulates (lb/MWh) <0.04L <0.10" 0.01 1
0.044J
Sulfur Removal, % >98 >98 >99 99,9
NO,, ppmvd (@ 15% 03) w 2? < lO" <10n
IGCC Power Plant with Gasification (PRENFLO)
Power
r
Air f
+ + Steam
, Gas
turbine /
i
On-site use Flue gas
'/I
i
turbine
o
i i
\
<D /\
N
=®
FI eat recoveryv C:
steam generator I --
Air
separation 0 Combustion
chamber
Nitrogen
Boiler feedwater Water
preparation
Steam
Oxygen
t
Raw water
t
Feed Sulphur
Feed PRENFLO" Desul¬
preparation phurization Claus unit
gasification
Slag / fly ash
Emissions Comparison
Estimated New Plant Emissions Performance
2
1.5
lb/MWh
1
0.5
~80% 95%+ ~0 ~0 ~0
NOx SO2 PM Hg NOx SO2 PM Hg NOx SO2 PM Hg
SCPC1 IIGCC2 NGCC1
1Based on emissions levels in EPRI/NETL, Evaluation of Innovative Fossil Fuel Power Plants with CO2 Removal, Dec. 2002, SCPC and NGCC 7FA base cases.
2 222
Levels proposed for qualification in 3 Party Covenant federal incentive program. Based on performance characteristics provided in NETL, Major Environmental Aspects of Gasification-Based Power
Generation Technologies, December 2002; and performance estimates from Eastman Chemical Company.
Coal Based IGCC Plants in Operation
Project/ Combustion Gasification Net Output Start-Up

Location Turbine Technology MW Date
Wabash GE7FA EGas 262 Oct 1995

River, IN (ConocoPhillips)
Tampa GE7FA Texaco 250 Sept 1996

Electric, FL (GE Energy)
Nuon Siemens Shell 253 Jan 1994

(Formerly V 94.2 (Offered jointly
Demkolec) with Krnpp-
Buggenum Uhde)
Netherlands
ELCOGAS Siemens Prenflo 300 Dec 1997
Puertollano V 94.3 (Offered jointly
with Shell)
Spain_
I able 11 Barriers m [kploÿiiÿ IGCC
ht'plovmviL Calt'ieur* IGCC Dt'pluvmtnl Biirritri11
—
noil **• "
Tech no logy
--
ItL'hnaJusjcul Fitmiss
Acceptance und
Issues
•l.ttw prl LI ii L uYjjljliility*
•Kawtr
General lack of operating experience
Blÿnicnw wi(tmnnn]aci#l facilities
Plant operators’ lack of familiarity with [GCC
I rid miry C'uLture: IGCC marc like chcinieitl plant than A
J'i'iijcvl Siii.ii” K'-UL-S l>|iital p*wer pkml unJ power utilities understand com bistkxi, mil
chemical units
* Lack of uppreciadon for fuel diversity fe.g.., IOCC fuel, flexibility):
Poor perception of coal by the general public

Lack of appreciation for social henefits
Project Bcoaomic and

Financial Issues
- Higher capital costs Ihan other fossil power plants, particularly PCI
plants
•Doubts about plant financial viability wirliou.tsLibsid.ies

Concerns with the ability to obtain s iable performance guarantee*
sndnarrantics
* IGCC performance
Increased risks associMed with up-front dcvclopmcnd costs
Ay aiLi bilily of turnkey ICCC veindors
*'
*ÿ History of construction and siairap problems
*- l ong construction Lead limes
Market Competition Competition include* SCPC 'CSCPC. nuclcat. distributed general ion
[e.y., mi nolurbines"). renewables. and fuc-J/tec hnoIcryy uptLans with
LNG
Application of carbon constraints favors greater adoption of gas-
kiiscil [eehraoluj'yn nuclear, and .renewables
4 LN'G is viewed as bodi a compel Mot and substitute.
" Key barriers are murked in bold lbn1.
b Availability refers to the percentage of time that a plant is available to operate when required
Vmm
Production of Methanol, Hydrogen &
Ammonia from Syngas
UPES , Dehradun
27-9-2017
G.S.Dang
gurbax49@gmail.com
29-9-20172-
9-2017
Methanol & Uses
• Methanol is an important chemical
• It is used in Production of formaldehyde,

acetic acid, light olefins, DME (dimethyl ether)
and direct gasoline blending
• China at present consumes 54 percent of global

methanol demand
Uses of Methanol
Use of methanol is increasing in the production of
• Olefins or methanol-to-Olefins (MTO) ,
• Methyl tertiary butyl ether (MTBE), a gasoline additive

that improves air quality, and
• Dimethyl ether (DME), a clean-burning fuel with similar

properties to LPG
Methanol as Fuel
• It's a cleaner-burning, alternative source of energy
• Approximately 45 per cent of the world's methanol is used

in energy-related applications
• Methanol blended into gasoline produces a high-octane,

efficient fuel with lower emissions than conventional
gasoline
• Methanol is also emerging as a clean-burning marine fuel

that can cost-effectively meet the shipping industry’s
increasingly stringent emissions regulations
Methanol- Uses
• Methanol is also a key component in making

of :
 Biodiesel, a renewable fuel that can be

used in place of, or
 Blended with, conventional diesel fuel

Methanol- Feedstocks
• The primary feedstock for methanol is natural gas,
representing as much as 85 percent of installed global
capacity
• Methanol capacity additions has been more in areas

like Middle East, Africa and South America where low-
cost natural gas is available
• With the growth in Chinese methanol demand and the

it’s rich coal reserves, the industry has seen a sharp rise
in coal-based methanol production in China
Syngas to Products
Natural Gas
11
Rsflning Wax
Fischer-
HydrthgEn Syngas + Trz p 5:h
Chemicals
FsrtilizErE \ N az hth a
Fuel Cells
Methanol
\ Light jiifi
Fa nr aid:-yd: ME
S as-z line
Methyl Ethyl: ne
Ac:tic Acid
Ac:tat: Prapylen:
- Paly me rs
Ac:tic Vinyl
Ket:n: Eÿt= rs
Anhydrid: Mona me r
2015 Global Methanol Demand By End-Use
Solvents Others
I
MTO 4% 1 7%
18%
Chloromethanes
2% Formaldehyde
27%
Methylamines
3 :
DME
8%
Biodiesel y7
3% V_ Acetic Acid
GasolineV 9%
Blending MMAVÿ MTBE/TAME
9% 2% 8%
Methanol Demand Growth- Global
2011 Methanol Demand by End Use 2016 Methanol Demand by End Use
DMT/Others DMT/Others
m
Solvents 8 5%
Solvents
MTO/MTP, 4% Formaldehyde
kT
6% r Formaldehyde
32%
25%
Chloromethanes.. MTO/MTP
1%
22%
Methylamines _/i
4%
4k
Acetic Acid
Chloromethanes 8%
Dimethyl Ether j
1%
11%
w Acid
Methylamines J
3% 7%
10%
11% Dimethyl Ether \ Methyl
Methyl I 8% Methacrylate
Methacrylate MTBE/TAME Gasoline/Fuel 1%
2% 10% 16%
Demand = 55.4 Million Metric Tons Demand = 92.3 Million Metric Tons
Currently around 32 percent of methanol is consumed in the production of formaldehyde. This is anticipated to fall to 25
percent by 2016 with Gasoline/Fuel applications becoming the largest demand sector, totalling 31 percent.
Formaldehyde uses are very diverse, common applications are into the wood industry as adhesives, disinfectant / biocide and
photographical industries
Methanol to Olefins (MTO) and methanol to propylene (MTP) demand is anticipated to become a high growth sector, rising
from 6 percent of end use demand in 2011 to 22 percent by 2016, the vast majority of which is forecast to take place in China
Global Methanol Demand Crude Derivatives vs.
Traditional
Global Methanol Consumption
too
80
ifl
£=
O
O 60
03
c 40
o
20
0
10 11 12 13 14 15 16 17 18 13 20
Traditional derivatives MTO/MTP Fuel

Global Demand of Methanol
China V/s Rest Of World (ROW)
Million Metric Tons
120.0
China Demand AAGR 2006-2011: 23.8% China Demand AAGR 2011-2016: 19.5%
ROW Demand AAGR 2006-2011: -0.15% ROW Demand AAGR 2011-2016: 3.1%
100.0
80.0
nil
60.0
40.0
20.0
0.0
2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Demand - ROW •Demand - China
Methanol Use by Region
22%
Ex China
China
39%
L America
N. america
Europe
Asia Pacific
13%
Methanol vs Crude Oil
Methanol vs. Crude Oil Pricing

800 140
e 700 120
£ Crude Oil oS
-
o 600
100
(0
ffl
o
500 0.
5 80 w
S2 400 £o
£o Methanol
60 Q
o 300 O
o"
% 40 %
200 £
€
0) o
100 20
0 0
2000 2002 2004 2006 2008 2010 2012 2014 2016
Methanol-to-Olefins
• Light olefins (ethylene and propylene) are the basic building
blocks used to produce many plastic products
• Olefins can be produced from feedstocks like methanol, naphtha,

liquefied petroleum gas and ethane
• Demand for methanol in the production of olefins or methanol-

to-olefins(MTO) has grown rapidly In recent years,
• The MTO process is cost competitive compared to the use of

naphtha, and MTO demand is expected to continue increasing in
China
Dimethyl Ether
• Dimethyl ether (DME) is a clean-burning fuel that is typically
produced from methanol
• It can be stored and transported like liquefied petroleum gas

(LPG)
• DME is being produced on a large scale in China, where it is

primarily being blended with LPG for household cooking and
heating
• DME can also be used as a clean-burning substitute for diesel

fuel, but this in not widespread today
Methyl Tertiary Butyl Ether
• Methanol is used to produce methyl tertiary butyl

ether (MTBE), an oxygenate blended with gasoline to
increase octane and reduce motor vehicle emissions
• MTBE is an efficient, clean-burning and cost-

competitive gasoline component used in many regions
of the world
Methanol - Biodiesel
• Biodiesel is a renewable fuel made from plant

oils or animal fats that uses methanol in the
production process
• Methanol is also used to manufacture the

catalyst employed to produce biodiesel.
Methanol for Power
• Methanol is a cost effective, liquid fuel alternative for

power generation, particularly in remote regions
which use diesel and are not situated near gas
pipelines
• Only minor modifications and expenditures are

needed to adapt existing power plants and
associated infrastructure to accommodate the use of
methanol as a fuel for power.
Methanol for Power
• Methanol is a cleaner burning fuel for power

generation than diesel and can help meet
environmental regulations and improve air
quality
• Methanol also offers utilities fuel flexibility
• Power plants operating on diesel that convert to

methanol can operate on either fuel
Methanol Synthesis
Methanol Synthesis
• The production of methanol consists of three steps
independent of feedstock :
 Synthesis gas preparation,
 Methanol synthesis and
 Methanol purification
Methanol
Syngas Production Options

Steam Methane Reforming
• Methane gas and steam are reacted at high

temperature (≈850 °C) and pressure in presence of a
catalyst forming carbon monoxide and hydrogen
(Equation 4)
• Steam reforming
2CH4 + 2H2O ⇌ 2CO + 6H2 ΔH298K= 49.1 kcal/mol -(4)
• Water gas shift

CO + H2O ⇌ CO2 + H2 ΔH298K= -9.8 kcal/mol
• Carbon dioxide is added to the gas mixture before the

methanol synthesis (may also be present in the natural
gas used as feedstock)
• Steam reforming produces an excess of hydrogen

which needs to be utilized ( H2/CO ratio as 2 for
methanol Synthesis)
• The synthesis gas producing is endothermic and requires

a lot of thermal energy
• The methanol synthesis produce some heat that can be

used or else required heat is normally provided by
burning a part of the natural gas
• One step reforming through steam reforming is today

mainly considered for smaller plants up to 2500 MTPD
where CO2 is available at low cost or contained in the
natural gas
Two-step Reforming
• A combination of steam reforming and partial oxidation process
provides better control on composition of the produced
synthesis gas
• Two step reforming requires that the steam reforming operates

with high methane slip( 35- 45 %) to provide a higher methane
content for the partial oxidation step
• The process is new and was first used in Norway in 2007 for a
2400 MTPD commercial plant and a 5000 MTPD plant with
similar technology in Saudi Arabia 2008
Dry Reforming
• Methane and Carbon dioxide react to produce synthesis
gas in a process called dry reforming as no steam is used
• Dry reforming
CH4 + CO2 ⇌ 2CO + 2H2 ΔH298K = 59.1 kcal/mol
• Reaction is more endothermic than steam reforming and

produces a gas with significant hydrogen deficit for
methanol synthesis
• This is disadvantage only for methanol synthesis but the

gas mixture has right composition for other applications
Methanol Synthesis
• The ideal syngas composition for methanol production
is H2/CO = 2 and 5 Vol% of CO2
• Methane reacts with steam (steam-methane reforming)

on a nickel catalyst to produce syngas at 4 MPa and
850°C producing carbon monoxide and hydrogen ( or
alternate Syngas generating process is used)
• In a secondary reaction at 5-10 MPa and 250°C carbon

monoxide and hydrogen react on a catalyst (mixture of
copper, zinc oxide and alumina) to produce methanol
Methanol Synthesis
• Synthesis of methanol is highly exothermic, takes place

over a catalyst bed at moderate temperatures
• Most plant designs make use of the extra energy to

generate electricity
Methanol Synthesis
• The process consists of the three following

equations:
• CO + 2H2 ⇌ CH3OH ΔH298K= -21.7 kcal/mol –(1)
• CO2 + 3H2 ⇌ CH3OH + H2O ΔH298K=-11.9 kcal/mol-- (2)

-----
& Reverse WGS
• CO2 + H2 ⇌ CO+H2O ΔH298K= 9.8 kcal/mol ----(3)
Methanol Synthesis
• All reactions are reversible and so the process

conditions i.e. temperature, pressure and synthesis
gas mixture are important to control
• First two reactions are exothermic, i.e. the processes

produce heat and require cooling
• Heat is normally recovered and used in synthesis

process
Efficient Utilization of Process Heat
NG
O2
\f
—
LD LJ-
Conversion
Process
Syngas
Reformer
CO2
•© • NG Partial Oxidation and Conversion Process generate
heat
V
• CO2 Reforming requires heat
Separation
• System is balanced consistent with the Conversion
Process
V Products
Methanol Synthesis
• The main process that produces methanol is the

reaction between carbon monoxide / carbon dioxide
and hydrogen (equation 1 &2)
• The methanol production showed that CO2 was active

and important in the reaction
• It is reported that mainly the CO2 gets converted into

methanol while CO acts as a reducing agent for oxygen
at the surface of the catalyst
Methanol Synthesis
• Equation (3) is the reverse water gas shift reaction that

produces carbon monoxide from carbon dioxide and
hydrogen
• The carbon monoxide then reacts with hydrogen to

produce methanol
• To synthesise methanol a specific H2/CO ratio of 2 in

the syngas is needed also a (H2-CO2)/(CO+CO2) ratio,
called stoichiometric number, to be equal or above 2
Methanol Synthesis
• High pressure synthesis ; 25-35 MPa , 300-450oC

• Catalyst ; Zinc oxide and Chromium oxide
• ->
Low pressure synthesis ; 5-10 MPa, 200 -300oC
• Catalyst for low pressure ; Copper oxide & Zinc
oxide
• Methanol converter - different types contains
catalyst, quench cooled, adiabatic , tube cooled and
steam raising
Methanol Synthesis
Product
• Crude methanol- contains water and other
impurities like DME, higher alcohols, ethers,
ketones etc
• Purified in a series of distillation columns

Methanol Purification
• Crude methanol produced contains impurities; the

largest impurity is generally water, going up to 18 %
• The first step in a two-step purification process is to

remove the low boiling light ends in a “topping
column” producing a mixture of methanol and
water
• Another column is used to separate water and

methanol ; Methanol is recovered as top product
Methanol Synthesis
Processes for Methanol Synthesis
• ICI Process
• Krupp Uhde GmbH
• Lurgi Oel-Gas Chemie GmbH
• Synerix Low pressure process
• Haldor Topsoe
ICI low-pressure process is described in next
slide
Methanol Synthesis
Purge Light ends
€>
jS[iÿ
1 ... Methanol
J i
HrjiV.ir
'ÿ, . 1 HP steam alcohols
( ST Air steam
(2S ft
—
Synthesis gas
Wastewater
-* O * *
Reactor Separator Light encfc Pure methanol
column column
Flow scheme of methanol plant (ICI low-pressure process)

Value Chain - Methanol
Other Products
UF/PF Resins
From
Acetic Acid
Natural Gas Methanol
MMA
Methanol
MTBE
DME
Coal
Gasoline
MTO/MTP
Biodiesel
• Products used in making of Resins ( UF/PF), Polyacetals, PTA, Fuels etc
• further used in construction, automotives, electronics, paints solvents , bottles etc
Hydrogen Production
Key Processes
 Syngas generation
 Water gas shift
 Desulfurization
 Hydrogen purification
 CO2 Removal
 Final polishing
Production of H2 from Coal Gasification
through PSA
200-400 °C, 300 psig 75-90%

recovery
WGS Reactor Pressure
Gasifier Swing H2
CO+HIO « COa+Hz Adsorption
Coal
n
Steam O2
HiO i
CO2 enriched waste gas
Hydrogen Purification
Pressure swing adsorption (PSA)

 Solid molecular sieve adsorbents
 Regenerated by pressure swing
 Hydrogen purities >99.99%
 Hydrogen recovery > 90%
Membranes
 Partial pressure separation by polymer membranes
 Effective for recovery dilute H2 from process streams
 Low pressure hydrogen product
Hydrogen Purification
Cryogenic Separations
• Low temperature (-130 to -155ºC) phase

separation
• Poor operation in the presence of acid gases

 Plugging
Hydrogen Production
Light Hydrocarbons (Methane , Naphtha)
Steam Export Steyn
T Pressure
Feed Feed Pre- Steam Heat
CO-Shift Swing
treatment Reforming Recovery
Adsorption
Fuel 1 Fuel Gas
Heavy Hydrocarbons (Heavy residues)

Oxygen Sulplyr
Steam Export Ste|m
T Pressure
Feed Feed Partial CO-Shift/ C02,H2S,C0S Hydroggn
Swing
Preparation Oxidation Heat Recovery Removal
Adsorption
Fuelgas
CO,-Byproduÿt
PSA Process
The pressure swing adsorption process has four basic

process steps:
• Adsorption
• Depressurization
• Regeneration
• Repressurization
To provide continuous hydrogen supply, minimum 4
Adsorber vessels are required
PSA Process
• Adsorption of impurities is carried out at high pressure
being determined by the pressure of the feed gas
• The feed gas flows through the adsorber vessels in an

upward direction
• Impurities such as water, heavy hydrocarbons, light

hydrocarbons, CO2, CO and nitrogen are selectively
adsorbed on the surface of the adsorbent material
• Highly pure hydrogen exits the adsorber vessel at top

PSA Process
• After a defined time, the adsorption phase of this

vessel stops and regeneration starts
• Another adsorber takes over the task of adsorption

to ensure continuous hydrogen supply
PSA Process
• The hydrogen is concentrated typically from 70 % to

99.99 % (recovery 67.5 %) in the H2/CO2 system and
• to 97.09 % (recovery 67.5 %) in the H2/CO system

Pressure Swing Adsorption
Hydrogen weak
Oxygen
Argon
Nitrogen
Carbon monoxide ,
Methane
Carbon dioxide .. /
b
Ethane
Ethylene
—
L
Propane
Butane TT i
Propylene
Ammonia
Hydrogen sulfide
Mercaptanes
V
BTX
1.
Water strong
jV
. 'frs- ; r
flMt W w ' -» •
***rs».
H2 Purification
Pressure Swing Adsorption
Pressure Swing Adsorption *

for high Purity H2
based on selective adsorption
using different kinds of
adsorption materials (e.g. l
molecular sieves)
H2 Purity up to 99.9999 % I
: ___
. I
H2 Recovery up to 90 % S
m
hoi n
PSA Process
• Pressure swing adsorption (PSA) is utilized to separate CO2
and H2 from the effluent of water-gas-shift reactor through
H2-PSA and CO2-PSA at room temperature by two different
adsorbents
• PSA is a cyclic process - separates gas mixtures based on the

difference of adsorption capacity of each component on an
Adsorbent
• Gas adsorption is at high pressure and desorption is at low

pressure to produce high-purity products
• It is required to concentrate the captured CO2 into >90 %

concentration ; suitable for underground storage
PSA Sequence
$
Adsorption isotherms
Adsorption loading
o°c
fS
1 30°C
|
I 50°C
Desorption loading
200°C
Po Partial pressure PA
Desorption pressure Adsorption pressure
PSA process (2-bed 8-step) at room
temperature
top product flow rate:
top product flow rate:
82000 L($TP)/min
351508 L(STP)/min
H2 purity: 99.98 % H2 purity: 87.82 %
H2 recovery: 78.55%
H2 recovery: 78.55%
75.87 % C02
41.4 %C02 C02-PSA
H2-PSA 2.27 %CO
1.30% CO Adsorbent: 13X-Ca
57.3 % H2 > Adsorbent: AC5-KS
21.86% H2 *
Feed flow rate: 303.14K
Feed flow rate: 303.14K
431315 L
792444 L
(STP)/min bottom product flow
(STP)/min bottom product flow
rate:338390 L(STP)/min
rate:431315 L(STP)/mir
C02 purity: 91.97 %
C02 purity: 75.87 %
C02 recovery: 100 %
' C02 recovery: 97.80 %
PSA Results
• First stage H2-PSA achieves 99.98 % purity and 79 %

recovery of H2 as the top product and
• Second stage CO2-PSA could obtain about 92 % purity

and 98 % recovery of CO2 as the bottom product
• By PSA process, the goal of energy generation and

environmental protection could be achieved at the
same time
Hydrogen Uses
• The main uses of Hydrogen are :
 Refining / desulphurization in oil industry

 Fertilizer Industry
 Fuel Cells
Ammonia Synthesis
• Reaction takes place at high pressure over a
catalyst - Iron or Ruthenium
• N2 + 3H2 ⇌ 2NH3
N2 : H2 1 : 3
(in new processes excess nitrogen is required)
CO +CO2 : < 30ppmw
Sulphur : < 1ppm
Phosphorus , Arsenic, Chlorine : < o.1 ppm chlorine
Inerts including methane : minimum , <2%
Reaction Conditions
• Reaction between nitrogen and hydrogen

is reversible:
nitrogen + hydrogen ammonia
• N2(g) + 3H2(g) ⇌ 2NH3(g)
Operating conditions In the Haber process:
• High temperature - about 450°C
• High pressure - about 200 atmospheres
• An iron catalyst is used to increase the rate of
reaction
Ammonia Synthesis
• Ammonia plants based on gasification technologies
normally surpass these specifications
• Most ammonia plants are built in conjunction with urea
plants
• CO2 from ammonia plants directly used for urea
production
2NH3 + CO2 ⇌ NH2CONH2 + H2O
Typical Requirements:
CO2 > 98.5 mol%, H2S +COS < 2mg/Nm3 , H2 < o.15mol%
Methanol < 10ppmv
Ammonia Synthesis
Ns from the air
H2 from
natural gas
Iron catalyst
beds
N2, H2, NH3 out
vl
Cooling
*1 tank
— t
Liquid
1
Ammonia
ammonia out
Ammonia Synthesis
Stage Having obtained the hydrogen and nitrogen gases (from natural gas and
1 the air respectively), they are pumped into the compressor through
pipes.
Stage The gases are pressurised to about 200 atmospheres of pressure inside
2 the compressor.
Stage The pressurised gases are pumped into a tank containing beds of iron
3 catalyst at about 450°C. In these conditions, some of the hydrogen and
nitrogen will react to form ammonia,
Stage The unreacted nitrogen and hydrogen, together with the ammonia, pass
4 into a cooling tank. The cooling tank liquefies the ammonia, which can
be removed into pressurised storage vessels.
Stage The unreacted hydrogen and nitrogen gases are recycled by being fed
5 back through pipes to pass through the hot iron catalyst beds again.
Ammonia yield at Different Temps. & Pressures
70 -
BO . m
50 .
,<c
c
O
£ 40 . [>K
o 30 .
>- 20-
10 .
0
0 100 200 300 400
Pressure (atmospheres)
Graph shows the yield of ammonia at different temperatures
Ammonia Synthesis
• At 200 atmospheres pressure and 450°C, the yield of
ammonia is only about 25 %
• At 400 atmosphere pressure and 350°C the yield is 65 %
• This means that chemical companies using 450°C

temperatures and 200 atmospheres of pressure are not
maximising their percentage ammonia yield
• Optimization of operating conditions is therefore must

for higher yield of ammonia
Ammonia
• Over 90% of world’s Ammonia capacity is based on Steam
Methane Reforming ( SMR) of natural gas
• The rest 10% is based on gasification of coal or heavy oil
• Plant sizes today are 1500 to 2000 t/d and going up to

5000 t/d
• Global ammonia consumption around 190 million tonnes

( in 2016)
Ammonia Uses
• Ammonia is used to make fertilisers (as a source of

nitrogen for plants), explosives, dyes, household
cleaners and nylon
• It is also the most important raw material in the

manufacture of nitric acid
Vmm
Sulphur Recovery

UPES, Dehradun
13-9-2017
G.S.Dang
gurbax49@gmail.com
Sulphur Recovery
• Prior to 1970 major reason to recover sulphur from
refinery gases was economic one (typical recoveries -
90/93 % )
• H2S was commonly used with other gases as refinery
fuel and SO2 emissions was within the acceptable
limits
• Strict environment regulations now require sulphur
recovery of 99 % or more
• This requires two stage process with modified Claus
( H2S > 50%) unit for the first stage followed by second
stage such as tail/ off gas treatment process
294
Typical Recovery System
Plant Feed Gas
Acid Gas Removal Sweet
Gas Treat Gas
Acid Gas {H2S + CO2}
* H2S Recycle
Tail Gas ¥
Claus S.R. Incinerator Stack
gas
Treating
Sulphur
295
Sulphur Recovery from Acid gases
H2S Recovery
• Refinery processes give rise to large quantities of sour gas ( H2S)
as by product
• Removal of H2S from such gases is achieved by absorption /
chemical processes using alkanolamine solution ( MEA, DEA ,
MDEA, DGA etc)
• Physical solvent processes use solvents like Selexol, Rectisol ,
Sulfinol, Propylene carbonate
• Dry adsorbents processes use Molecular sieve, Activated
charcoal, Iron sponge and zinc oxide etc.
Among above mentioned processes Diethanolamine (DEA) /
MDEA processes are most widely used 296
H2S Recovery Unit using Amines
H,S ©
Sweet gas ©
absorber
Lean H S to
amine CW Sulphur
plant
Amine
regenerator
<§> CW >
Sour gas w
Rich
amine
HÿS recovery unit
297
H2S Recovery using Amines.. contd
• A typical H2S recovery unit consists of packed
absorber, an amine regenerator
• H2S is recovered from amine solution by heating it

at low pressure
 Absorption operating conditions:

Temperature 30 – 40oC, Pressure of 15 bar
 Regenerator conditions:
Temperature 100-120oC and pressure slightly
above atmosphere pressure
298
Sulphur Recovery
• Most commonly sulphur recovery process used is the “CLAUS
PROCESS”
• Claus process consists of a thermal stage followed by two or

three catalytic reactor stages
• In thermal stage a part of H2S is burned / oxidized in the

process in a carefully controlled stream of air to SO2
2H2S + 3O2 2SO2 + 2H2O
• Each catalytic stage consist of a feed heater, catalyst bed and a

sulphur condenser allowing following reaction at each stage
2 SO2 + 4 H2S S6 + 4H2O
299
Sulphur Recovery
• For maximum sulphur recovery it is important to
maintain H2S : SO2 mole ratio of 2:1
• Sulphur recovery efficiency from three catalytic

reactor stages is about 96 to 97 %
300
Sulphur Recovery - Claus Process
REHEAT GAS
___
(
I
<
A
i v
450°F
X v
400°F
X TAIL
GAS
A STM
r /
BFw BFW
*
ACID i i \
x
/
/ \
X
/
GAS C 7-10
V PSIG J-
/
/ s
\
BFW
«*ÿ
X
/ \ BFW
Mr
t BFW
350°F
T
250°F
fez 560°F ) V
s
440°F J
s
BURNER WASTE HEAT FIRST FIRST SECOND SECOND

AND BOILER CONVERTER CONDENSER CONVERTER CONDENSER
REACTION
CHAMBER
NOTE:
BFW = BOILER FEED WATER
Once-through Claus sulfur process.
Most plants have three converters , use bauxite catalyst
301
Tail Gas Treatment-Scot Process
• Claus tail gas contains small amount of carbonyl
sulphide and carbon disulphide in addition to H2S &
SO2
• In scot process the tail gas, combined with small
quantity of hydrogen, is heated to about 250 to 300 oC
and is passed through a fixed bed catalyst
• Various sulphur compounds are converted to hydrogen
sulphide by reaction with hydrogen
• Reactor effluents are cooled to ambient temperature ,
H2S is absorbed from the gases in aqueous Amine
solution
302
Scot Process
• H2S regenerated from solvent in conventional amine
still and recycled to Claus unit feed
• Gas exiting from amine absorber typically contains 50
to 400 ppm of H2S. The gas is incinerated to convert H2S
to SO2 before venting
• Sulphur recoveries > 99 % are obtained by addition of
tail gas units such as Scot process
• Addition of tail gas treating processes increases the
sulphur recovery cost by a factor of about 2
303
Tail Gas Desulphurization / Scot Process
Reactor Absorber
Hydrogen
*ÿ
iy To Disposal
H
Lean Amine ->ÿ
Claus Unit Fat Amine

Tail Gas
Cooler
Shell Claus Off-gas Treatment (SCOT) process.
304
Vmm
Syngas Cleanup

L 10 & 11
G.S.Dang
gurbax49@gmail.com
12/13-9-2017
Syngas Cleanup
• The production of clean synthesis gas (syngas) free
of contaminants such as particulates, sulphur,
ammonia, chlorides, mercury & other trace
metals and carbon dioxide is crucial to final
product ( CO + H2) quality for
• Protecting downstream units like gas turbines,

• Catalytic reactors,
• Fuel cells, and achieving
• Low environmental emission levels
Syngas Clean up
• Syngas cleanup is also used selectively to remove and

concentrate specific gases, such as carbon dioxide
(CO2)
• Contaminants , if not removed , can
 Plug up reactors,
 Cause corrosion,
 Poison downstream catalysts, or
 Prevent the plant from complying with
environmental norms
Syngas Cleanup
• The major components of syngas produced in gasifier

are CO and H2
• Other gasses like CO2,H2S and COS etc are also present
in considerable amounts in syngas along with some
char particles and ash
Gasification Chemistry
Gasification with Oxygen

C + l/2 o2 CO Gasifier Gas
Composition
Combustion with Oxygen (VoI %)
c + o2 *
H, 25-30
Gasification with Carbon Dioxide CO 3ft - 60
c + co2 2CO co2 5-15
H2O 2 -3ft
Gasification with Steam CH4 0-5
Oxygen C + H2O — -CO + H2
H2S 0.2-1
Gasification with Hydrogen COS 0-ft.l
*—
C + 2H2 CH4 0.5-4
Ar 0.2-1
Water-Gas Shift NH3+HCN 0-0.3
Steam CO + HjO H2 +CO2
Ash/Slag/PM
Methanation
CO + 3H3 CH4 + H2O
Produced Syngas may have unburnt solids , Tar and all above gases depending upon
the feedstock , type of gasifier and operating conditions. All constituents except CO &
H2 are removed in gas clean up
Syngas before & after Shift Reaction
Parameter HJ NI CO Ar EH-I CO] H.S C05 HjO Total

.',l"i:t, (befcn shift
neaedan) 41D1 035 49.HE 4UU5 (1.30 43$ l.til Oiti me 100
MolS (after shift rtafltidrl) 61.53 024 1,12 000 0,26 05 60 1,14 0005 0,Lfl 100
Syngas Quality for Downstream Applications
Duwnstream use Power Hydro-processing Chemical

Sulfur (wppm) 10-15 <1 <0.01-1
C02 (voLSB) <0.1 0.05-2,0
CO <50 wppm H2/CO control as per requirement
Syngas Clean up
• Among the components of syngas, H2S, COS and CO2
are termed as acid gasses
• These gasses produce acidic solution on dissolving in
water and are corrosive under moist conditions
• Further CO2 is also a global warming gas
• Removal of these gasses from syngas is essential to
reduce its corrosiveness , as well as the CO2 emission
from downstream units such as turbines
• Cleaning of syngas also includes the separation of
char/soot particles(particulates) along with acid gasses
Syngas Cooling, Conditioning & Clean up
Reducing syngas temperature

– Extract valuable energy
– Use conventional/commercial processes
Removal of chemical species that
– Foul, corrode, or erode system components
– Are environmentally unacceptable for release
Target Syngas purity
- H2S and COS concentration
- CO2 concentration
Adjustment of H2/CO ratio
Syngas Clean up
• Syngas requires clean up for meeting specific

requirements for downstream processes ; this
includes
 Removal of particulate matter (PM),

 Sulphur compounds, chlorine compounds,
nitrogen compounds,
 Unreacted hydrocarbons, and
 Heavy metals
Syngas Clean up Processes
Particulate Removal Process
• Particulate matter (PM) in the syngas stream is made up of ash,
unreacted carbon char, and condensed chlorine and alkali
compounds
• PM removal depends primarily on the downstream use of the

syngas
• For use in direct firing (boilers, HRSGs, thermal oxidizers, etc.)

PM can be tolerated and is restricted by emissions limits
• The PM limits in syngas are more stringent for downstream

conversion processes and gas turbines
Particulate Removal Processes
PM can be removed using various dry or wet processes :
• Water quench systems

• Cyclones and rotating particle separators
• Mesh-type filters
• Candle filters (ceramic or sintered metal)
• Water and/or oil scrubbers
• Electrostatic precipitators (wet or dry)
Tar Removal Processes
• Syngas from gasifiers operating at relatively low

temperatures contain
 unreacted carbon in the form of tars ( Aromatic
organic compounds)
• Tars form sticky deposits at locations that can affect

equipment performance, and are difficult to remove
Tar Removal Processes
Tar removal processes include:
• Thermal
– Thermal cracking
– Catalytic tar cracking
– Partial oxidation
• Physical
– Scrubbers
– Wet electrostatic precipitators
Mercury Removal
• Mercury removal is required for protecting downstream

sensitive catalysts and meeting environmental limits when
the syngas is combusted
• Mercury removal from syngas is achieved by use of

sulphur-impregnated activated carbon
 Proven technology with a wide range of gasifier types and

syngas
 Mercury removal occurs after PM and tar removal, and
prior to sulphur and CO2 removal
Gas Clean up - Hg Removal
• Hg is removed by adsorption in carbon beds
• 90 to 100% Hg is removed from the syngas depending

upon the efficiency of the carbon bed adsorption
process
• Addition of system for Hg removal from syngas causes

incremental increase in plant capital cost and also cost
of electricity generation goes up marginally
( Hg removal essential from environmental angle)
IGCC with Mercury Removal

CONDENSE
ACID GAS
COAL SLURRY REMOVAL
*ÿ
OXYGEN
COS yg
HYDROLYSI — jH
BFW I T
WATER
MERCURY
SYNGAS
noni FF? i
J REMOVAL
L
CmD -( O
AIR
GAS
<D )
m
STEAM | PARTICULATE
REMOVAL
TUBINE
r BFW
HRSG
FINES
SI AO STEAM TURBINE
( HD
COS Hydrolysis
• Depending on the gasification temperature approximately 3 to
10% of the sulphur is converted to carbonyl sulphide (COS)
• In applications very low sulphur (< 10 ppmv) syngas is required
• Converting COS to H2S before sulphur removal is necessary,

because most current commercial AGR processes do not
efficiently remove sulphur in the form of COS
• Achieved by passing syngas from the water scrubber through a

catalytic hydrolysis reactor - over 99% of the COS is converted to
H2S according to the following reaction:
COS + H2O ↔ H2S + CO2
Acid Gas (Sulphur) Processing
CO2 Gas CO2

Compression
Enrichment
(Sequestration)
CO2
*
(Atmosphere)
Raw COS Acid
Gas Clean
Syngas >
Hydrolysis
¥
Removal * Syngas
Gas
(H2, CO, CO2,
COS + H2O  CO2 + H2S *
H2O, H2S,
COS, and H2S Gas Sulfur Tail
trace Recovery ¥ Gas
Enrichment Treatment
contaminants)
T
Sulphur
COS Hydrolysis
• COS hydrolysis uses an activated alumina-based catalyst, and is
normally designed to operate at 350°F to 400°F (180 to 205 °C),
The reaction is largely independent of pressure
• The equilibrium for COS conversion is favourable at low

temperatures due to the exothermic nature of the reaction
• COS hydrolysis product gas is cooled in the LTGC system by

generating low pressure steam, preheating boiler feed water,
and heat exchanging against cooling water before going through
the acid gas removal system for sulphur removal
Sulphur and CO2 Removal Processes
• Sulphur and CO2 removal occurs in the process referred as the Acid
Gas Removal (AGR)
• Sulphur contaminants are in the form of Hydrogen Sulphide (H2S)

and/or Carbonyl Sulphide (COS)
The AGR Process
 Removes the sulphur contaminants from the syngas to a level as

required in downstream catalyst systems
 Selectively removes CO2 to provide a clean stream of syngas

constituent (such as H2) or when the CO2 will be compressed and
transported by pipeline for either permanent underground storage or
for use in enhanced oil recovery
Sulphur and CO2 Removal Processes
• Most common technologies for acid gas removal are

cyclic, regenerable , solvent absorption processes
• In all processes, a liquid solvent is counter-currently

contacted with the syngas in an absorption tower to
selectively remove the H2S and/or the CO2, and then
• It is thermally regenerated in a stripping tower, to

liberate the acid gases, and is recycled
Acid Gas Removal Solvents
• Chemical solvents ( aqueous ) that undergo reversible
reactions with the H2S and CO2 ; the absorption processes
operate at room temperature
– Examples: Methanolamine (MEA), Methyl-di-

ethanolamine (MDEA)
• Physical polar solvents, having positive and negatively

charged portions, attract the polar H2S and CO2molecules (no
chemical reaction; polar bonding). The absorption processes
operate at low temperatures and require cooling or
refrigeration
– Example : Selexol, Rectisol, Purisol etc

• Physical-chemical or mixed solvents - are mixtures of
chemical and physical solvents. Cooling or refrigeration is
required for the absorption processes
– Examples: Sulfinol , Amisol processes
• Oxidative solvents - react with the H2S and oxidize it to

elemental sulphur in the solution. The sulphur is recovered
as a solid
– Example : Sulferox, Lo-Cat processes

Selection of an AGR process depends on:
• Capital cost of technology
• Operating and maintenance costs
 Solvent make-up costs
 Power and steam
 Refrigeration needs
• Selectivity of H2S Vs CO2
• Ability to capture carbonyl sulphide (COS)
AGR Technologies
"Clean Syngas"
(AGR - Acid Gas Removal)
CO, H2
Clean
Solvent Major Technology Options:
4
••••••• • MDEA (methyl diethanolamine) – Chemical
4 ••
*•• absorption, 98% to 99% +S removal, large CO2
4
slip (unless use a second stage for CO2
recovery), moderate operating temperature,
4iji lowest AGR capital cost
• • 9
•••• V
• SELEXOL (primarily dimethyl ethers of
polyethylene glycol, DEPE) – Physical
4
4 Dirty absorption, 99% +S removal, variable CO2 slip
4
Solvent (based on design), higher AGR cost than MDEA
but overall AGR/SRU system costs similar
"Dirty Syngas"
CO,H2,CO2,H2S
AGR Technologies
"Clean Syngas"
(AGR - Acid Gas Removal)
CO, H2
Clean
Solvent Major Technology Options:
4
••••••• • RECTISOL (methanol) - Physical absorption,
4 ••
*•• 99.5% to 99.9+% S removal, complete CO2
4
removal possible, highest AGR cost, coldest
operating temperatures
4iji
• • 9
•••• V
• Warm Syngas Cleanup - New technologies
(e.g., RTI/Eastman) being developed that
4 Dirty
4
4 operate at high temperatures (> 205-315 C) and
Solvent
at sub-ppm S levels
"Dirty Syngas"
CO,H2,CO2,H2S
Selexol Process
• Selexol process / unit preferentially removes H2S as a product
stream and then later also removes CO2 as a separate product
stream
• The syngas enters the first absorber unit at approximately 32 bar

and 40 ◦ C where Selexol ® solvent dimethyl ethers of
polyethylene glycol, DEPE , preloaded with CO2,
preferentially removes H2S
• The H2S free gas obtained at the top of the absorption column,
with a large amount of CO2 , is sent to the second absorber for
CO2 removal
Selexol Process
• The rich H2S solution leaving the bottom of the first
absorber is partially decompressed and then is
regenerated in a stripper
• The stripper acid gas stream, consisting of more than

25% H2S (vol.), is partially oxidized into a Claus unit to
elemental sulphur (which is a by-product of the
process)
Selexol Process
• After the desulfurization unit, the CO2 is removed, in the second
absorption column, with regenerated solvent resulting from H2S
and CO desorption (this is called ‘lean solvent’)
• The cleaned gas obtained from the top of the second absorber
contains a very small amount of carbon dioxide (less than 1
vol.%) and the rich CO2 solution, leaving the bottom of the
absorber, is regenerated by gradually reducing the pressure
• The rich CO2 stream obtained is then dried, compressed and

cooled for transportation and storage
Flow diagram for the SelexolTM Process
TruM-d
I
GIL
:.:J
L
-
»p tr |ij
UJ
flfr,D*"r 4#t
* KWIIIJ
Fiirur AIT LKWifpKv
IXatfor
-Cli Md J¥up
W-dhr
IJi-aivcr-r M ftfnhi
sU-j Cunÿr"!"#ÿ Lipwt

Wrier
pjtAmax
ffl Srrÿpjwr
flfi!"HICT
Rectisol Process
• Rectisol ® process removes both sulphur and CO2
• The Rectisol process uses refrigerated methanol as solvent, to

clean syngas derived from the gasification of heavy oil and coal
• The process operates at a very low temperature (between − 40 ◦

C and − 60 ◦ C) and is more complex compared to other physical
solvent processes ensuring very deep H2S removal rates (down
to ppm level in the cleaned gas)
• The syngas, cooled to around − 30 ◦ C to − 40 ◦ C, enters the first

absorption column where Rectisol ® preferentially removes H2S
Rectisol Process
• The rich H2S solution leaving the bottom of the absorber is
regenerated first by flashing at medium pressure to recover the
useful gases (H2 and CO – which are recycled back to the
absorber) and then by heating to boiling temperature and
stripping with methanol vapour
• The stripper acid gas stream, consisting > 95% H2S, is then
partially oxidized into a Claus unit and elemental sulphur
recovered
• The desulphurized gas enters in the CO2 absorption column

where CO2 is removed. The rich CO2 solution, leaving the
absorber, is regenerated in a flash regeneration unit
Rectisol ® process flow diagram for
Acid Gas Removal (AGR)
ILS - free syngas
Rectisol preloaded with CO
<fri Purified gas

rarhon
r\ Refrigerator ItS to
JL Claus
—
A dio\ide
m r-$h unit
COi
absorber
flash
Syngas regenerate)!
TT:S
desorber
[ k'll
CO?
absorber>a V-fe
0 Y_
solvent to COi absorber
H:S stripper U1
Purisol process
• The Purisol process uses N-Methyl-2-pyrolidone as

solvent, to physically absorb H2S and CO2 from gas
streams
• The flow scheme used for this solvent is similar to

the one used for Selexol ® solvent and the process
can be operated at ambient temperature
Properties of Solvents
Properties Sc p\ti
l\i
KeelisoIx
Viscosity at 25"C (cp> 5.8 Q.fi
Density (kg/ni1 ) 1030 785
Molecular weight 280 32
Vapour pressure at 25DC 0.00073 L26
Freezing point ( T) -28 -92
IS o L!ing point| 275 65
COz solubility ftVUfc gal 0.485 0.425
AGR Removing Processes- Comparison
Solvent and process KemovaJ (S) Process parameters Quality of treated gas Developed by Remarks
MDEA HjKSWe KHIpJlMSt HjS lO-SOHWIv (Jninn carbide, WP LPWHI MHUI cost, inoderaie
(Chemical) a>=:E30 (Ambient} Dow chemical. SIKLI operatic? temp., only limited
Rr;*ZMMPl physical QK ahsoipnlon rakes place
Seleruil
(Physical)
KaSiffl
CO,', variable
-
Tempt 7 to A "C
Pr fi.BT MPa
HÿSt ppmv Allied Chemical Corp„
Union Carbide
Higher cosl than MDEA but overall
system cost including sulfur recovery
UOP (SR) process and (ail gas treating
(TCT) could he more cost effective
ReClisol KjS:fflu5-99,9 Tempt -35 to -60 'C HjE ppm* LINDE AC HitKheSI Cost, a minimum Concentration
(Physical) CCÿc 93.5 PrtS.MMPa OOit several mol& to few ppm of the H'S is required to maintain the
activity of (he caralÿt. high selecrlvlry
far H2S over CO-2, ability to remove COS
a) Tempi: temperature, b) Pi: pressure.
Syngas Clean up
Recent Development
on
Hot Gas Clean up
Warm Gas Cleanup
• Raw syngas leaves the gasifier at high temperature but
the gas cleaning is carried out at low temperatures by
scrubbing the syngas using chemical or physical
solvents
• These require cooling the gas to typically below 38 °C
• Need of cooling equipment and reheating the syngas
before its utilization in a combustion turbine or
synthesis reactor, result in
 Economic and thermodynamic penalties which
decrease the efficiency of a gasification plant
Warm Gas Cleanup
• Gas cleanup operating at higher temperature while

removing multiple contaminants is thus
 a way to get efficiency improvement in gasification-

based processes
• For this reason warm gas cleanup is being developed

off-late
Syngas Cleanup
• An efficient technique developed recently for separation of
particulates is the use of hot gas filters
• Ceramic cross-flow candle filters are mostly used for dust

removal from hot syngas
• Recently, moving bed filters are also being developed for

economic removal of these char particles by dry processes
• Many Organizations like Coal Research Institute (CRI), UK,

University of North Dakota Energy and Environmental Research
Center (UNDEERC) etc. are engaged in research on the
development of new hot gas filters for particulate removal
Dry Particulate Removal
• Solid particulate removal achieved with either filters

and/or cyclones
• Cyclones , a commercially proven technology , can be

refractory-lined for high temperature operations
• High temperature candle filters have also been

developed and can remove particulates from raw
syngas at temperatures between 550°F and 900°F (~
300°C to 500°C)
Dry Particulate Removal
• Use of candle filters in dry solids removal systems is

now considered commercially available technology
• In some current gasification designs, candle filters are

being used upstream of a wet scrubber for effective
overall solids removal
Wet Scrubbing
• Syngas leaving the candle filter is quenched and

scrubbed with water for final particulate
removal in commercial gasification operations
Scrubbing also removes chlorides, ammonia,

some hydrogen sulphide (H2S) etc
Wet Scrubbing
• The spent water is decanted into a gravity settler to

remove particulates
• Solid from the settler bottom are filtered to recover the

fine particulate as a filter cake - discarded or recycled
to the gasifier depending on its carbon content
• Water from the settler is recycled for gasification reuse

Candle Filter System
Outlet
Clean Gas
Common
Plenum
m
Hoi
Metal
Structures
0
Inlet
* 1 Oust
Seal
j <2> s ~ Oety
Candle X
X Gas
X
Cluster Array
U
N
X
Assemoiy x
0
*Asn
©
Candle Mount
Discharge ano Seal
Fdter System
Candle Filter Vessel
n
i t
n
i FILTER
CANDLES
JQC, 4 *
GASI i
i
»
i
SOLIDS
V*
J§
;
Candle Filters
II ||if |
H
3fc 1 1
1;
J
ms
f i t
l
fr
V
$s
SSaflEÿjiS
Candle Filter Element Picture of a Candle Filter System
Hot Gas Cleanup - Challenges
• Heterogeneous nature of coal /carbonaceous feedstocks

present challenges in syngas cleaning
These challenges include:
 Multiple contaminants and their removal , including

trace elements
 Process, materials and equipment handling issues
Hot Gas Clean up
• Hot gas cleanup focuses on a maximum operating

temperature of about 540°C for syngas cleanup i.e.
removal of particulates, sulphur, chloride etc.
• Even for temperature of 540°C substantial syngas

cooling was required
• Particulate removal (via candle filters) and sulphur

removal have only been commercially demonstrated so
far
Hot Gas Clean up
• Under high temperature clean up serious material

durability issues/problems are encountered
• With these issues and challenges DOE desired gas

cleanup at a lower temperature of 350 - 430°C
• This is called warm gas cleanup (WGCU) - to minimize

equipment and material handling problems
Adsorption (warm process)
• Some adsorbents like ZnO / CuO, Cr2O3, Al2O3 etc. adsorb
acid gas components
• In such adsorption processes, H2S is converted to metal
sulphides in the temperature range of 315–530 °C, which
produce SO2 during regeneration through oxidation at
590-680 °C
Reactions for the conversion of sulphur in the above

processes using ZnO as adsorbent are:
• Desulfurization
ZnO + H2S → ZnS + H2O
• Regeneration
ZnS + 3/2O2→ ZnO + SO2
Adsorption (Warm process)
• These metal oxides also adsorb CO2

Sorbents for Trace Metals
• WGCU technology tends to remove a significant part of
trace metals such as mercury along with the major gas
contaminants (sulphur, etc.) found in syngas
• Yet mercury and other trace metals in syngas following

WGCU may exceed the amount permitted by the
stringent regulations on emissions (air pollutants)
Sorbents for Trace Metals
• In conventional syngas cleanup systems operated at low
temperatures, activated carbon is used for complete removal of
trace species
 but temperatures of the WGCU conventional activated carbon

cannot be utilized
• Alternative sorbents (Palladium-based) are the most promising

candidates for the high-temperature, one-step capture or
polishing to extremely low levels of trace elements from coal-
derived fuel gases
361
http://www.gasification-
syngas.org/technology/syngas-
cleanup/
Syngas clean up
https://www.netl.doe.gov/research/c
oal/energy-
systems/gasification/gasifipedia/rd-
syngas-cleanup
Underground Coal Gasification (UCG)-
Commercial Trials & Results
B. Tech APEG Course

G.S.Dang
gurbax49@gmail.com
20-9-2017 B 1,2/
25-9-2017
364
Underground Coal Gasification
Some Important UCG Projects

Undergoing Development in
the world
UCG field trials around the world- Examples
Important UCG Field Trials and Scheme
Site Coal Type Depth/Dip Thick (m) Year Injectants

USSR
Podmoskovna Lignite 50m 2.5 1947-62 Air

Li&gitchan&k Bituminous Steep (35o) 9 1948-62 Air / 02
Juschno-Abmsk Sub-bitumen Steep{6Qo) 2.5 1955-89 Air
Ahgren Lignite 150m 9 1962-89 Air
Schatska Lignite 40m 2 1965-74 Air
USA
Hanna Sub -bitumen 85m 5 1972-79 Air
Air
Hoe Creek Sub-bitumen 85m 9 1976*79 02 / Steam
Pricetown Bituminous 270m 2 1979 Air
Air
Rawlins Sub-bitumen Steep (60dJ 7 1979-31 02 / Steam
Air
Centralia Sub-bitumen 75m 11 1981-83 02 j Steam
Rocky Mountain 1 Sub-bitumen 110m 7 1987-88 OZ / Steam
UK
Newman Spinney Sub-bitumen 75m 1 1949-59 Air
UCG field trials around the world- Examples
Contd.
Site Injectants
Coal Type Depth/ Dip Thick (m) Year
FRANCE
Djcrada (Marocco) Anthracite Steep( 70o) 1 1950-55 Air
Bruay-en- Artois Anthracite 1200m 1.2 1981 Air (Rev comb)
Haute-Deule Anthracite 8S0in 2 1985-86 Air (Rev comb)
BELGIUM
Bois-la-Dame Anthracite Steep (87o) 1 1948 Air
BELGIUM AND
GERMANY
Air
Thulin (Belgium) Anthracite 860m 6 1979-87 Q2/foamy water
SPAIN
El Tremedal
(Teruel) 850m 1992-99
AUSTRALIA
Air
Chinchilla 1999-
(Queensland) Lignite 100m 2003 02 / Steam
UCG Gas Production History
* Former Soviet Union - over 15 million tonnes coal gasified since 1950s
* Approximately two-thirds of this at the Angren plant in Uzbekistan
' Angren has been the only commercial size UCG plant generating gas for
equivalent 100-150 MW of power
• USA / European Union - less than 100,000 tonnes gasified
* Australia - Chinchilla pilot plant gasified 35,000 tonnes

*
A
I
if; r
m *
'
j
4r
v ; n
i
L
E2
-
- ~-j'H i
.*ÿ]
| JSk
- *~
l>]
1ÿ.
.44/
> -ÿ*
V
<
" ii. '
L J
, »
V ,
L •A.
. /
u.
_JH
Angren Open Cut
A
\
554* •t- t
V
feC -
PM ®JjaK
•
•f >
4
sÿ«i
/
*%* LL.
%
*“-
.» .
w • -‘
%
"J
«*»
>j
V r
<
***
v
* I
••
‘
t
r •EBBSEI- .
-
*
M
- '-* * 'ÿ> LJ.
7P
5f ' - •T
*2 d3 kfI"*
%L 1 **t x
S*2 i.
Hk#
•9 c
c'l
1
X*- R* **
%
VfP
?)»
n
‘
I
,
rfU.
*
~x \y
L, <#
-
& I
7JL\ £••§*>. A
t .w %
rf»-
/
n **
lUSiMfijJu j
IL
w«v, w r*i.r
' •
sa
1.
•T1L1 ;IM
UCG in Angren, Uzbekistan
• UCG at Angren since 1961 is the most powerful industrial
example of underground coal gasification
• It transforms brown coal into power generating gas with it’s use
in Angren thermal power station
• It was developed as part of Angren brown coal deposit which
was not suitable for underground and open cut mining on
account of technical (mining / geological conditions) and
economical reasons
• Over 50 year experience of operation showed that
Underground coal gasification produces power generating gas
in large industrial scales and provide it’s uninterrupted delivery
to the consumer
UCG in Angren, Uzbekistan
Energy gas consumer Gas purification
and
- Angren power station Air-blowing
machine
in
m
tj 1 Air-blowing
inlet holes
Gas outlet holes
...djjj
,ÿ *
Coal seam
Underground Coal Gasification in
Angren , Republic of Uzbekistan
• Depth of coal seam occurrence, m : 130-300
• Coal seam thickness, m : 0,2-15
• Heat value of coal, kcal/kg : 2800-3200
• Ash content of coal, % : 15-21
• Moisture content of coal, % : 30-35
• Hole diameter, mm : 150-200
• Heat value of gas, kcal/m3 : 800-1000
• Chemical efficiency of gasification, % : 70-85
• Underground loss of coal, % : 5-15
• Gas yield per 1 kg coal, m3 : 3,0-3,4
• Air consumption per 1 m3 gas, m3 : 0,8-0,9
• Power efficiency of the station % : 80-86
Gas Composition (Vol.%)
Syngas- Typical Composition

CO2 : 20-22
CO : 4.0-7.0
O2 : 0.5-0.3
H2 : 22.0-22.4
CH4 : 2.2-3.0
CmHn : 0.2-0.3
N2 : 50.6-44.4
Linc Energy Ltd: Chinchilla Pilot Project,
Queensland, Australia
• Syngas was first produced from this demonstration unit in Dec’
1999, and production continued thereafter for two years
• Linc developed three additional modules at Chinchilla. Module 3

was commissioned in 2007 combined with gas-to-liquids (GTL)
demonstration plant ( successfully produced synthetic fuels)
• Module 3 is exhausted now , Module 4 produced syngas and

lasted for another two years
• Linc also owns over 75% of the Uzbek UCG company, Yerostigaz,
which has been operating the world’s oldest UCG project at
Angren, Uzbekistan; Syngas being utilized for a local electric
power station for more than 50 years
UCG- Chinchilla Demonstration Facility
>Chinchilla is the site of the largest and most

successful western world UCG trial
> Approximately 40,000 tonnes of coal gasified
> Over 3 years continuous operations since 1999
Significant capital expenditure (A$50 million)

>Latest UCG Generator is most advanced
completed world first
> Commissioning of 5 barrels/day GTL plant
Significant environmental data from over 10 years
sampling and analysis
> No measurable impact on surrounding ground water
Clean Coal Technology
UCG – Chinchilla, Australia
Chinchilla
F*' &u V
L'A A
«.
1
i»
Jt
<
AUSTRALIA
tJ
r
%
•«
t»
-
%
. y?i •*
-A
'
'

r UCG Operations -
Chinchilla
Q®
'
'
r
ON1 0k ft.
I » JsT.V1
•T-
y
i
—-
&k- '
UCG- Chinchilla GTL Plant
W-
r
: Oil
fSt
['At'.
\
•v
Iferv \
r>£
U
* •u -ÿrrfe
G
* M* i
M i
wsiii;
.u
11
os £±
' '. {\ '
w ~ smM
I. y
. :f_
• A

Carbon Energy Ltd: Bloodwood Creek Project,
Queensland, Australia
• Carbon Energy successfully produced syngas from its unique UCG
module based on parallel controlled retractable injection point
(CRIP) method in Oct’2008
• During the trial runs for 100 days, coal gasification rates
reached to around 150 tons per day and produced a high-quality
syngas
• Carbon Energy installed two more modules and constructed a 5-

MW electric power plant to be fed with syngas
• A second project in Queensland, known as the Blue Gum Energy

Park, is in the early stages of planning
Swan Hills Synfuels: Alberta, Canada
• Swan Hills Synfuels produced syngas from its pilot
project in Alberta, Canada
• This project was the deepest UCG pilot ever

undertaken, at a depth of 1,400 meters, and used the
linear controlled retractable injection point method
ENN Group Co. Ltd - Inner Mongolia, China
• The ENN Group Co. Ltd. (a subsidiary of the Xinao

company) produced syngas from a pilot project in
Walanchabi City, Inner Mongolia, China, for 26
months, gasifying more than 100,000 tons of coal
• There were initially seven injection and production

wells, which were first fired in October 2007 using air
Eskom: Majuba, South Africa
• Majuba UCG project has been producing syngas since Jan’
2007 and began delivering UCG syngas to cofire with coal at
Majuba Power Station in late 2010
• The project contributes about 3 MW to the overall output of

650 MW from the electric power station using the linked
vertical well method
• This project is now the longest running UCG trial in the

western world. Plans are in place to expand the facilities to
1,200 MWe output, with 30% of the plant’s fuel provided
by syngas
UCG -Indian Context
• UCG is a major part of India's energy policy
• India looks to utilize its vast coal reserves, to reduce

dependency on oil and gas imports
• For meeting the growing energy demand UCG will be

used to tap India's coal reserves that are difficult to
extract using conventional technologies
UCG-Indian Coal Reserves
• India's known reserves will be exhausted in less than 40
years if conventional mining methods continue and
• Much of its reserves may not be extractable with current

mining technologies
• Coal gasification likely to be a major energy source for

achieving the country's economic growth; contributing
as much as 9% to 10% to the country's domestic energy
needs in next decade
.
Environmental Impact
In general, the potential environmental

impacts of UCG can be minimised through:
Appropriate site selection

Effective operational process control
Adoption of an appropriate shutdown
procedure
Environmental monitoring
Results of
Trial Underground Coal Gasification
Underground Coal Gasification –
Concerns and Impacts
• Underground coal gasification is an experimental technology
with a track record of limited success along with failures-
polluting the air, groundwater and soil
• The process of burning coal underground for gas is difficult

to control and produces many toxic / carcinogenic by -
products; carbon monoxide, benzene, toluene and other
substances
• Gas processing, handling and transport in pipelines also

poses risks to people and environment
Underground Coal Gasification –
Concerns and Impacts
• After disastrous trials, underground coal gasification
was banned in Queensland in 2016, and production
does not occur anywhere in Australia
• Underground coal gasification was also banned in

Scotland in 2015
• Countries like China, Russia and the USA, that explored

the potential of underground coal gasification are
backing away from this dangerous form of mining
What went wrong with UCG in Queensland?
• In south-east Queensland near Chinchilla, Linc Energy

ran an underground coal gasification project involving
the trial of five different gasification operations
• In 3-year test period Linc burned approximately 35,000

tonnes of coal into gas, that was mostly flared
• Linc Energy used too much pressure in its injection

bores which cracked the land above the seam, causing
gas and other contaminants to leak out
• Gas, liquid and solid waste were all released into the
environment creating severe pollution
• It caused
 Permanent acidification of hundreds of square
kilometres of farming land,
 High concentration of hydrogen in the soil at
explosive levels and
 Abnormal amounts of methane
• The Queensland government investigation was the

“largest and most protracted” in history with many
investigators working on the case
• It found the project caused widespread,

contamination of high impacts and, in part,
irreversible and complaints from Linc Energy workers
were “consistent with exposure to the known
chemical constituents of syngas”
• The investigators at the site complained of nausea,

headaches, nosebleeds and tests showed high levels
of carbon monoxide in their blood
• High levels of cancer-causing benzene were detected

at the site / nearby areas afterwards ; the possibility
of ongoing underground coal fire could not rule out
What does this mean for South Australia?
• Underground coal gasification is an unproven and

extremely risky technology with major threats to human
and environmental health
• There are some differences between South Australian

brown coal and Queensland black coal, but any process
of burning coal underground creates gas – which is risky
• After three failed pilot projects and contamination in

Queensland, the government brought in a ban
What does this mean for South Australia?
• South Australia moved to immediately ban

underground coal gasification for the safety
of workers and the protection of the
environment
Summing Up
• Coal gasification technologies are developing but safety
(controlled operation ) is still a big issue
• Surface & Underground coal gasification are gaining

higher importance currently, with carbon dioxide
capture & storage
• Smaller environmental footprint than conventional

process
• Gasification provides better utilisation of coal reserves

Vmm
Underground Coal Gasification (UCG)
B. Tech APEG Course

G.S.Dang
gurbax49@gmail.com
397
Underground Coal Gasification (UCG)
Contents
• Surface & Underground Gasification
• Underground Gasification (UCG)
• Syngas clean up & utilization
• Present status of UCG / commercialization
• Summary
Coal- Sustainable Source of Energy
• The global demand for energy is increasing but the
traditional form of energy (fossil fuel - oil , gas and
coal) is becoming more difficult / expensive to produce
• Coal utilization has mainly been in thermal power

generation
• Fertilizer plants have been using coal as a source for

hydrogen through coal gasification (Surface Gasification)
Coal Reserves compared to Oil & Gas
S Bp
2sa is u
Ntfth Ammo
|
r
P
w
__
VWr*e~4
Soulier* £vr opr
J,r.r.C In
2 179 110
M4a#E*ti 1
2H 21 06
Former
Sov.rtlWon
6«i 1 1 US t s
!**• CM*
SS 2S 21 I
Afnc# fT
f*
W.
»
22 25 II
SoutfrAmmc* 94 6 17
Mi*
40c***u
COM. OH GAS
Protos Consulting International Pty Ltd

Coal Feedstocks - Types
Coal formation- Wood , Peat, Lignite, Sub - Bituminous, Bituminous & Anthracite
HIGH
HIGH « T
I
I
LOW HANK COALS HAHO COAL
1
5 2A<*
W
o
r
I
cl
I
iiCMrrc
l
VAIITUMIMXA
t 1
AMTUMtlll
2«* J1H < 1H
R
s
o
I
u
r
I 1
C TMtM»IAl MttAltVW iiCAL
T T ?
uses Larjety pO'M-or Power t*n«riuon Donwiut/
(cncoKCfl Cwwi ot *r«« a )<J tnduatml
InOut trial utrs ««rl mdudftj
MnoLcJm fur!
Large base of feedstock for CTL Souroe: Coal diagram, World Coal Institute
Coal Gasification
• For surface coal gasification coal has to be
mined; transported to the site and gasified for
generation of Synthesis Gas ( CO +H2)
• Surface coal gasification has been commercial for

over sixty plus years
Gasification
Gasification Reactions
• Gasification
c + o2 <;—s co2
C + C07 2 CO -1 10 MJ/kmol C
C+ £=> CO +H2 131 MJ/kmol C
C + 2 H2 £=> CH4 75 MJ/kmol C
Syngas : CO + H2
• Water gas shift

Gasification Parameter
CO + H20
<—S C02 + H3
• Inverse Methanation (only below 11 00°d Petcoke
Temperature 1500-1700 C
need higher Temperature (1650 C) to
CH4 <ÿ HjO —S
C CO + 3H, ensure the Full conversion
Optimize operating conditions to maximize CO and H2

production, with minimum C02 and CH4
Surface Coal Gasification
 Surface gasification- Overview
• Coal (or other fuels)
• Partial Oxidation ; carefully controlled
• H2, CO2, COS & other products
• CO - H2 clean ; used in power generation, chemicals etc
• Ash/slag leftovers ; used as construction material
 3 types of gasifiers (surface coal gasification)

• Moving Bed , Fluidized Bed and Entrained Bed
 Underground Coal Gasification( UCG)

• Vertical wells and pathway creation
• Controlled retraction injection point
Coal Gasification

Why UCG now?
• Security of Energy Supply
• Carbon Capture & Storage : Pre-combustion processing
• Flexibility of Syngas for poly-generation – Existing or

new power stations, GTL, SNG, H2 and other chemicals
• Advances in UCG Technology – Drilling, Completion &

Control
• Coal mining is not economically viable from the

deeper coal mines
• Attempts have been in the past and are still

continuing to tap the vast energy source in-situ
• Gasifying the coal in-situ without mining is

called “Underground Coal Gasification” or UCG
UCG - History
• The technology was first used in the USA during

the later 1800s
• In India (Kolkata & Mumbai) in early 1900s
• Lamp lighters in many cities used to light street

lights by “town gas”, the product of early and
relatively crude forms of coal gasification
UCG Principle
• Underground Coal Gasification (UCG) converts
coal into a gaseous form (syngas) through the
same chemical reactions that occur in surface
gasifiers
• The economics of UCG look promising as capital

expenses appear to be considerably less than
surface gasification
UCG- Production Process
• Underground coal gasification (UCG) involves drilling
boreholes into the coal and injecting water/air or
water/oxygen mixtures
• It combines an extraction process and a conversion

process into one step, producing a high-quality synthesis
gas (Syngas)
• UCG is poised to become a future major contributor to

the energy mix in countries around the world (still in
the early stage of commercialization, safety issues etc )
UCG PRODUCTION PROCESS
Raw
Air Combustible
UCG Gas
mi
i1
| jk Ground Level •
V
Water Table
-
J . J -r7''-J-
i-.
j
rt
---
< rai
* /
.jr;
- .V- 51
j>TT
Oxidization Raÿr Gas

1 Process , »
*-*-»ÿ
*
L_V
v
S I
IVkii Pi
_ÿ __T
UCG - Production process
In underground coal gasification (UCG)
 Air and/or oxygen are introduced to coal (in the

ground) by pumping it down boreholes (called
injection wells), which are drilled into the coal
seam from the ground / surface
 Some part of coal is ignited & generated raw

syngas comes to surface via production well
Schematics of UCG
Low Air Emissions CQ2 Separation

Electricity Gas Cleaning
Production
C02 separation
Stream to unmineable coal
Injection Production Well
Well H2.CH4.CO
Oxygen + Water C02 + mil tor
constituen s
Stressed & Contaminated Zo le

Coal Seam z
Ash + Char
• “Controlled retraction injection

point “ from oil technology
(CRIP)
– The oil industry’s horizontal |l«IJKlty
CCCT plifil
CO,
G*1
CJfPlUft
drilling is used for injection 111 AMhfr
wells CÿahciMTi
*
a [yfab
– Only one injection well, the 4 i
Itiwrtpon v*r<
l\ (OpfcmiH, y a
ignition continues through j
the inseam ; y Ohjÿrti

ct>jt i
A
KquSUHfen fir*.*
I Md
T A (MrtliKI
– The product is collected in a I

i D.-ritnriir>i 3“
product well f-
r
CiMl
– Concerns about ground 4

water inhibit the use of UCG
Figure 6: CRIP UGC
• Vertical wells, soviet technology

– H2 and O2 are injected and Underground Coal Gasification
ignited to create syngas, CO2
and methane
– Coal deposits do not allow W fly.too
for transport of the gases
from the injection well to
Coal Seam
recovery well very easily zoom tram
Striae*
t
– Closely spaced wells and
reverse combustion methods i
are employed to create a Coal
cavity between wells

– This process works, but
requires many wells to be
constructed Figure 5: Current UGC
Underground Coal Gasification – Injection well site
Figure-1
*«
« %3II
*
—
j' x-
—
4 -
- +•
PÿVf1
r
rÿs
J
rÿ
- r
WL-
*» I4 L
,* - i
<Z
i %
Ml i.v
*
—
V
r
/ -.•ÿ6.
«I -
v.v
HL
. *
«»
-
*•.
Making coal cleaner. The underground gasification of steeply dipping coal seams was
demonstrated in a pilot project near Rawlins, Wyo. In the underground coal
gasification process, air and/or oxygen is introduced to the coal while it is still in the
ground by pumping it down boreholes (called injection wells), which are drilled into
the coal seam from the ground surface
UCG– Surface Infrastructure
m
-
r
\\ - i
, %
v.
!
r
liO l/vvl
I1 i
'
*cJ
Surfacing. After syngas is formed in the coal seam, it

then flows back to the
surface under pressure via a second borehole (the pro
duction well), which is
linked through the coal seam to the injection well.
UCG-Positive Factors
• UCG is the only feasible technology, which enables

exploitation of deep (> 500m) coal reserves, which are
not amenable to known conventional mining methods
• UCG offers an environmentally clean way to harness

energy from coal without mining ( Safety concerns )
• UCG brings no solid waste to the surface

UCG- Positive Factors
• Even at shallower depths (< 500m), UCG can be more

economical than conventional mining
• UCG reduces capital investment, operating costs, and

the output gases cost by 25 to 50% as compared to
surface gasification
• Possibilities of transport of medium calorific value

gas over a distance of 100 km. exist
Criteria for UCG
UCG requires special properties of coal seam:
• Coal seam lays underground between 100 and 600

metres (preferably more than 300 metres)
• Thickness more than 5 metres
• Ash content less than 60%
• Minimal discontinuities in seam
• No good water aquifers
How does UCG Work?
• Coal site is located

• Drilling of boreholes
• Linking the boreholes
• Ignition of the coal
• Injecting oxygen and steam
• Extracting the syngas
UCG Techniques
Vertical Wells
CRIP (Controlled Retracting

Injection Point)
SDB (Steeply Dipping Bed)

UCG Techniques
Air
s
Product Air/Ox ygen Product
Vertical Wells
.
LKIi' [&KKT
CRIP ( Controlled Retracting

j
I 1
1* LKU' ICKlOl
Injection Point)
UCG Techniques
A ir/Oxy gen
Product gas
Steeply Dipping Bed

Factors Controlling UCG
Geology of the coal seam
Overburden thickness and properties
Hydrogeology of the coal seam and
surrounding strata.
It is the overall appraisal of the many
technical aspects of a site that governs
its suitability.
Commercial factors such as the size of
the coal resource and the market for gas
are also critical to project development.
UCG- Syngas to Chemicals & Fuel
Pressure
Swing H2
Adsorptio
T
Tailgas
Air/02
. Shift
H2
Fischer
Tropsch
Naphtha
Diesel
UCG Conversion &

Selective
Acid Gas Removal
CO
T
Water Tailgas
T
Gas Cooling
DME & DME
Gasoline
Sulfur C02 Synthesis Gasoline
Recovery Compression
T
Sulfur
I
CG2
Methanol
Synthesis CH30H
1
Water Tailgas
SNG
Methanation
CH4
I
Water
Syngas to High value Products
Waxes Olefins
Diesel Gasoline
MTBE
Mixed
Alcohols
\/
Fischer-Tropsch
<1)
CD
re
Acetic Acid
o
£
£
6
O
Formaldehyde
4
c
|
2* y
/<?/*
0 2 o°
LL. O
ro
9
Syngas Cu/ZnO zeolites Olefins
Isosynthesis
/-C4<+ ThOj or ZrO, CO + H2
+> Methanol Gasoline
MTO
ft a MTG
H20
Q
A
# f &
C
WGS
Purify
ft A
DME
ftp
M100
N, over Fe/FeO vv Ethanol M85
NH3<*(KjO, AIjO,. CaO) H2 Aldehydes
DMFC
Alcohols
UCG- Advantages
• Much higher coal extraction – up to 95%, no pillars
• Multiple seams , thick and thin seam
• More economic – less capital expenditure
• Economic on a smaller scale
• Potential to be cleaner technology – smaller
environmental footprint
• Little or no rehabilitation required
• No fine coal, no ash, Safer
UCG Advantages..contd.
Cleaner energy lower emissions intensity - 25% less than

conventional black coal-fired power stations
Cheaper energy up to 50% cheaper cost of gas generation

(as feedstock) than natural gas
Efficient resource utilisation about 75% energy content of

coal is retrieved in UCG process vs. ca. 5% in the coal seam
•Cleaner energy
gas process •Cheaper energy
•Efficient resource utilisation
Safe safest method of extraction with no open cut or
underground mining
Reduced environmental impact minimal ground disturbance, ash content

remains underground, minimal waste water production
UCG-
Advantages & Disadvantages
AnVtJxygeri A Stcacn FTtiAJHifWftfTCfeCO* Hi. CH* A9um> tndfc*
*
I
•Advantages over conventionai process are

•Low dust and noise
•No ash handling at power stations
•No coal stocking and transportation
•Larger coal resource exploitation
•Converts sulphur (S) to H2S and nitrogen (N) to
NH3 instead of S02 and NOx
•Disadvantages
-Surface subsidence
—Aquifer water contamination
431
Coal
Power
Gasification Synthesis Gas F T Liquids
Steam, H2
t
\
Methanol Chemicals
Alternative Gasification
/ Feedstocks:
Petroleum coke
Resid
bio-residue
Future Fuels
1. Generation: 2. Generation:
RME (bio-diesel), ethanol CtL(Coalto Liquid)
(alcohol additions) GtL (Gas to Liquid)
MtG (Methanol to Gasoline) BtL (Biomass to Liquid)
T
Reanimation of the Fischer- "fhopsch method
Developmenttrends for fuels in EU to produce synthetic fuel („Synfuel“)
since 2000: based on mineral oil
Steps:
50 ppm S Production of synthesis gas (2 H2, CO)
about2008: based on mineral oil Gas cleanup (dust removal, desulfurization)
< 10 ppm S catalytic high-pressure synthesis (Cÿ-paraf fins)
Hydro pro cessing (naphtha, kero sine, diesel, benzine)
asof about 2010: based on natural gas
Synfuel Properties of Synfuel:
(virtually S-fnee) Mery clean, high cetane number, non-polluting,
but expensive
asof about 2015: based on biomass
Synfuel (i;Sunfuel11) Implementation is dictated by environmental
as of about 2020: Hydrogen standards/regulations:
regenerative Only Synfuel will be able to fulfill future EU exhaust gas
regulations in terms of emission of particulates, freedom
from sulphur, NOx, CO, HC content
World Coal Proven Reserves
Rank Country/Region Million tonnes % Share of Total

1 US 242,721 28.6
2 Russia 157,010 18.5
3 China 114,500 13.5
4 Australia 76,600 9.0
5 India 56,498 6.7
6 South Africa 48,000 5.7
Rest of world 152,159 18.0
WORLD TOTAL 847,488 100.0
Source: 6P Statistical Review od Energy 3008

World Coal Major Producers
Rank Country/Region Million tonnes/yr % Share of Total
1 China 2,537 39.7
2 USA 1,039 16.2
3 India 478 7.5
4 Australia 394 6.2
5 Russia 314 4.9
6 South Africa 269 4.2
Rest of world 1,365 21.3
WORLD TOTAL 6,396 100.0
Source BP Statistical! Review Energy 20M

G.S.Dang
gurbax49@gmail.com
UPES , Dehradun
2nd Nov’ 2017
3rd Nov, 8th Nov 2017

9th Nov 2017
Biomass
• Biomass is a natural available substance, which stores
solar energy by the process of photosynthesis in the
presence of sunlight
• It contains cellulose, hemi cellulose and lignin, with an

average composition of C6H10O5
Types of Biomass
|r ( i*
ft *1
L
Coconut Shells Wood Saw dust briquettes
n
•
(A i *1
s
f<3
A
V
(MS >
Grass Briquettes Bamboo Wastes Groundnut husk briquettes
Types of Biomass
LUCANA CRATHINE YUCH COCONUTS SHELL RICE HUSK
*
t
I
rrrr ri- . -ÿ - . assessÿ
SAW DUST PALM LEAF STEM MARIGOLD CORN COB

K
12 SF* tj*
# r
;-s-«
'
—
TAPIOCA STEM
3**ÿ 2 -
TAPIOCA SKIN
L>.
COFFEE RESIDUE
5
SLUDGE
d•v r
Types of Biomass
v 4
{£*
Tapioca
Leaf
sw
_
Cassava Leaf Cassava Plantation
1 -
Tapioca
Stem-1
Stem-2
sl$2§§
Hi
Stem-1 rejected at
field
Tapioca Stem-2
rejected at the process
s
mm
fs
4E
- Kip
& > Tapioca r jr vW*
root
f 4/} tSh
3
Tapioca Root Tapioca Skin
Biomass Sources
Biomass sources include:
 Clean wood chips at 50% moisture,
 Urban wood residues ; dry contaminated with
other materials,
 Agricultural residues,
 Animal residues, sludges, and
 Organic component of municipal solid waste
(MSW)
Potential Biomass Gasifier Feedstocks
Lit imate Analysis (Tvt% dry basis) Fruximate Analysis (wt% dry basis)
Heating
Fixed Value HHV
C H N 0 s Ash Moisture Volatiles Carbon (MJ/ka)
Agricultural Residues
Sawdust 50 fr.3 0.8 43 (|J(I3 0.03 7.S 74 25.5 19.3
Bagasse 48 fr.O 42 4 I ao 15 17
Com Cob 45 5.4 0.4 44.fr l 5.S 763 15 17
Short Rotation Woody Crops
Beech Wood 50.4 | 7.2 0.3 | 41 | 0 | 1.0 18.4
Herbaceous Energy Craps
Switchgrass 43 5.6 0.5 4fr 0.1 43 8.4 73 13.5 15.4
Straw 43.5 4.2 O.fr 40.3 0.2 |:i.l 7.6 68.8 13.5 17
Miscanthus 45 4.fr 0.4 4fr 0.1 1.9 7.5 79 11.5 12
Municipal Solid Waste
Dry Sewage | 203 | 3.2 2.3 | 173 | 03 | 56 41.6 | 23\ 8
Coals
Subbitumiuous 67.8 4.7 0.5 17.2 O.fr 8.7 31.0 43.6 47.7 24.fr
Bituminous 61.5 4.2 1.2 fr.O 5.1 21.9 8.7 36. L 42-0 27-0
Compositions are approximate and may not sum exactly to 100.0%.
Biomass moisture contents reported are for dried feedstocks.
What Biomass Contains?
• Biomass contains a high percentage of moisture (along

with carbohydrates and sugars)
• Moisture reduces the temperature inside the gasifier;

reduction in efficiency of the gasifier
• Many biomass gasification technologies require the

biomass be dried to reduce the moisture content prior to
feeding into the gasifier
• Biomass can come in a range of sizes

Why Biomass Energy ?
• Can deliver energy in all forms

- Solid, Gas & Liquid for application as
- Heat, Electricity, Transportation
• Gasifier produces fuel at relatively lower cost
• Energy Security
• Poverty Reduction
• Positive Environment effects
- Carbon dioxide neutral
- Restoration of degraded land, water retention etc
 H/C Ratio
• Similar issues to coal
 Ash
• Biomass aggressively forms ash
 Impurities (Sulfur, Nitrogen)
• Necessitates greater syngas cleanup
 Moisture
• High moisture levels lower energy efficiency
 Size Reduction
• The fibrous nature of biomass makes size reduction difficult
Basic Process Chemistry

* Conversion of solid fuels into combustible gas
mixture called producer gas CO + H2 + CH4)
• Involves partial combustion of biomass
* Four distinct process in the gasifier viz.
• Drying
• Pyrolysis
* Combustion
• Reduction
Gasification -
Basic Process
I Drying Zone
•
> 1•
ChemistLi' I
y Ida a
rM
Schematic Mr
m i
i
-
y%
HI
a«
J • — yUJlfl***"'
7W
Biomass DRYING AIR Heat Absorption
Feed Exchanger Chiller
T
Moisture
< 15% HAir Water
Tneatment
Chiller 4
Unit Unit HEAT POWER
1"
Flare Air
r
V
Gasification
Air Mixer
Reactor
>=3
-err1 Cytybne
Ash
ILJB
| | Q iTUn Blower Filter
Radlat&r
Engine Generator
5% of Raw Material
r { Biomass Gas }
Heat Utilizationÿ Dryer for Biomass ,Food Process
H2 18—20% CO 18-20%
Electricity CPP CH4 1—2% COz 12—14%
N 45—48% 1-2%
Ash
> -i
HHV 4.5— 4.8MJ/ma
• In biomass gasification systems, the biomass must be
processed to a uniform size / shape to feed into the
gasifier at a consistent rate
• Gasification converts these materials into carbon- and

hydrogen-rich fuel gases
• Gases can be easily utilized with a gain in efficiency

and environmental performance compared to direct
combustion of the biomass
Biomass Energy
• 11% of the world’s primary energy requirement is met
through biomass
( much higher share in the energy supply of developing countries)
• Gasification is a preferred route of biomass
conversion; thermo-chemically conversion into
producer gas (PG) which can be utilized for
- process heat purposes,
- electricity generation, or
- combined heat and power applications
• Gasification can convert biomass into products such as
ethanol, methanol, fuels, fertilizers, and chemicals
• The ratio of air-to-fuel required for the complete
combustion of the biomass; stoichiometric
combustion is 6:1 to 6.5:1, with the end
products being CO2 and H2O
• In gasification the combustion is carried at sub-

stoichiometric conditions with air-to-fuel ratio
being 1.5:1 to 1.8:1
• The gas so obtained is called producer gas,

which is combustible
• This process is carried out in a device called

gasifier, where biomass is burnt in a limited
supply of air
Gasification Principle
BIOMASS
--- /
Drying
Methane production reaction
C
C
H2
+
+
2H 2
Oxidation
O 2
+
= CH 4
= CO 2
’I/2 02 = H20
p
Reduction
Air
’ Oxidation1* *ATÿ
Boudouard reaction
/ CO 2 + C = 2CO
TJZl Water-gas reaction
C + H2 O = CO + H 2 I
:••••' Ash ••••
. DRYING f~\
mm MI t*oma«|»[H.O | Hfi
V
PYROLYSIS
biomass
Tar
CH.
COMBUSTION
•Z
OOÿfCOj
l
HEAT 4H Q, 9 2H;0
C>lw <rtf?»i*4l 0»-5* rCO,
nV3 K,0 / r co,
HO
XAA-
H
REDUCTION
C*CO, « 2 CO CO
•
C M,0 S» CO H, H,
C>L nHO J nCO <m/2*n» M,
CK •"CO » 2nCO •nV2 H,
Biomass Gasification -Scale of Plants
• Biomass gasification plants are much smaller than the

typical coal or petroleum coke gasification plants used
in the power, chemical, fertilizer and refining industries
• Are less expensive to build and have a smaller facility

“footprint”
• A large industrial gasification plant may take up 150

acres of land and process 2,500-15,000 tons per day of
feedstock (such as coal or petroleum coke)
• Smaller biomass plants typically process 25-200 tons of

feedstock per day and take up less than 10 acres
Biomass to Ethanol and Liquid Fuels
• Biomass, such as wood pellets, crop wastes, and “energy crops”

such as switch grass and waste from pulp and paper mills can
be used to produce ethanol and synthetic diesel
• The biomass is first gasified to produce the synthetic gas

(syngas), and then converted via catalytic processes to these
downstream products
• Gasifying agricultural waste products to produce ethanol and

synthetic fuels such as diesel and jet fuel can help break
energy-food competition
Biomass Gasifiers
• The Gasifier unit is a chemical reactor ; many thermo-chemical
processes such as Pyrolysis, Pyrolysis , Oxydation, and Reduction
take place
• Most biomass materials like Wood , Charcoal , Rice Husk etc can
be converted into a gaseous fuel known as producer gas ( PG)
• PG comprises carbon monoxide, hydrogen, carbon dioxide,
methane, and nitrogen. It has a lower calorific value (1000–1200
kcal/nm3) compared to natural gas or LPG
• Each kilogram of air-dry biomass (10% moisture content) yields
about 2.5 nm3 of producer gas
• In energy terms, the conversion efficiency of the gasification
process is in the range of 80%–90%
Producer Gas Composition/ Properties
Particulars Rice Husk as Woody Biomass

biomass
CO 15-20% 15-20%
10-15% 15-20%
CH4 Upto 4% Upto 3%
45-55% 45-50%
C02 8-12% 8-12%
Gas C.V. in kcal/Nm3 I Above 1050 Above 1100
Gas generated in 2.5
Nm3/kg of biomass
Biomass to Power
• Biomass can be used to produce electricity-either
blended with traditional feedstocks, such as coal or by
itself
• Nuon’s IGCC plant in Buggenum, Netherlands blends

about 30% biomass (chipped wood) with coal in their
gasification process to produce power
Biomass based Power Production Technology
Four routes for biomass based power

– Combustion, Gasification, Anaerobic digestion and
Pyrolysis
• Biomass gasification works well for small scale power

production, up to a maximum capacity of 2 MW
• Combustion, on the other hand, works well at higher

MW scales
Biomass based Power Production Technology
• Anaerobic digestion can work well for both small and

medium scales
• Pyrolysis can work well in the range of 2-30 MW
All the four routes have their own unique characteristics

and provide more benefits than others, under specific
circumstances
Bio based Power generation
• The three primary routes for biomass to power are:

Combustion, Gasification and Anaerobic Digestion
• Combustion of biomass is used to produce steam that runs a

turbine. Combustion of biomass for power could either be in the
form of co-firing (burned along with coal) or pure biomass based
combustion
• In Gasification the biomass is first gasified and this gas in turn

produces power in a gas engine
Bio based power generation
• Anaerobic digestion is applied to biomass having high amount of

water ( like kitchen waste and sewage waste ). Microorganisms act
upon the organic matter present in the biomass under anaerobic
(absence of air) conditions and convert it into biogas
• In emerging Pyrolysis route the biomass is rapidly heated to 450 -

600°C in absence of air, that results in a bio-oil called the pyrolysis oil,
which can in turn be used for firing the boilers
- Typically, 50 - 75 % (by weight) of the feedstock is converted into

pyrolysis oil
Air-blown Gasification
• Most biomass gasification systems use air instead of oxygen for

the gasification reactions
• Oxygen is typically used in large-scale industrial and power

gasification plants
• Gasifiers using oxygen require air separation unit to provide

oxygen; usually not cost-effective at the smaller scales used in
biomass gasification plants
• Air-blown gasifiers use the oxygen in the air for the gasification
reactions
Biomass based Power Generation
Legend :
1 Reactor 7 Chiller
2 Cyclone 3 Venturi
3 Water Scrubber 9 Gas Glower
4 Moisture Trap 1 10 Flair

5 Chilled Scrubber 11 Fabric filter
6 Moisture Trap 2 12 To Engine
i
w 1
2
i
5
cut
A
10*
+4 ' '
TO niTir.iiTE
lm & *DJA
!
I 1
7 9 11 12
(For Power Generation)
A.ppHcaci OTIS
Power Generation Tliermal Application
•Village electrification • Low temperature ( drying, etc.,)
•Captive power generation • High temperature ( furnaces, kilns, Boilers, etc.)
•Grid linked power generation
Gasification power plant -Typical
Specification
Suranari University
Nakhonrachasima
Thailand
I
Capacity: 100 kW
Rice 1lusk Briquette:

9 130 kg/h
Wood
n 100 kg/h
•>
<
_V
1
ISI
ir I
mk
1
\
M .1
Biomass Gasifier
• A gasifier system comprises of a reactor generating gas

followed by gas cooling and cleaning system
• The gasifier is usually a refractory lined vessel &

gasification is carried at temperatures of 750-850ºC at
either atmospheric or elevated pressures
• The clean combustible gas (called Producer Gas) is

available for Power Generation & Thermal application
Gasifier Types
Biomass gasifiers- major classifications:
• Fixed-bed updraft, fixed-bed downdraft
• Bubbling fluidized-bed and circulating fluidized bed
• Differentiation is based on the ways of

 supporting the biomass in the reactor vessel,
 the direction of flow of both the biomass and oxidant &
 the way heat is supplied to the reactor
Gasifiers Types
Hiomasw Blomgs* Binmcm
| I
:;;e:s
m
?'s Pf<KtUCW
mmm mmm
m
ft
m
g<M
Prod UM t
Air - &
Types of gasifier i 90s
i A* 33
58
Asn
I
Prpdiiccr
90s ABU
oral ash
Updraft DoYrndrafi Crossdraft
Fixed bed Gasifiers gasifier gasifier gasifier
•Up-draft gasifier: Efficient but gives comparatively

dirty gas, good for thermal applications
•Down-draft: Comparatively clean gas, good
for power generation
•Cross draft: in between above two.
Updraft Gasifier
• Air is introduced at the bottom- counter current to fuel
flow and the gas is drawn at higher location
• The updraft gasifier achieves the highest efficiency as

the hot gas passes through fuel bed and leaves the
gasifier at low temperature
• The sensible heat given by gas is used to preheat and

dry the fuel
Updraft Gasifier
• These gasifiers are best suited for applications where

some amount of dust in the fuel gas is acceptable and a
higher flame temperature is required
• Typical applications of updraft gasifiers are:
Boilers , Thermic Fluid heaters, Rotary type roasters ,

Aluminium Melting /Annealing Furnaces etc
.vnj
IDowndraft Gasifier Air is introduced downward and i

gas is drawn off at the bottom.
A lower overall efficiency and difficulties in handling W

t (•
higher moisture is the limitations in downdraft gasifiers /
The time (5-10 minutes) needed to ignite and bring

plant to working temperature with good gas quality 'i
Air Air
\ >
1« \ Combustion/
These gasifiers produce clean fuel gas and can be can be
used in applications requiring moderate temperatures m
mm
up to 600 Deg C. Typical applications where the Down K ~
draft gasifiers have been successfully used are:
Continuous Baking ovens ( Bread, Biscuits, Paint)

Batch type baking oven – rotary oven for bread
Dryers & Curing – tea, coffee, paper drying
Boilers / Thermic fluid heaters
Annealing furnaces
Direct fired rotary kilns
Internal combustion Engines
Types of Gasifiers
Fluiv Direction
Gasifier Type Fuel Oxidant
Support Heat Source
Updraft FixedBed Down Up Grate Combustion ofChar
Downdraft Fixed Bed Down Down Grate Partial Combustionof Volatiles
Bubbling Fluidized Bed Up Up None Partial Combustionof Volatiles and Char
Circulating Fluidized Bed Up Up None Partial Combustionof Volatiles and Char
Producer Gas - Applications
Power Generation Thermal Applications
• Irrigation Pumping • Hot Air Generators

• Village Electrification • Dryers
• Captive Power (Industries) • Boilers
• Grid-fed Power from Energy • Thermic Fluid Heaters
• Simultaneous Charcoal and • Ovens
Power Production • Furnaces & Kilns
Uses of Producer Gas -Thermal
* Dryers: Drying applications in farm products, food

and spices industry like rubber, tea and cardamom
(Temp, requirement 110 - 130°C).
* Kilns: Baking of tiles, potteries (Temperature

requirement - 800 - 950°C).
* Furnaces: For melting metals and alloys in non-

ferrous (Temperature requirement ~650-1000°C).
• Boilers: Process industries, which require steam or

hot water like silk reeling, dyeing, cooking etc.
* Cooking and hot water

Efficiency of Different Technologies of Gasification
Characteristics Fixed bed Fluidized bed

Updraft I Downdraft I Bubbling I Circulating
Carbon conversion **** **** ** ****
*+* +
Thermal efficiency ***** **** ***
CGE ***** *** *** ****
Turndown ratio *** ** **** ****
Management facility **** **** ** **

Control facility ** ** **** ****
Scale-up potential *** * *** *****
*Poor, **Fair, ***Good, ****Very good, *****Excellent.

Gasifier Systems and Gasifier Fuels
Biomass Gasifier type Capacity Application
Wood blocks -
Fi xed bed /down -dra ft <500 kWel Electricity / shaft power
Charcoal -
Fi xed bed /down -dra ft < 50 kWel Electricity / shaft power
Rice husks Fixed-bed /down-draft (also called < ZOO kWel Electricity / shaft power
Fixed-bed / open-core)
Coconut shells -
Fi xed bed /down -dra ft < 500 kWel Electricity / shaft power
Wood / ch arcoaI / -
Fi xed bed /c ross- draft < 5 MWth Electricity / shaft power
coconutshells
Note: kWel = kilowatt electric; MWet = megawatt electric; MWth = megawatt thermal
(Source: World Bonk Technical Paper No. 296- Energy Series)
Benefits of Biomass Gasification
• Converting a waste into high value products
• Reduced need for landfill space for disposal of solid wastes
• Decreased methane emissions from landfills
• Reduced risk of groundwater contamination from landfills
• Production of ethanol from non-food sources

Biomass Gasification-Limitations
Biomass gasification technology currently suffers from the
following issues:
• Low pressure operation results in high capital and

operating costs due to the need to compress syngas from
the gasifier to high pressure
( to be compatible with downstream processing technology)
• Typically an air‐blown operation which increases

compression costs and equipment costs of downstream
equipment in direct proportion to the nitrogen content of
the syngas
Biomass Gasification-Limitations
• Utilization of feedstock system design, specific to the
type of biomass being used
• Suffer from poor internal mixing due to large biomass

particles in the feedstock which causes soot, tar, and
slag formation and results in lower overall efficiency
• Rely on excessive use of steam to minimize tar and

soot formation which results in high H2/CO ratio
syngas (less liquid product yield by as much as 50%)
Indian Biomass Gasification Scenario
• India has a wide variety of crop and agricultural biomass

suitable for gasification
• The key market segments in India for biomass

gasification are the small and medium industries,
commercial sector and rural communities
• A considerable number of biomass gasification plants

are in operation in India at different scales and using
diverse biomass
Current Status of Biomass Gasification in India
Size (Capacity) Distribution for Gasification and Combustion Technologies
Size
Small Not prevalent Prevalent
(10 kW - 25kW)
Small-medium Not prevalent Prevalent
(25kW-250kW)
Medium (250 kW-2MW) Not prevalent Prevalent
Large (2 MW and above) Prevalent Not prevalent
Biomass Gasification Plants installed in India
State Location of the plant Built/Supported

New Delhi UNIDO C6PL
Gujarat Sped, Vallabha Vidyanagar CGPL
Maharashtra IIT Bombay CGPL
WB Tezpur University CGPL
WB Banahut CGPL
Bihar Chief Executive Officer, Shri Domen Mehto, OVN
C.G.CVaishali, Vaishal (Dist)
UP Ann Shah CAPART, Janak Puri, New Delhi-58 OVN
WB Dimapur SYNERGY
WB Kolkata SYNERGY
CGPL – Coastal Gujarat Power Ltd,

Data up to 2012
What is a Biogas Plant?
• Basically Methane & CO2 Gas Producer
• Methane – Odorless, Colorless, Good Calorific Value,

Green House Gas
• Sources : Animal Manures, excreta, kitchen waste,

Industrial Chemical Processes, Sea Water Bed, etc.
• Animal Manure & Excreta contributes around 16 % of

the total global methane emission
Schematic of a typical Biogas Plant
Gas:
O to combustion
or other uses
Gas-holder
Dung Water <CH4 + CO, + ...)
Feed
scurry
Sludge
77W,
YJ
Y,
/
X
X
//X
Digester 9,.
%
X
9
'"/////////S////JP
w\\iL?y / »vÿK1
V.WvbJi.
t
- •
II B
/ V.
SC
V
. I I
I I
III
< 4 I
I
VJ •- h
VS * T ivl i' i*
>AVVV*
i
'
i
'*
4
m£Jk
/
/ x
*
•* y
* - r
* *
r
E?
m9gp Im&* •* 5Sÿ
r*FJT r B 5 *« »
— Kb«U'
i
•%* S -**5 r.-v3i

4.1. "
•
• 1
jBk-,,1 _
r«"i
•_r
% y 4i
m.y .-% «%¥
*
WgTfSBPi
. i
%
r*
A
mt:.,-s
-3VA *
Benefits of Biogas Plants
• Contributes substantially in reducing Global
Warming
• Cost effective replacement for Fossil Fuels
• This Smoke Free gas emits less carbon dioxide as

compared to other fuels
• A very efficient and environmentally friendly

solution for disposing off various organic matter
Biogas Plants - Reduction in
Global Warming
Methane
• Contributes largely in Global Warming
• Traps 21 times more heat than CO2
• Over the 100 years – 25 times more temperature
impact than that by CO2
-------------------------------------------------------------------------------------------------------
-
Biogas Plant  Traps Methane 
Fuel  Carbon Dioxide.
Biomass to Bio-oil
• In the case of gasification , the biomass is first gasified
and this gas in turn produces power in a gas engine
• An emerging route for biomass based power is pyrolysis
• Biomass is rapidly heated to 450 - 600° C in absence of

air, and result s in a bio- oil called the pyrolysis oil,
which can in turn be used for firing the boilers
• Typically, 50 - 75 % (b y weight ) of the feed stock is

converted into pyrolysis oil
Vmm
Background Slides
Fluid bed Gasifier
L_
Cyclone - Syngas
Freeboard
Ash
Char/Fluidizing Sand
Fluid Bed
Feedstock
Plenum
Air/Steam
Updraft Gasifier
• The most commonly used gasifier for biomass and solid waste
materials
• In this gasifier feedstock is fed from the top and the material
moves downward through the drying, pyrolysis, reduction and
char oxidation zones
• Air is injected through a grate in the bottom of the gasifier, which

provides a bed for the feedstock and char, and
• Produced syngas flows upward, counter-current to the feedstock

flow, exiting at the top of the gasifier
Updraft Gasifier
Feedstock
r Syngas
‘ *
Drying
Pyrolysis C + C02 2CO
C + H20 CO + H2
Reduction
c + o2 co2
Air
Ash
Downdraft Gasifiers
• Downdraft gasifiers have the same general constraints on feedstock
properties as updraft gasifiers
• The biomass needs to be of fairly uniform particle size with few fines
to maintain bed physical properties and minimize channelling
• The feedstock moisture content to be less than 20% to maintain high

temperatures, required for tar cracking (too high a moisture content
cools syngas)
• The biomass to have low ash content and high ash fusion temperatures
to prevent slagging
Downdraft Gasifier
Feedstock
Drying
Pyrolysis C + 02 co2
- _ . ..
• Oxidation of Volatiles
- -I C + C02
C + H20
2CO
CO + H2
Syngas
Ash
Downdraft Gasifiers-
Characteristics
• Feed rates up to approximately 65 tons/day
• Requires low moisture (<20%) and low ash contents
• Fines can cause feeding problems
• Operates at relatively high temperatures, which destroys
tars
• Heat source for gasification reactions is partial oxidation of
volatiles produced in the pyrolysis zone
• Operates at 1,450 – 2,200°F, with syngas exiting at 1,100 -
1,500°F
• Low tar content in syngas
Updraft Gasifier-Characteristics
• High feed rates up to approximately 150 tons/day
• Feedstock is pre-dried before it reaches pyrolysis and
gasification zones
• Good for high moisture (up to 50%) biomass and wastes
• Heat source for driving gasification reactions is the partial
oxidation of char
• Operates at 1,450 - 2,000°C with syngas exiting at 500 -
1,400°F
• High amount of tar in syngas
• High efficiency
Benefits of Biomass Gasification
• Conversion into a high value product(s)

• Reduced need for landfill space for disposal of solid
wastes
• Decreased methane emissions from landfills
• Reduced risk of groundwater contamination from
landfills
• Production of ethanol from non-food sources
Advantages and disadvantages of different gasifier types
Gasifier type Advantages Disadvantages
1ligh amount tif tar and pyrolysis

Simple design
products _
Extensive gas cleaning required if used
IJigh charcoal burn-out
Updraft for power application _
1liÿh fuel to conversion efficiency
Accepts fuels with higher moisture content
Accepts fuels of different sizes
Low tar Limited scale-up
At low tempera tures,, more tar
Downdraft Best option for usage in gas engines
p roduced _
At lower loa ds,. fewer particles in the gas I ligh amounts of ash and dust
Fuel requirements are strict
Applicable for small-scale operations I ligh amount of tar produced
Cross-dr aft
Due to high temperatures, gas cleaning
requirements are low _
Gas stream contains fine particles of
Compact construction dust
Uniform temperature profile
Complex system due to low biomass
hold up in the fuel bed _
Fluidized bed
Variety of biomass can he used but
Accepts fuel size variation fuel flexibility is applicable for biomass
of 0-1 cm to 1 cm size
Iligh ash melting point of biomass does not
lead to clinker formation
Entrained- flow' Applicable tat large systems I ligh investment
Short residence time for biomass Strict fuel requirements
GAS
CYCLONE
rJT RFCIRCUI ATIDN Of THE
m FUEL
IIUIOI/ID BID /
DISIMl HUIOR
PLATE
AIR /OXYGEN/
SHAM
ASH
Fluidized bed gasifier

Conditions /requirements for Biomass
Feeding
Biomass gasifier needs uniform-sized and dry fuel for smooth and
trouble-free operation.
• Most gasifier systems are designed either for woody biomass (or
dense briquettes made from loose biomass) or for loose, pulverized
biomass
• Woody biomass:
 Pieces smaller than 5–10 cm (2–4 inches) in any dimension,
depending on design
 Bulk density of wood or briquettes: less than 250–300 kg/m3 Loose
biomass:
 Pulverized biomass, depending on design
 Moisture content up to 15%–25%, depending on gasifier design
 Ash content below 5% preferred; with a maximum limit of 20%
 Bulk density of loose biomass is less than 150 kg
Entrained-flow Gasifier
COALWATER
SLURRY .. OXYOES
$&.
GAS AND SLAG
Entrained-flow gasifier
Entrained-flow Gasifiers
• In entrained-flow gasifiers, fuel and air are introduced from

the top of the reactor, and fuel is carried by the air in the
reactor
• The operating temperatures are 1200–1600 °C and the
pressure is 20–80 bar.
• Entrained-flow gasifiers can be used for any type of fuel so
long as it is dry (low moisture) and has low ash content.
• Due to the short residence time (0.5–4.0 seconds), high
temperatures are required for such gasifiers. The advantage
of entrained-flow gasifiers is that the gas contains very little
tar.
Fischer Tropsch Synthesis (FTS)
Gas To Liquid (GTL) Technology
B. Tech. APEG Sem. V

University of Petroleum & Energy studies,
Dehradun, 14-11-2017
G.S.Dang
gurbax49@gmail.com
Contd .
22/11
Fischer Tropsch Synthesis (FTS)
• Kaiser Wilhelm Institute,
c Mülheim, Ruhr
S
w
i
%
-1M r
T
1 y/'
• 1920s
• Coal derived gases
(Syngas)
• Aim to product
Franz Fischer Hans Tropsch hydrocarbons
• Commercialized in
1930s
FTS Industrial History
Germany
– 1923, Franz Fischer and Hans Tropsch
– 1934, first commercial FT plant
– 1938, 8,000 barrels per day (BPD)
U.S.A
– 1950, Brownsville, 5,000 BPD
South Africa
– 1955, Sasol One, 3,000 BPD
– 1980, 1982, Sasol Two and Sasol Three, 25,000 BPD
Malaysia and Qatar
– 1993, Shell, Bintulu, 12,500 BPD
– 2007, Sasol, Oryx GTL, 35,000 BPD
China, Nigeria etc.
Fischer Tropsch Technology
Natural Gas (2n+1) H2 + n CO → Cn H(2n+2) + n H2O
Coal Key Issues : FT Reactor & Catalyst
Pet Coke
Biomass
Wastes CO Tail
L- Synthesis Gas
Production
FT Liquid
Synthesis
Product
Recovery
Gas
Power
Generation
i
\
Oxygen _O, * Liquid Wax Hydrogen
Air Plant Fuels Recovery
H2 I
, H2 Option ii
Hydrogen Wax
Separation Hydrocracking
T Liquid
Fuels p Transportation
Hydrogen
Fuels
*
Process Chemistry
• The Fischer-Tropsch process is a catalytic chemical
reaction in which carbon monoxide (CO) and hydrogen
(H2) in the syngas are converted into hydrocarbons of
various molecular weights according to the following
equation:
(2n+1) H2 + n CO → Cn H(2n+2) + n H2O
• Where n is an integer, For n=1, the reaction represents

the formation of methane, which in most CTL or GTL
applications is considered an undesirable by-product
Process Chemistry
• The Fischer-Tropsch process conditions are chosen to
maximize the formation of higher molecular weight
hydrocarbon liquid fuels (higher value products)
• Other side reaction taking place in the process, water-

gas-shift reaction is predominant
CO + H2O → H2 + CO2
Process Chemistry
• Depending on the catalyst, temperature, and type of
process employed, hydrocarbons ranging from
methane to higher molecular paraffins and olefins can
be obtained
• Small amounts of low molecular weight oxygenates

(e.g., alcohol and organic acids) are also formed
• The Fischer-Tropsch synthesis reaction, in theory, is a

condensation polymerization reaction of CO
Fischer Tropsch Synthesis
CO + 2H2 → -(CH2)- + H2O
Process Operation Mode Catalyst Reactors

The Sasol Slurry
Phase Distillate
%
Reactor
LTFT Cobalt Slurry Bed 'Ul

(200°C - 250°C)
1993 - present
Diesel & Wax
The Tubular Fixed Bed

Reactor
Fischer- Precipitated Fixed Bed
Tropsch Iron
Synthesis
(FTS) Pre-WWII - present
The Sasol
HTFT Advanced Synthol
(300°C - 350°C) Reactor
Gasoline &
Light Olefins
Fused Iron Fluidized Bed
T
1989- present
- (CH2)- is a hydrocarbon molecule

• Reactions and Products

Reactions in FTS
Main reactions
1. Paraffins (2n+1)H2+nCO— CnH2n+2 +nH20
2. Olefins 2nH2+nCO—* CnH2n +nH20
Side reactions
3. Water-Gas-Shift (WGS) CO+H2OÿCO2+H2
4. Carbide formation yC + xM <->MxCy
5. Alcohols 2nH2+nCOÿ CnH2n+20 +(n-l)H20
6. Boudouard reaction 2COÿ C +C02

MxOy + yH2 <ÿxM + yH20
7. Catalyst reduction and oxidation
MxOy + yCO<->xM + yC02
8. Coking H2 + CO — C + H2O
Standard LTFT Product Distribution
low sulfur, nitrogen
14%
12%
Gasoline Range Diesel Range Wax Range
10%
! I \
Jet Fuel Range
8% i i
2*
> 6%
u
01
<U 4%
CO
2%
0% I
1 6 11 16 21 26 31
Carbon Number
Fischer-Tropsch Products
• Syngas is catalytically converted via Fischcer-Tropsch (F-T) reaction into a
spectrum of hydrocarbons and oxygenates ranging from methane to waxes
• Based on catalyst function and operating conditions, product distribution can

be focused on light hydrocarbons, naphtha fraction, or middle distillate,
diesel fuels, or heavy products, waxes
• One of the most attractive features of F-T synthesis is that its products are
extremely clean, free of sulphur, nitrogen, and aromatics; and its diesel fuel
product has high cetane number, ranging from 76 to 80
• Diesel fuels with such a high quality are extremely difficult and costly for
refiners to produce from petroleum, if ever possible
Fischer-Tropsch Products
(Hydrocarbons Types)
• Olefins
– High chemical value
– Can be oligomerized to heavier fuels
• Paraffins
– High cetane index
– Cracking relatively easier
• Oxygenates
• Branched compound (primarily mono-methyl
branching)
• Aromatics (HTFT)
Fischer-Tropsch Synthesis
 Catalysts and Reactors

Fischer-Tropsch Catalysts
• Iron (Fe) is relatively low cost and has a higher water-

gas-shift activity, and is therefore more suitable for
syngas having a lower hydrogen/carbon monoxide ratio
(H2/CO) such as those derived from coal gasification
• Cobalt (Co) is more active, and generally preferred over

ruthenium (Ru) because of very high cost of Ru
• In comparison to iron, Co has much less water-gas-shift

activity, and is much more costly
A variety of catalysts are used for Fischer-Tropsch
synthesis, the most common are iron, cobalt, nickel
and ruthenium
FT catalyst development has been focused on the preference for

high molecular weight linear paraffins and diesel fuels
production
Among these catalysts, it is known that:
• Nickel (Ni) tends to promote methane formation ; generally it is

not desirable
• Iron Catalysts (Fused) – HTFT
– Products are high olefinic
– Cheaper
– Reactor: Fluidized bed
t \
\
I
Iron oxide
1500 °C Molten Magnetite Cooled rapidly
K2O Crushed in a ball mill Fused Iron
Air (Fe3O4)
MgO or
i
\
Al2O3 /
/
• Iron catalysts ,Precipitated - LTFT
– Co-precipitation method
– Cost more than fused iron catalyst
– Reactor: slurry phase or fixed bed
/"
\
/ \
Fe(NO3)3
Na2CO3
K2CO3
\ /
\
\
s
s
'4
Precipitate
pH = 7 Washing Drying Calcination
Iron Cat.
\ I
S /
• Cobalt catalysts – LTFT

– Oxide support: silica, alumina, zinc oxide
– Products: predominantly paraffins
– Low resistance towards contaminants
\
/ Co(NO3)2 \
I
I
I Supported
Support Drying Calcination
Co Cat.
I
\
• In addition to the active metal, the catalysts contain a
number of promoters like potassium and copper, as well
as supports such as silica and/or alumina
• FT catalysts are sensitive to the presence of sulphur

compounds in the syngas and can be poisoned
• Catalyst sensitivity to sulphur is higher for Co-based

catalysts than for their iron based, which contributes to
higher catalyst replacement costs for Co
• Co catalysts are thus preferred for FT synthesis with

natural gas derived syngas, where the syngas has a
higher H2: CO ratio and is relatively lower in sulphur
content
• Iron catalysts are preferred for lower quality feedstocks

such as coal
Comparison of Co and Fe LTFTS Catalyst
Parameter Cobalt catalyst Iron catalyst
Cost Expensive Inexpensive
Negligible
WGS reaction Significant
(more noticeable at high conversion)
Less flexible
Flexibility (significant influence of T* and p* on Flexible
hydrocarbon selectivity)
Sulphur
<0.1 ppm < 0.2 ppm
tolerance
H2/CO usage 2.0-2.15 0.5 -2.5
ratio
Attrition
Good Poor
resistance
Fischer-Tropsch Reactors
• The Fischer-Tropsch reaction is highly exothermic; heat
removal is an important factor in the design of a
commercial reactor
• Three types of reactors are used for FT synthesis:
 Fixed bed reactor

 Fluidized bed reactor
 Slurry bed reactor
FT reaction- Reactor Type
Reactor types
Slurry Bubble Column Reactor
GAS PRODUCT OUT
Fixed Bed Reactor
SYN GAS IN
STEAIM OUT STEAM OUT LIQUID

< > PRODUCT OUT
55i
:
* WATER IN
:iE
Hi
iJi
333
CATALYST
PACKED
TUBES
Fluidized Bed Hams CATALYST
SLURRY IN F-T
LIQUID
: :: Reactor
fii;
WATER IN
X X GAS PRODUCT OUT
SYN GAS IN
\ PRODUCT OUT
STEAM OUT -r v
WATER IN f\ :::P
::: ::::: CATALYST
Svv
r .‘. S "ÿ "ÿ“r >ÿ
SW
"•'ÿ"iV i1
w
FLUIDIZED BY
% VW A % W AAA
Ji VW
THE GAS
SYN GAS IN
• All three types of reactors are in use commercially
• The multi-tubular fixed-bed reactors commissioned in 1955 were

used by Sasol to produce heavy FT liquid hydrocarbons and waxes
in Sasolburg ( Low-Temperature FT Synthesis Process) aiming for
liquid fuels production
• Most of these reactors have now been replaced by slurry-bed

reactors (state-of-the-art technology for low temperature FT
synthesis)
• Slurry-bed FT reactors offer better temperature control and

higher conversion
• Fluidized-bed FT reactors were developed for high

temperature FT synthesis to produce low molecular
gaseous hydrocarbons and gasoline
• Originally developed in a circulating mode but have

been replaced by a fixed fluidized bed (advanced
reactors)
• These types of reactors have high throughputs

FTS Reactors
lyngac
l ( A k OUBK
f .y.
I -•X-.
<XC€t
Coblyot
Tu:«s C33fyS
\
Slurry
Eeo ASD
CtCOT ou
Olevn 3*
Car.a ystj
saroppe. Bed
Cooing ’ Cooing
! vixv
CasCuie: IH. LrSJ
\ -r'5«
•
et :r:;;
ret
1
\’x•
-y~*
irm
MullUuLultfi Circulating
(ARGE) Fixed Fixed
(Synthol) Slurry Eed
(Sasol Advanced Synthol)
Fixed Bed Fluidized Red
Fluidized Bed
FTS Reactors
High Temperature Processes Low Temperature Processes
Gas phase reactions and products Liquid phase reactor products
Products - mostly diesel
Original 1950’s
technology
developed for The Sasol Circulating The Tubular Fixed Bed
current application Fluidized Bed Reactor
Reactor
> 1950 - present Pre-WWII - present
Advanced reactor The Sasol

The Sasol Slurry
Phase Distillate
%
technology for Advanced Synthol Reactor
21st century
>
Reactor
1
.... 'Ut••
1989 - present 1993 - present
LTFT Reactors
CO + H2 → -(CH2)- + H2O
1800 oC Adiabatic Temperature Rise
• Fixed Bed (Gas Phase Reaction Media) – Shell SMDS

– Excellent reactant transport
– Simpler design
– Poor product extraction, heat dissipation
– Limited scale-up
– Potential for thermal runaway
• Slurry Bed (Liquid Phase Reaction Media) – Sasol SPR
– Thermal uniformity
– Excellent product extraction
– Excellent economies of scale
– Requires separation of wax from catalyst
– Higher cost
FTS Reactors & Catalysts
• The state-of-the-art F-T technology uses slurry-phase

reactors for uniform temperature control and lower
reactor cost
• Harsh hydrodynamic conditions in slurry-phase

reactors require F-T catalyst to possess high attrition-
resistance in addition to high catalytic activity
• Prevalent F-T catalysts are either iron- or cobalt-based

FTS Reactors & Catalysts
• Many iron-based F-T catalysts ( made by co-precipitation

method) quickly breaks down into very fine, even sub-
micron size particles which are extremely difficult to
separate from wax products
• This has been a major obstacle for its commercialization
• Cobalt based catalysts are resistant to catalyst breakdown

and facilitate catalyst/wax separation problems but
catalyst costs are high
FTS Polymerization Process - Steps
c HI¬ H? GH,
 Reactant adsorption
alia
+ CH2
 Chain initiation
CiH,
+ Hi
C:H4 CzH*
 Chain growth
 Chain termination atfa + CH2
 Product desorption C.-J-U GJHE

t H;-
CJHB
 Readsorption and further reaction -llfl
etc.
Summary of Syngas Conversion Processes and Conditions
Process Catalyst Process Conditions % conv Product Selectivity

T(X) P (bar) H2:CO (CO basis)
Fe 300-350 10-40 1.7:1 50-90% with a-olefins ASF -48% (max)
recycle gasoline 15-40% actual
Fischer-Tropsch
Synthesis
Co 200-240 7-12 2.15:1 Waxes -
ASF 40% (max)
diesel
Ru Waxes
ZnO/Cr203 350 250-350 3:1 99% (25% > 99% with recycle
Methanol Synthesis Cu/Zn0/Al203 220-275 50-100 max/pass
4-7%
- Methanol
actual/pass)
Ammonia Fe/FeO additives 430-480 100-500 2-3:1 H2:N2 10-35%/pass Ammonia > 99% with recycle
(550 max)
Alkali/Zn0/Cr203 300-425 125-300 1:1 5-20% Branched
primary
alcohols
Alkali/Cu/ZnO( Al203 ) 275-310 50-100 2-3:1 20-30% Primary 3045% Cÿ
alcohols 17-25% CP2
Alkali/CuO/CoO 260-340 60-200 05-4:1 5-30% Linear primary ASF
alcohols
Aikali/MoS2 260-350 30-175 1:1 10% Linear 75-90% C2«. in liquid
alcohols product _
Co carbonyl 110-200 200-300 1:1 olefin
Oxosynthesis
Co - P modified 160-200 50-100 1:1 olefin Cn-Cu
alcohols
Rh - P modified 60-120 7-25 1:1 C« aldehydes >90%
propylene
Isosynthesis ThCb 400-450 100-1000 0.85:1 40-50%
(300) *-C4
Zr02 300-425 350 1:1 30% 15
Steam Methane Ni 850 15-30 na 100% CH4 Syngas/
Reforming conversion
hydrogen
Fischer-Tropsch Synthesis , FTS
Two types of processes- ARGE & SYNTHOL
ARGE Process:
• Syngas is converted into straight chain olefins and
paraffins over Co containing catalyst at a temp
about 200 C and pressure 20-40 bar( LTFT)
• Reactor- large no. of parallel fixed bed reactors

placed in a pressure vessel with boiling water for
cooling and ensuring an essentially isothermal
process
FT- ARGE Process:
• The product is hydrogenated in case where st chain

paraffins are desired product
• Products - solvents and waxes, completely free from
sulphur and nitrogen compounds as well as from
aromatics
• Hydrogenation catalyst with acidic functions helps to
crack heavy products formed
• Due to absence of aromatic fractions kerosene fraction
has high smoke point, excellent blending component
for aviation turbine fuels and gas oil fractions ( high
cetane no>70)
SYNTHOL Process
• Syngas is converted into aromatic rich product over an iron

containing catalyst at temp above 300 C and pressure 25
to 40 bar (HTFT)
• The reaction takes place in large fluid bed reactors
• Product rich in aromatics is used for making gasoline of

high octane no and as a diesel blending component
• This process is used at Sasol plant in Secunda and in Mossel

bay both in South Africa
Selectivity of Fischer -Tropsch Process
(at Sasol)
Product, %age ARGE SYNTHOL
CH4 47 7
C2 To C4 Olefins 4 24
C2 To C4 paraffins 4 36
Gasoline 18 36
Middle Distillate 19 12
Hy Oils and waxes 48 9
Water Soluble 3 6
Oxygenates
% age Values are up to the number mentioned above

Operating Conditions of ARGE and
SYNTHOL
ARGE SYNTHOL
Temperature oC 220-225 320-340
Pressure 25 bar 23
H2 / CO 1.7 2.54
SMDS ( Shell Middle Distillate Synthesis)
• Further development is has been made in the area
• SMDS(Shell Middle Distillate Synthesis) process uses a

fixed bed reactor similar to that of AGRE
• Sasol has developed an advanced slurry bed reactor
• Exxon , BP, Statoil, and others have demonstration

plants in operation or under construction
Gas to Liquid
FT process
• CO + H2 = -(CH2)- +H2O -152MJ/kmol
• -(CH2)- is a building block of the hydrocarbon

molecules
• The product depends on catalyst , operating conditions,

and syngas composition
FT- Gas to Liquid
• FT synthesis require different H2 to Co ratios
• Addition hydrogen is required for product work up

Syngas Specifications
Synthesis H2/CO Remarks
ARGE 1.3 to 2.3

SMDS 1.5 to 2
Synthol 2.6
Methanol 2.4 to 3 (H2-CO2)/ CO+CO2)
= 2.05
Syngas Specifications for FT
Gas Component Max Allowable
Concentration
H2S+COS+CS2 < 1ppmv
NH3+HCN <1ppmv
Solids ( soot, dust, ash) nil
Tars including BTX Below dew point
Phenols and similar <1ppmv
Sulphur is a catalyst poison

SNG from Coal
• Shortage of Natural Gas is a one reason to
manufacture SNG
• One plant in North Dacota , USA is operating currently
• SNG requires a min H2 content as 10%
• Any Excess CO2 in product is removed by Rectisol
process
• CO+ 3H2 CH4+H2O
• CO2+ 4H2  CH4 + 2H2O
• Catalyst ----- Nickel
 Economy
XTL Technology Economy
• Cost Distribution
• NTL case 1: 25% for the gas, 25% for the operations and 50% for the capital
• NTL case 2: 15% for the gas, 21% for the operations and 64% for the capital (28%
reforming, 24% FTS system, 23% oxygen plant, 13% product enhancement and 12%
power recovery)
• BTL capital (21% for biomass treatment, 18% for gasifier, 18% for syngas cleaning,
15% for oxygen plant, 1% for water-gas-shift (WGS, CO + H2O → CO2 + H2) reaction,
6% for FTS system, 7% for gas turbine, 11% for heat recovery / steam generation, 4%
for other)
• Recycle, power and heat integration

• CO2 transport and storage
(NTL- Natural Gas to Liquid, BTL – Biomass to Liquid)
Syncrude Upgrading
 Extraction and Purification
• Terminal Olefins, Oxygenates, and FT Wax have high value
 Hydrocracking
• Converts wax into liquid fuels
 Oligomerization
• Converts light olefins to liquid fuels
 Other Reactions
• Alkylation, Isomerization, Aromatization, etc.
 Polymerization
• HTFT ethylene and propylene can be made into polymers
 Hydrogenation
• Promoted fuel stability
GTL & CTL
Liquids from Fossil Fuels
Gas-to-Liquids Frail Energy
K& l> PTfljrtm
i
Ctmvmitlftnal Admncad
Hi-fircrivi
VJIIJI:II EBCFB ]' ad i'v\h
:
vir
jfjpf Air tj2S Edldac)
AltiriMtlve Fuel
"V
I'..,
Vctatki
Slijni ItL'furiDur L Pun:

OnyÿLTi
: .ÿ :n;
:
j Ihil run
Mwitoranjcj Scpanlfca
Jkÿnl
/
s Synthesis Gas
isdirr-
TrOfisili
hl.iuu.id t uL'Is
CoaJ-to-LiquicIs /* Ill> iLni(fi iii -

i arlion MumNtult
ChHnbah
m
.
ladlnKt
[JijtiL-fAiiii'ii
..
— GaiHIfr
t \
Ki-rif r ('Hlalysi* H i cui'h1' Impnn tncota
(r.j;. : Starry IrijhN-r
Kossil Entergy ILLIIIIIILMIIL I
li& D Progi'iim
GTL , CTL Through FT
• Liquid transportation fuels can be produced from
syngas via catalytic chemical reaction called Fischer-
Tropsch (FT) synthesis
• Many refinements in the technology have been made,

including catalyst development and reactor design
• Depending on the source of the syngas, the technology

is referred to as coal-to-liquids (CTL) and/or gas-to-
liquids (GTL)
GTL , CTL Through FT
• Examples of current operating CTL plants include

Sasol’s Sasolburg I & II plant and an example of a GTL
FT process is Shell’s plant in Bintulu, Malaysia
• Many world-class GTL and CTL plants are currently at

various stages of engineering and construction in
Nigeria, Qatar and China
• Recently, methanol synthesis with new methanol-to-

gasoline process have become a competing technology
for the traditional FT approach
GTL Process ( Gasification, Fischer-Tropsch & Hydroprocessing )
Natural gas, Long chain Finished
Synthesis gas
coal, biomass paraffins XTL products
CO + 2H2
hydro-
syngas
manufacture a—
cleaning &
Fischer-Tropsch
synthesis
processing
& separation
refinery/
chemical
A conditioning products: e.g.
A • LPG
oxygen O2 • naphtha
H2O out for GTL,
• kerosene
in for CTL
Air air • gasoil
separation • base oils
• chemicals
1973 1983 1993 Project ramp up 2011

!
I
—fplf
7 — 'l
4 1 ,o *5L& i
-& t.
• r
« i*
>. i’
Oj
u
ra»
>;!
4
i i* ;_-
V
SB
twm
f L TT— -o— «-«*—* «x »*+"
-o
w TTT
Shell GTL Projects
Laboratory Pilot plant Bintulu Malaysia Pearl GTL Qatar
Amsterdam Amsterdam 14700 bbl/d planned 140000 bbl/d
FT Synthesis
FT is making a “comeback” in a big way

 High Cetane ( sulphur free) diesel / other chemicals
 Improving economics
Key Issues
 FT Reactor
 Catalyst
GTL Advantages
• Energy from natural gas production can be used & the
reserves of natural gas are expected to last longer than
those of mineral oil
• No additional infrastructure or changes in the vehicles
are necessary
• GTL fuel can be mixed with conventional fuels (e.g.
with Diesel from fossil production) without any changes
to the engine
• As the GTL fuel is the product of a chemical
transformation and refining process, possibilities exist
for the design of a fuel with excellent qualities and
thus a reduction in environmental impairment
GTL-Benefits
• Cleaner Environment
• Lower Greenhouse Gas Emissions
• Expended, More Diversified Fuel Resources
• Stronger, More Competitive Energy Industry
• More Jobs
Economics
• Economics are dominated by the gross margin in the
fuel industry
• The gross margin is defined as the difference between

feedstock costs and revenue derived from products
sales
• The objective is to minimise feedstock costs, while

maximising the product revenue
Economics
• It is beneficial to obtain access to gas reserves that are

cheaper compared to commercial gas
• Cheaper gas exists in the form of remote or stranded

gas reserves, flared gas and associated gas reserves.
• The economic feasibility of GTL plants is highly sensitive

to the oil price, which has shown extreme variability
over the last forty years
Economics
• World leaders Sasol and Shell experienced the same
problem. They overcame this by moving away from
fuel production and produce high valued chemicals,
lubrication products and waxes instead ( exploited
the versatility of the GTL technology)
• Oil production, together with oil discoveries have
peaked and show a downward trend. This provides
another economic driver for GTL
• The world has already realised that crude will become
less and less available, and have turned their attention
to finding viable alternatives, such as GTL
FT Diesel vs Petroleum Diesel – Emission Performance
Emissions Reduction Relative to

Low Sulfur Petroleum Diesel
Hydrocarbons 41-46%
CO 45-47% are
NOx 9%
Particulates 27-32%
W V
Emissions Reduction Relative to

Low Sulfur/Low Aromatics
Petroleum Diesel
Hydrocarbons 25-31%
CO 34-38%
NO* 5%
Particulates 23-29%
Gas Hydrates
B.Tech. APEG, Sem V

Dehradun, 7-11-2017
G.S.Dang
gurbax49@gmail.com
9/ 10-11-2017
GAS HYDRATES
••
Sediment I
/ v
y\
Gas Hvdrate
564
Gas Hydrates
Methane Hydrate Burning Ice (Methane Clathrate)
\vv/
Methane clathrate . also
"The Burning called methane hydrate or
Snowball" methane ice, is a solid
Methane hydrate
supporting
form of water that
its own combustion contains a large amount of
methane trapped within
its crystal structure
565
What are gas hydrates ?
 A gas hydrate consists of a water lattice in which light
hydrocarbon molecules are embedded resembling dirty
ice
PIIPIPIPP
Hi mm
m
iim
is:
IK . ,<a V*
, o 01 #1111
i
- HH
i
.
.
dfi
/.ÿ
«rSB
:-y ... - ." aBBBlif
I
* rsEiUSGs
566
Gas Hydrates Structure
H2O)
:
*
i \
CH4
#
567
What are gas hydrates (contd.)
 Naturally occurring gas hydrates are a form of water

ice which contains a large amount of methane within
its crystal structure
 These are restricted to the shallow lithosphere (2000-

4000 m depth)
 Under pressure these remain stable at temperatures up

to 18°C
568
What are gas hydrates (contd.)
 The average hydrate composition is 1 mole of methane

for every 5.75 moles of water
 The observed density is around 0.9 g/cm3
 One liter of methane clathrate solid would contain 168

liters of methane gas (at STP)
569
Gas Hydrates Occurrence
• Gas Hydrates lie deep in the oceans, at high pressures

and low temperatures found at ocean depths greater
than 500 metres
• Source of this methane is biogenic; from the organic

waste or detritus (dead organic material) that
descend to the ocean floor where bacteria act on
them to generate methane
570
Where does the gas come from?
Biogenic Hydrate Thermogenic Hydrate
Microbial activity in the upper Thermal breakdown of
several hundred meters of organic material at
deep-sea sediment (about 99%) greater depths
••
%Kr
i
&&
-tV Qm
;
it
4
i
i
A
/ *
£
*
i•
*
a r
%
>
m
p
* '
. V
A
r f
Gas Hydrates -Formation
• Gas Hydrates are formed at high pressure (8-30 MPa)
and low temperature (10 to 20°C) in shallow sediments,
and are stable up to a few hundred metres below the
seafloor (defined as the gas-hydrates stability zone)
 Hydrates are found in situ in the deep oceans on the

ocean floor or in the sediments below the seafloor
 Hydrates are also found in situ in permafrost regions
572
Where are Hydrates found?
 Conditions for hydrate formation are satisfied in more
than 90% of the ocean floors but
 Hydrates will only form if there is a source of natural
gas and a structure suitable for gas accumulation
 It has been estimated that total worldwide hydrate
16 3
resources are as much as 10 m , or twice as large
the combined fossil fuel resource
 Gas contained in naturally occurring gas hydrates may
exceed 16 trillion tons of oil equivalent
573
Where are Hydrates found?
 Possibly as much as 98% of the hydrate resource

is below the world’s oceans
 The remaining 2% that is found on land, below

permafrost, is estimated to be twice the size of
the conventional natural gas resource
574
Location of known and inferred gas hydrate occurrences
in deep marine and arctic permafrost environments
Arctic Ocean Arctic Ocean
•l I
0?
0 0
'*ÿ f
Atlantic
Ocean « i l
oP K
JL. 0
mr I
[*T» 1T~ m
0 Ocean 0 0
‘
I 0
v
0 Recovered Gas Hydrate
• Inferred Gas Hydrate *
575
Where are gas hydrates located?
»«
e." -
1,
* K
-
-+~
*
/M
[. . •V
?!
ii
'ÿ•/i
It is present in oceanic sediments along continental margins and in

polar continental settings.
576
Gas Hydrates along Coastal Line ( India)
220J V meters
Si
900
20°J INDIA
800
Bombay
18oJ 700
Visakhapatnam
rn
* 600
s P
160-
V
« 500
-J 14°-
Madras f 400
120- \ 300
to \ i
10°-
r4dv/T\
*b
n1/
- •»
80- 100
68° 70° '

72°
VJ
74° 76° 78° 80° 82° 84° 86° 88° E
0
Locations (black ovals) in the eastern offshore,

superimposed on gas-hydrates
stability thickness map along the Indian margins from
which gas-hydrates samples
have been recovered by drilling (2006 , NGHP Expeditio 577
n 01)
Indian Scenario
 With no major findings of gas reserves in India it is

essential to look for other alternative resources such
as gas hydrates
 Substantial sediment thickness and organic content,

provide favorable conditions for occurrence of gas
hydrates in the deep waters adjoining the Indian
continent
578
Gas Hydrates
Gas-hydrates have attracted the global

attention due to their
• widespread occurrence,
• potential as future major energy resource,
• role in climate change and
• submarine geo-hazards
Natural gas recovery from Gas Hydrates
• Gas hydrate is stable only under certain pressure /
temperature conditions
• Two most commonly proposed techniques for
producing gas from these rely on changing the
pressure and temperature conditions
• Thermal stimulation heats the gas hydrate beyond its
zone of stability, while depressurization decreases the
pressure below the point of gas hydrate equilibrium at
a prevailing temperature
• A third technique relies on shifting the gas hydrate
stability conditions by injecting an inhibitor such as
methanol or glycol or other additive 580
Methane Recovery from Gas Hydrates
Modifying the equilibrium conditions by
• Depressurization: At fixed temperature, operating at

pressures below hydrate formation pressure
• Thermal stimulation: At fixed pressure, operating at

temperatures above the hydrate formation temperature
which can be achieved by heating
• Inhibitor injection: Inhibition of the hydrate formation

conditions by using chemicals like methanol and salts
581
Gas Hydrate Production Methods
(a) Steam or (b) (c) Inhibitor or

Gas
Out r Hot Water gas
Out
Gas
Out r Other Additive
Impermeable Rock Hydrate Cap Impermeable Rock
Dissociated Dissociated
Hydrate Hydrate Dissociated Hydrate Zone
Hydrate
Hydrate
(M (M
* -*- Free-Gas Reservoir
Impermeable Rock Impermeable Rock
(a) thermal injection (b) depressurization, (c) inhibitor or other additive
582
Gas hydrates: A gift wrapped in problems
The real hazard is
• Mindless mining can cause landslides, release/ bursts of

methane into the atmosphere and accelerate global
warming, with consequences that are well known
• All this is because, gas hydrates where they are, are

stable; but once dislodged can be dangerous - due to
their great expansion ratio and being very volatile
583
Risks of Mining of Hydrates
Gas hydrates are a significant hazard for drilling and

production operations; There are two possibilities that
can combine to cause major disaster
• Ist Possibility - there is 3000 times more methane down
there than there is now in the atmosphere; methane is
21 times worse than carbon dioxide as a climate warmer
• IInd Possibility - methane hydrate sediments are close to
coastlines; they can be in layers that are more than 10
kilometres deep; mining for them can set off ‘landslides’
down there
584
Summary
• Gas Hydrate is a potentially vast, but yet untapped,
global energy source for natural gas
• Most of environmental, safety, regulatory and social

considerations related to its exploitation appear to be
similar to those associated with conventional gas
production
• No big technical problems are foreseen in producing

gas from gas hydrate except that it is more cost
intensive ( compared to gas production from
conventional reservoirs)
585
Summary…..contd.
• The most promising method of production appears to

be to dissociate gas hydrate via pressure drawdown
within a reservoir
• The most favourable conditions are when gas hydrate

occurs in marine and sub-permafrost sand formations
• Commercial production of gas from gas hydrate would

likely begin in association with natural gas fields,
developed to exploit conventional resources
586
Summary…..contd.
• Gas hydrate production could share, to the extent possible,

established infra structure, particularly for gas transport
• Need is there for further exploration and appraisal of the

gas hydrate resource as well as construction of new
transport infrastructure
• Stand-alone commercial production of gas from gas

hydrate is not likely to take place around the world within
at least the next two decades !!
587
Gas To Liquid (GTL) Technology

G.S.Dang
gurbax49@gmail.com
Energy Scarcity
Energy scarcity happens when resources are limited or

the costs for production are too high
• The world mineral oil production is not expected to
increase further but scarcity of oil supply is very
unlikely before 2040
(due to the exploitation of unconventional sources and
natural gas liquids)
• With measures, already being taken to increase the

energy efficiency of appliances / vehicles the mineral
oil supply is expected to be sufficient until 2050
Global oil production scenario
2006 Peak
History I
32.00 -|
1999 t
t
World Gil
Forecast
1973
1979
1
/ 2000-2046'
t 1
OFEC/non-QPEC
Crossover event
2COB
£S
<= 16.00 -
NorrOPEC
I t
OPEC
\
-3::
\ 3 2 a
0_ 1 /
1979
i /
m
dominance
Non-C'FEC
0.00 T T T 1
1960 1930 2003 2020 2040
Source: ASPO 2006
OPEC countries in domination from 2008

onwards
Natural Gas To Liquid ( NGL)
• Natural Gas is a cleaner fuel compared to petroleum

or coal
• Its conversion into liquid helps to

Transport it with much reduced volumes &
 as fuel in more environmentally sound way
through syngas / FT route ( Cleaner Fuel)
What is Gas To Liquids (GTL)?
Methane+ Oxygen Hydrogem- Carbon Fischer-Tropsch distillates- Water
monoxid
0* « •» Catalyst *
Raw
Natural
Gas CH Syngas
CO + 2H. - CHj-
° 2
_ Ethane Bintulu SMDS

LPG
GTL Naphth
LPG
fc— GTL Gas Oil
Condensate
n-Parafflns
Sulphur GTL Base
Lli"1 foil Oils
Conversion of natural gas to clean, high quality fuels

& products via the Fischer Tropsch process
Ultra-clean Transport Fuels
100%
I o
n fi
r 80% -
Other Fossil Fuels
0
? (Nat.Gas, etc.)
9
a.u-
*5 3 60% -
h IL
Petroleum
40% -
20% -
Renewables
0%
Current 2015
Developing Advanced Major Transition to Fuel
Petroleum Based Fuels I Blends and Neat
4
and Blends ** Alternative Fuels
Fuel Quality & Engine Design for Emission Control
Technology Integration
21st Century Ultra-Clean Transportation Systems
so
O'
4? °oo
/ Integration
O
%
o'
System Requirements
• Ultra-low emissions
• High performance Fuels
• Long-term durability
• Low toxicity
• Affordability
The fuel is made from mineral oil, natural gas
or biomass
hydrogen
emission and CQ2 fneE
Based on renew. Erf
Synthetic fuels jEJTL)

Low Emissions, low COi
emissions
Based on biomass
Synthetic fuels (GTL), Low

Emissions
Based on natural gas
Clean convent- Fuels

so ph or- free, no anomalies
based On crude G U
Conventional fuels
Containing sulphur and
aromatics
Natural Gas
• Bridge fuel gas will play a significant role in the 21st

century transition to a post-fossil economy
* Cleaner burning fossil fuel -- lower sulfur, particulates,

NOx; with lower capital
investments required
• As an energy source, natural gas offers part of the

solution to global efforts to reduce greenhouse gas
emissions - up to 50% less C02 than coal and
20-30% less than oil
GTL - Liquid Fuel
• Natural gas is used today as a direct fuel as CNG or
LNG re-gasification
• This direct use requires an additional filling
infrastructure and bulky fuel tanks in the vehicles
• Both disadvantages are avoided if gas is transformed
into a liquid fuel which can then be transported,
distributed and consumed in the already existing
infrastructure
• Today, the most frequent GTL fuel is diesel
GTL Process
Carbon Bearing Synthesis Gas Fischer- Tropsch Product Separation

Feedstock Generation Synthesis & Upgrading
+ Hj)
Natural gas • Steam Methane • Slurry Refining

Coal Reforming • Fixed-Bed Oils
Refinery Bottoms • Auto-thermal • Fluidized Bed Wax
Associated Gas Reforming Diesel
Biomass • Gasification Lubricants
Partial-oxidation Petrol
Natural Gas Conversion Processes / Technology
N Physical Conversion -> Using Low Temperature Liquefied Natural Gas (LNG)
a
Partial Oxidation
t and Synthesis
u
Indirect Conversion Steam Reforming Diesel, Hydrogen, Ethers,
r * (To Syngas) and Synthesis Methanol, Gasoline, Jet Fuel
a Dry Reforming
1 and Synthesis
Direct Conversion Methane Dissolution

G (To Acetylene) and Oligomerization
Gasoline, Aromatics
a
s Direct Chemical Oxidative Coupling Petrochemical and
Conversion and Oligomerization Fuel Blendstocks
XTL Technology
X G L
Coal
Fischer- Syncrude Fuel
Biomass Gasification Syngas Tropsch Refining & &
Natural Gas Processing Synthesis Upgrading Chemicals
n,
#
\ r
L X
* B*.
a
*•
i\' e9
'*!!,. k Art
« A.
**
.>44 •44
*
Natural Gas Gasification
 Steam Reforming
• CH4 + H2O → CO + 3H2 (Ni Catalyst)
• H2/CO = 3
• Endothermic
• Favored for small scale operations
 Partial Oxidation
• CH4 + ½O2 → CO + 2H2
• H2/CO ≈ 1.70
• Exothermic
• Favored for large scale applications
 Auto-thermal Reforming
• A combination of Steam Reforming and Partial Oxidation
Syngas Processing
 Water Gas Shift Reaction

• CO + H2O ↔ CO2 + H2
 Clean up
• Particulates
• Sulfur (<1 ppm) - ZnO Sorbent
• Nitrogenates (comparable to Sulfur compds) etc
GTL Technology and Syngas Processing
Synthesis Gas(H2/CO)
Fischer- Tropsch Methanol Higher Alcohol

Synthesis_ Synthesis Synthesis_
I I
Alcohols
Wax Diesel Gasoline Methanol
IQ- C6jÿ
t
Methanol MTBE
to Gasoline
Synthesis
process
MTBE
Conversion of NG to liquid fuel – Why ?
• Need for economic utilization of Natural Gas

( particularly for stranded NG)
• Reduction in cost of transportation of NG from
producing to consuming regions (same principle as
with LNG)
• Environmental concerns
- development of clean fuels throughout the world
( gasoline , diesel & fuel oils)
Main Drivers
• GTL fuels are clean, compared to those that are
derived from crude oil
• It contains almost no sulphur, and its carbon dioxide

footprint is also less than that of coal derived fuels and
comparable with crude derived fuels
• Environmental pressure to reduce the amount of

flaring of associated gas, which means a reduction in
the amount of green house gas emissions
Main Drivers
• A large market growth in the use of diesel driven

vehicles. GTL is geared towards making more diesel
than petrol
• An increase in known gas reserves of natural gas that

can add value to the economies of especially developing
countries
Ultra Clean Fuels for 21st Century _ Goals
• Produce ultra-clean petroleum fuels from domestic and imported crude

• Produce ultra-clean fuels from alternative hydrocarbon feedstocks
(natural gas, petroleum coke, refinery bottoms, coal, waste materials,
biomass) that are equal to or better than current petroleum fuels
• Ensure fuel/engine/emission control combinations that meet future

vehicle emission standards
Proposed Ultra-Clean Transportation Fuels
Ultra low sulfur, increased octane gasoline

Ultra low sulfur, high cetane diesel
On-board reformer fuel (hydrogen fuel cells)
Fuel additives and blending components
Ultra low sulfur lubricants
Ultra clean jet fuel
GTL Chemistry
•Production of synthesis gas (“syngas") occurs using

either partial oxidation or steam reforming
-Partial oxidation: CH4+ 1/2 02 CO + 2 H2
(exothermic)
- Steam reforming: CH4 + H20 CO + 3 H2
(endothermic)
- Other possible reactions:
•
CO + H20 £* CO, + H2
•
CH4 + C02 2 CO + 2 H2
• Fischer-Tropsch synthesis
- CO + 2H2 -> —CH2— + H20 (very exothermic)
Key Steps in GTL Process
Natural Gas
) Gas Separation
and Purification MS H Product
Upgrade ) Liquid
Fuels
>
Methane,
n{CH2}-, Liquid
Methane [ Oxygen.
Water Fuels
Steam
GTL & CTL
Liquids from Fossil Fuels
Gas-to-Liquids Frail Energy
K& l> PTfljrtm
i
Ctmvmitlftnal Admncad
Hi-fircrivi
VJIIJI:II EBCFB ]' ad i'v\h
:
vir
jfjpf Air tj2S Edldac)
AltiriMtlve Fuel
"V
I'..,
Vctatki
Slijni ItL'furiDur L Pun:

OnyÿLTi
: .ÿ :n;
:
j Ihil run
Mwitoranjcj Scpanlfca
Jkÿnl
/
s Synthesis Gas
isdirr-
TrOfisili
hl.iuu.id t uL'Is
CoaJ-to-LiquicIs /* Ill> iLni(fi iii -

i arlion MumNtult
ChHnbah
m
.
ladlnKt
[JijtiL-fAiiii'ii
..
— GaiHIfr
t \
Ki-rif r ('Hlalysi* H i cui'h1' Impnn tncota
(r.j;. : Starry IrijhN-r
Kossil Entergy ILLIIIIIILMIIL I
li& D Progi'iim
Summary
Why Gas to Liquids?
Energy security -> Strategic diversification of energy
supply
-> Biomass and Coal to Liquids
Environment Trend towards cleaner fuels
Economic development Remote gas reserves
commercialisation
Most cost effective alternative fuel
-> Strategic diversific
_ M. • _
*
____--
I M.
GTL Fuel has unique properties:

— A.
*
-Virtually free of sulphur and r
aromatics
- f
<
_
-High cetane number

Liquefaction of Fuels
(Coal , Natural gas & Biomass)

G.S.Dang
gurbax49@gmail.com
Fuel Liquefaction??
• Conversion of Fuels into liquid state
• The purpose of the process is to produce

liquid fuels from fuels like coal , biomass and
natural gas
XTL Technology
X G L
Coal
f f
R i *_
e9
**
« 4.
U4
Hi
 Steam Reforming
• H2/CO = 3
• Endothermic
• CH4 + ½O2 → CO + 2H2
• H2/CO ≈ 1.70
• Exothermic
Syngas Processing

• CO + H2O ↔ CO2 + H2
 Clean up
• Particulates

I I
Alcohols
IQ- C6jÿ
t
Methanol MTBE
to Gasoline
Synthesis
process
MTBE
Coal Liquefaction??
• Fuels have certain H/C Ratios One of the key

differences between coal and petroleum is the much
lower H/C atomic ratio of coal (0.7 vs 1.5 for petroleum)
• To make liquid fuels from coal either hydrogen is added

or carbon is rejected
• Producing liquid fuels from natural gas require

rejection of hydrogen or addition of carbon
Direct Coal Liquefaction (DCL)
• Direct coal liquefaction, DCL started just before World

War II by Germany, continues through 1950s and 1960s
with the research by the U.S.
• DCL refers to reaction of coal with hydrogen to form

liquid
• The hydrogen is required to be added to increase H/C

ratio and the coal is liquefied
Coal To Liquid ( CTL) –
• DCL involves addition of hydrogen to coal in a solvent

slurry at elevated temperature and pressure
• Coal liquefaction is accomplished under high

temperature (~400 oC) and pressure (~100-200 kg/
cm2)
Fuels H/C Ratios
CTL
Shale oil 1
Premium
products
Asphalt & Petroleum
Peat tar sand "Heavy” "Light„ Distillate
Coals
Coke & i / \
anthracite
coal Residue Natural Gas
"
0.5 0.5 07 0ÿ 0.0 1.0 1,1 1J 1,3 1.5 1.6 17 1.8 1,9 2.0 4.0
GTL
Hydrogen/carbon mole ratio t I
• To make liquid fuels from coal - need to add hydrogen or reject
carbon
• To make liquid fuels from natural gas - need to reject hydrogen or
add carbon
• Adding hydrogen and rejecting carbon (or vice versa) may be
equivalent:
CO + H20 C02 + H2
Water Gas Shift (WGS) Reaction
• The principal products of a direct-liquefaction CTL plant are
naphtha and middle distillates ( syncrude to products)
• Direct-liquefaction products contain more aromatic and

cyclic hydrocarbons and fewer paraffins, and they have a
lower overall hydrogen content
• Prospective yields are reported to be between 2.7 and 3.0

barrels per ton of as-received coal
• Theoretical efficiency can be high…roughly 70-75%

Direct Liquefaction Process
• A single-stage direct liquefaction process gives

distillates via one primary reactor
• A two-stage direct liquefaction process is designed to

give distillate products via two reactor stages in series
• The primary function of the first stage is coal

dissolution and is operated either without a catalyst or
with only a low-activity disposable catalyst
Direct Liquefaction Process
• A single-stage direct liquefaction process
 SRC-II , Exxon Donor Solvent (EDS)
 H-Coal
DCL- EDS Process
• Coal is slurried with a distillable recycled solvent that
has been re-hydrogenated to restore its hydrogen
donation capacity
• The slurry is mixed with H2, preheated and fed to a
simple up-flow tubular reactor that operates at 425-
450 ºC and 170 kg/ cm2
• No catalyst is added to liquefaction reactor
• Yields of liquid - up to 47% for Lignites, 50% for sub-
bituminous coals and 60% for bituminous coals could
be achieved
EDS Process
Hydrogen Recycle
Gases Naphtha
Fresh
Hydrogen' rj
Vacuum
X Product
Tubular Distillation
Reactor
Slurry Distillate
Mixing Separation Fuel Oil
Coal
r _n
A I
Hydrogen
Preheating Fixed Bed

Hydrotreater
2
Flexicoker
Recycle Solvent \
Coke to
Gasification
Figure 6. Schematic diagram of the EDS process

H-Coal
• The reactor operates at temperatures of 425- 455°C and a
pressure of 190-200 kg /cm2
• H2 is added and the mixture is preheated and fed to an

ebullated bed hydrocracker
• A conventional hydrotreating catalyst, either Ni-Mo or Co-

Mo on alumina is used
• Liquid yields are dependent on the coal type ; >95%

overall conversion can be obtained with suitable coals, with
liquid yields up to 50% (dry basis)
H-Coal Process Schematic
Hydrogen Recycle
Gases Naphtlra
Flash
A Product
Separator
Fresh
Hydrogen' Atmospheric
Distiliation
L 2
Distillate
Slirry Hydror.ytlone Pmrt jrt
Mixing
Etullatod
Coal Bed
Hydrocr acker 1ÿ Vacuum
Distillation
Preheating
Lear1 Slurry Recycle
Vacuum
Middle DrstiUate Sok-ent Recycle Bettors
Schematic diagram of the H Coal process

H-Coal Ebullated-Bed Reactor
Product
i
Vapor
Catalyst Addition
Separator
Ebullated Bed Ht
Product Liquid
Fixed Bed Ht. Reactor
Catalyst
Withdrawal
Feed Coal, Slurry Oil, H2
Pump
Indirect Coal Liquefaction
• In Indirect Liquefaction (IDL) coal is first gasified to form

syngas
• Syngas is then converted to liquids by Fischer Tropsch

(FT) process using catalyst
• Synthesis Gas (Syngas) mixture of CO, H2, CO2, H2O etc
• Theoretical efficiency is lower… 60-65%

• The process begins with the gasification of coal
• Reacting coal with steam and oxygen at elevated

temperatures (1,000 to 1,500 oC ) and moderate
pressure(~35 kg/cm2)
• Conversion of synthesis gas to hydrocarbons is highly

exothermic (i.e., it releases heat)
Coal-to-Liquids
Methanol to Gasoline (MTGCTL)
• MTG CTL- Methanol-to-Gasoline Coal-to-Liquid
• The front end of an MTG CTL plant is similar to

producing methanol from syngas
• MTG Synthesis at 200 to 300 oC , about 50 kg/cm2
• Highly exothermic process

MTG CTL
• After upgrading and separations, the liquid-fuel yield

of an MTG CTL plant would be about 90% gasoline,
with most of the remainder being LPG
• MTG reactor does not produce any of the heavy

hydrocarbons
Coal Liquefaction Routes
A Direct Coal Liquefaction

Coal + Catalyst + Hydrogen Hydrocarbons (HxCy)
A Indirect Coal Liquefaction

1. Gasification
Coal + Oxygen + Steam 4 Syngas (H2 + CO)
2. FT Synthesis
H2 + CO + Catalyst -> Hydrocarbons (HxCy)
Coal Liquefaction Routes
A Direct Coal Liquefaction
- Partial dismantling of the coal structure under high H2
partial pressure
- Further hydrocracking of primary coal fragments
- Refining of coal liquids
- Products retaining ring structure
- Complete destruction of the ring structure in coal
Gasification to produce syngas (H2/CO)
- Removal of hetero-atoms (S, N) from syngas
- Catalytic synthesis of ultra clean paraffins
Hydrogenation and wax hydrocracking
Coal Liquefaction-Direct
H2S, NH3, COX

f
Recycle H2 Gas Recovery
Make-up Hydrogen. LPG
Treatment
I 1
Gasoline
Coal + Catalyst Coal Hydro-
Refining
Liquefaction treating Diesel Fuel
H-Donor
Slurry,
J
Slurry Heavy Vacuum
Fractionation
"Gas Oil (HVGO)
T
De-Ashed Solvent Ash Reject
Oil (DAO) De-ashing
DCL Background
A Originally developed in Germany in 1917
A Used to produce aviation fuel in WWII
A US spent $3.6 billion on DCL from 1975-2000
A Headwater DCL licensed to China in 2002
#11'
i
*4
•-••• it.
* V '
w -
|V
I
3* t
Jj
Ws r/
7
J
YJ
Lawrenceville, NJ Catlettsburg, KY Inner Mongolia, China
30 bpd 1800 bpd 17,000 bpd
Hybrid Plant - Block Flow Diagram
Raw FT products
Gasification Fischer Tropsch
Synthesis
FT tail gas
Recovery of Product Blending Final

Coal 1 Products
Hydrogen and Refining
H2
Direct Coal
Coal
Coal 2 Liquefaction
Raw DCL products
Commercializing CTL Technologies in U.S.
A CTL projects are capital intensive ($70,000- to

$120,000 per BPD)
A CTL products are compatible with and perform
similar to the petroleum -derived products
A Economy of scale is critical to project economic
(40,000 BPD + plant capacity)
A CTL project economic is very sensitive to capex
and world crude oil price
Economic Analysis Summary
A 44,000 BPD DCL Plant
A CAPEX = US$2.16 billion
A Annual Revenue = US$1,139 million
A Annual Expenses = 471 million
A Income before state tax = 668 million
A 1/3 Equity
A IRR of 30 % ($50/ton); 23% ($90/ ton)
A $962 Million NPV @ 12% Discount Rate
DCL
DCL --Summary
Summary
A CTL is a viable option to monetize coal reserve

A CTL technologies are commercially-ready
A Economy of scale and crude oil price are
critical to CTL project viability
A Government assistance in project finance is
needed for the first generation CTL plants
A Government guarantee on CTL product floor
prices is essential
A Future R&D efforts on plant efficiency and cost
reduction are needed
U.S. Direct Liquefaction Process History
Year Process Coal Capacity
1945-1953 Bergius 100 tons/day
- Louisiana, MO
1962-Early 1980s Solvent Refined Coal (SRC) 50 tons/day
- Pott-Broche
1963-1972 Consol Synthetic Fuels (CSF) 20 tons/day
- Two-Stage, Catalytic
1970s-Early 1980s SRC-I and SRC II (Gulf Oil Fort Lewis) 50 tons/day
- One-Stage, Non-catalytic
1965-Early 1980s H-Coal (Catlettsburg KY, HRI) 250 tons/day
- One-Stage, Catalytic
Late 1960s-Early EXXON Donor Solvent {Baytown, TX) 250 tons/day
1980s
Early 1980s-Late 1980s Integrated Two-Stage Liquefaction (ITSL) 6 tons/day
- Lummus
- Wilsonville (Southern Company)
- HRI
1990-1995 Multi-Stage Slurry Phase Liquefaction HTI 3 tons/day Proof-of-
concept
Non-U.S. Direct Liquefaction Processes
Capacity
Country Facility T ons/Dav Status
Germany BOTTROP Plant 200 Shut Down

-I.G. Farben Variant
Japan Brown Coal Liquefaction Plant 50 Shut Down (-1990)
- ITSL Variant
- Victoria, Australia
Japan Nedol Plant 150 Shut down {Late 1990s)
- ITSL Variant
- BIT. and SUBBIT. Coals
U.K. Point-of-AYR Plant 2.5 Shut Down (-1990)
- ITSL Variant
China Inner Mongolia 7,000 Start-up 2008

Natural Gas – Processing & Uses
B.Tech. APEG, Sem-V

University of Petroleum & Energy Studies
1st Nov’2017
G.S.Dang
gurbax49@gmail.com
2-11-2017
Gasification & GTL
Natural Gas
Natural Gas availability in India
Gas available in India (2010-12)... Estimated Gas supply (2010-12) in

mmscmd
242
210
RAJA' IN 2010 2012

AS'
CBM New domestic gas discoveries in

CAMBJ URII
KG basin are expected to spur
DAHEJ
HAZJRA domestic supply
SOUTH v"' Existing LNG terminals in India are
BASSEIN KG
currently undergoing capacity
expansion furthering the LNG
CAU' capacity in the country
S New CBM finds shall also augment
the natural gas supply
India consumed 59 billion cubic meters in FY 2009/10, up from 43 billion cubic meters in
FY 2008/09; Indian gas demand to increase to 94 billion cubic meters by 2020 and to 132
billion cubic meters by 2030
Natural Gas (NG)
• NG is a fossil fuel more evenly distributed worldwide
than crude oil
• It is found in reservoirs 3000 to 15,000 feet below the
surface of the earth, with reserves in about 90 countries
around the world
• Two-thirds of crude oil reserves & one third of NG
reserves are concentrated in the Middle East
• The Natural Gas is usually extracted from gas and oil
wells
• Smaller amounts are derived from supplemental
sources such as landfill gas and coal-derived gas
Natural Gas
• Natural gas consists of 90% methane (CH4) and,

depending on the origin gas fields, a mixture of other
gases such as ethane (C2H6), propane (C3H8),
carbon dioxide (CO2) or hydrogen (H2)
• There are two technologies for the direct use of
natural gas (CNG and LNG) and a third technology
which is used in the transformation of natural gas
into a liquid fuel (GTL)
• The term CNG (Compressed Natural Gas) stands for
natural gas which is compressed at a pressure of 200
bar
Natural Gas Processing
• Natural gas is processed to remove heavier

constituents ( heavier than methane) water vapour ,
acid gases ( CO2 ,H2S) , nitrogen, Mercury etc
• The block flow diagram shows a generalized, typical

configuration for the processing of raw natural gas
from non-associated gas wells
• It shows how raw natural gas is processed into sales

gas pipelined to the end user markets
Natural Gas Processing
Raw
gas o Gas
we1 1 s
TAIL GAS TREATING
ir
Tail Scat process Offgas to
Condensate to G' as Clauspol process
CONDENSATE i nci nerator
an oil refinery Others
AND
WATER REMOVAL
Wastewater Aci d SULFUR UNIT El ernent a I Nitrogen-rich

G' as Claus process Sulfur gas
ACID GAS REMOVAL

t
.“mine treating DEHYDRATION MERCURY NITROGEN REJECTION
Raw gas
Benfield process REMOVAL Cryogenic process
pipeline Glycol unit
PSA unit Mol sieves Absorption processes
PSA unit
Sulfinol process Act i u at e d car bon Adsorption processes
Others
ir
To sales gas-
pipeline
NGL RECOVERY
Ethane -P- SWEETENING UNITS -P FRACTIONATION TRAIN
Turbo-expander and
Propane -P Merox process -P Deethanizer -P demethanizer
Butanes -P- Sulfrex process -p- Depropanizer
Absorption (in older
Pentanes + -P Mol sieves Debutanizer plants]
LEGEND:
Located at gas wells Located in gas processing plant

Red Indicates final sales products Blue Indicates optional unit processes available
Condensate is also called natural gasoline or casinghead gasoline
Pentanes + are pentanes plus heavier hydrocarbons and also called natural gasoline
Acid gases are hydrogen sulfide and carbon dioxide
Sweetening processes remove mercaptans from the NGL products
PSA is Pressure Swing Adsorption
NGL is Natural Gas Liquids
Natural gas Processing
Processing of the raw natural gas yields Products / by-

products :
• Methane
• Ethane, Propane & Butane gases
• Natural-gas liquids (NGL): C5+ (which is the commonly used

term for pentanes plus higher molecular weight
hydrocarbons) with some traces of propane & butane
• Sulphur
LNG
Liquefied Natural Gas (LNG)
• LNG is a favourable form in which natural gas can be
transported
• LNG is liquefied natural gas transported& stored at –165° C
and at a pressure slightly above atmospheric
• In the condensed liquefied form, natural gas can be
transported very efficiently, e.g. in trucks or railway wagons
• Once it arrives at its destination, LNG can be transformed
into gaseous CNG (Regasification & Compression)
• Thus, LNG can enable a natural gas supply without
connection to the natural gas grid
Natural Gas Liquefaction Process
-161ºC
GAS GAS
Treatment
> and
Purification
>ÿ Storage >

J
•Removes condensate, CO2,
Mercury, and H2S
•Causes dehydration
Refrigerant
Loop
LNG
L
Compression
Natural Gas - Use
• Natural gas, a fossil fuel comprised mostly of methane,

is one of the cleanest burning alternative fuels
• It can be used in the form of piped natural gas (PNG),

compressed natural gas (CNG) or liquefied natural gas
(LNG) to fuel domestic appliances , cars and trucks etc
Natural Gas to Compressed Natural Gas
(NG to CNG)
• CNG is made by compressing Natural Gas (which is
mainly composed of Methane ,CH4), to less than 1% of
the volume it occupies at standard atmospheric
pressure
• CNG is odourless , colourless , and tasteless
• It is stored and distributed in hard containers at a

pressure of 200-250 bar, usually in cylindrical or
spherical shapes
Natural Gas – Automotive Fuel
• The concept of natural gas (NG) as an automotive fuel

dates back to the 1930s
• In Australia it was used as an automotive fuel in 1937
and France used it during the World War 1
• Canada and New Zealand started their conversion
programme in the early 1970s and some Asian and
South American countries in the 1980s
• Besides using NG to power vehicles, it has been tried
out for electricity and for heating homes and
commercial buildings
Natural Gas – Automotive Fuel
• NG in India is also being consumed mainly by the

fertilizer and power industry since 1984
• In 1992, the Gas Authority of India Limited introduced
a CNG network in India, but it failed to take-off due to
limited number of private vehicles switching over
• CNG has been an option as an automotive fuel since
1994 under the Central Motor Vehicle Act
• Major bulk of vehicles running on CNG is found in Delhi
and Mumbai as well as a few cities in Gujarat like
Vadodara , Surat and Ankleshwar
CNG compared to LNG
• CNG is often confused with Liquefied Natural Gas (LNG) ; both
are stored forms of natural gas
• Key difference is that CNG is gas and is stored as a gas at high
pressure, while LNG is in uncompressed liquid form
• CNG has a lower cost of production and storage compared to LNG
as it does not require an expensive cooling process and cryogenic
tanks
• CNG requires a much larger volume to store the same mass of
gasoline or petrol and the use of very high pressures (205 to 275
bar)
• LNG is often used for transporting natural gas over large
distances, in ships or pipelines, and the gas is then converted into
CNG before distribution to the end users
CNG - Alternate Fuel
• CNG is a safe fuel , lighter than air, it disperses easily into the
atmosphere
• CNG is 130 octane, higher than petrol ( 93 octane) ; consequently

CNG vehicle is more energy efficient
• Higher octane rating allows higher compression ratios and

improved thermal efficiency, reducing carbon dioxide (CO)
emissions
• CNG allows the use of catalytic converter more efficiently than

diesel
CNG - Alternate Fuel
Compared to petrol or diesel CNG vehicles emit
• 40% less of nitrous oxide (a toxic gas that creates smog)

• 90% less of hydrocarbons (which carry carcinogens)
• 80% less of carbon monoxide (poisonous pollutant)
• 25% less of carbon dioxide (a major greenhouse gas)
• Further, noise level of CNG engine is much lower than
that of diesel
CNG- Alternate Fuel
• CNG emits significantly less pollutants such as carbon

dioxide (CO2), unburnt hydrocarbons (UHC), carbon
monoxide (CO), nitrogen oxides (NOx),sulphur oxides
(SOx) and particulate matter (PM), compared to petrol
• CNG is thus is a cleaner fuel

Fuel Characteristics
CNG Gasoline/Petrol Diesel
Source/ feedstock Natural Gas Petroleum petroleum
Toxic to Skin No Moderate Moderate
Toxic to Lungs No Moderate moderate
Sp gravity lighter or
heavier than Air 0.55 (lighter) 3.4 4.0
(Air=1)
CNG as a fuel for IC Engine
• CNG is used in gasoline internal combustion (IC) engine
cars that have been converted into bi-fuel vehicles
(gasoline/CNG)
• CNG vehicles are increasingly used in the Asia – Pacific
region, Latin America, Europe, and America due to
increasing gasoline prices
• For environmental concerns, CNG is increasingly being
used in buses and trains
• CNG's volumetric energy density is estimated to be 42%
of LNG and 25% of diesel
CNG as a fuel for IC Engine
• Carbon monoxide emissions are reduced even further
• Due to lower carbon dioxide and nitrogen oxides

emissions, switching to CNG can help mitigate
greenhouse gas emissions
CNG - Safety
• CNG fuel systems are sealed, which prevents any spill or

evaporation losses
• Another practical advantage observed is the increased
life of lubricating oils, as CNG does not contaminate and
dilute the crankcase oil
• CNG mixes easily and evenly in air being a gaseous fuel
• CNG is less likely to auto-ignite on hot surfaces, since it
has a high auto-ignition temperature (540 °C) and a
narrow range (5%-15%) of flammability
Summary
• Natural gas/Metane is a fine energy source ,

relatively environment friendly
• It is being used a fuel (domestic & commercial) also

is used in power generation
• Energy demands are increasing and hence need to be

met through more and more use of Natural Gas
Condenser (HzS + CO2)
Sweet gas Acid gas
Makeup
-0ÿ
1r
water Reflux
drum
Rich Reflux
Top
tray
-+ÿ
c c
S E
•I'
—I iTl
cm
amine
Top
tray
-*ÿ
a
Pump
Absorber Regenerator
Sour Gas Bottom

%e- Bottom
Vapor
tray tray -*ÿ
Steam
>-1
Reboiler
Rich
amine
1—ÿ3 Lean
Liquid
nr
J c
Condensate
Typical operating ranges

amine
a
Pump
Absorber : 35 to 50 “C and 5 to 205 atm of absolute pressure

Regenerator : 115 to 126 "C and 1.4 to 1.7 atm of absolute pressure
at tower bottom
Amine Treating- General Operating Conditions

XTL Technology
X G L
Coal
n,
#
\ r
L X
* B*.
a
*•
i\' e9
'*!!,. k Art
« A.
**
.>44 •44
*
What is Gas To Liquids (GTL)?
Methane+ Oxygen Hydrogem- Carbon Fischer-Tropsch distillates- Water
monoxid
0* « •» Catalyst *
Raw
Natural
Gas CH Syngas
CO + 2H. - CHj-
° 2
_ Ethane Bintulu SMDS

LPG
GTL Naphth
LPG
fc— GTL Gas Oil
Condensate
n-Parafflns
Sulphur GTL Base
Lli"1 foil Oils
Conversion of natural gas to clean, high quality fuels

& products via the Fischer Tropsch process
Why Gas to Liquids?
Energy security -> Strategic diversification of energy
supply
-> Biomass and Coal to Liquids
Environment Trend towards cleaner fuels
Economic development Remote gas reserves
commercialisation
Most cost effective alternative fuel
-> Strategic diversific
_ M. • _
*
____--
I M.
GTL Fuel has unique properties:

— A.
*
-Virtually free of sulphur and r
aromatics
- f
<
_
-High cetane number

 Steam Reforming
• H2/CO = 3
• Endothermic
• CH4 + ½O2 → CO + 2H2
• H2/CO ≈ 1.70
• Exothermic
Syngas Processing

• CO + H2O ↔ CO2 + H2
 Clean up
• Particulates

I I
Alcohols
IQ- C6jÿ
t
Methanol MTBE
to Gasoline
Synthesis
process
MTBE

Biomass Gasification Search

Caricato da

Informazioni sul documento

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Biomass Gasification Search

Caricato da

Copyright:

Formati disponibili

What is Gasification ?

B. Tech ( APEG ) Semester V

• The product of gasiﬁcation is a combustible synthesis

• Gasiﬁcation processes operate in an oxygen-lean

H2S (Hydrogen Sulfide) Use

• The first public street lighting with gas took place in

• Baltimore in Maryland (USA) began the first

• Chemical industry (1960’s)

• Refinery industry (1980’s)

• Global power industry (2000’s)

• Current interest is to generate syngas as an

• Raw syngas from gasifier must be cleaned (removing

02/MAF Coal Feed Coal: Illinois #6

MAF coal - moisture & ash free coal

• Under gasifying conditions there is not enough oxygen available

• Consequently, instead of producing CO2, the carbon in the feed

• Both CO and H2 are excellent fuels for use in a combustion

• Combustion : Excess air

Gasification with Oxygen

Gasification of coal using steam and oxygen

•Carbon => C02 (carbon dioxide)

•Large volume of flyash & •Ash is converted to glassy slag

•Hg can be removed by •>90% of Hg removed by passing

• Another major difference is the amount of heat released by

 In combustion all the fuel’s chemical energy is released as

 In gasification most of the fuel’s chemical energy is not

 This is termed as cold gas efficiency

• Fate of Fuel’s Nitrogen and Sulphur

 Fuel bound nitrogen is predominantly converted in NOX

 In gasification it is converted into N2, NH3 and HCN

 which are removed from syngas during gas clean up to

 Sulphur in the fuel produces SOx in combustion but it is

 These compounds are removed efficiently in gas clean up

 Thus 99% of sulphur is removed from fuel and hence no

much more steam cycle some water needed for slurry,

The Gasifier / Reactor choice is very much linked to the

I Increasing heat and carbon content

Increasing moisture content

Peat Lignite Bituminous Coal Anthracite

Class Volatile matter Fixed carbon Heating value

Wt% Wt% MJ/Kg

Anthracite <8 >92 36-37

Bituminous 8-22 78-92 32-36

Sub-bituminous 22-27 73-78 28-32

Brown coal 27-35 65-73 26-28

Anthracite Bituminous Lignite Peat Crude Oil

It provides elemental composition ( %) of the coal

HHV in MJ/Kg = 33.86*C+144.4*(H-O/8)+9.428*S

HHV in MJ/Kg = 34.91*C+117.83*H-10.34*O -

• Coal ( ≈49 %) is largely used feedstock for gasification

• Coal has volatile matter( ≈20%) except in anthracite

• High ash containing coal creates various operation

• Petcoke is a product of refineries from delayed coking

• High sulphur material

• An attractive feedstock for gasification

• Petcoke has high carbon content but volatile matter is

• It is less reactive feedstock and requires high

• High sulphur content in petcoke ( >5%) requires

• Heavy petroleum residues including petcoke are

• Gasification is rarely applied to heavy oil feedstocks

Indian Coals in general :

Petcoke on the contrary:

Combination of Coal with Petcoke forms a balanced feed

• Orimulsion or emulsified bitumen-water mixture produced

HHV in MJ/Kg = 33.86C+144.4(H-O/8)+9.428*S

HHV in MJ/Kg = 34.91C+117.83H-10.34*O -