Technologies for Biogas Upgrading

Prof. Virendra K. Vijay

Head, Centre for Rural Development &
Technology, IIT, Delhi
vkvijay@rdat.iitd.ernet.in
Biogas Production & Utilization

(Source: OFGEM, 2011)

Upgraded & Bottled Biogas as a Replacement of
Existing Petroleum Fuels for Mobility
Applications
Biogas as an Alternate to Natural Gas!

Properties Natural Gas Raw Biogas Upgraded

Biogas(CBG/Biomethane)
Composition% (v/v) CH4 – 89.14% CH4 – 50- 65% CH4 Min - 90%
CO2 – 4.38% CO2 – 35-45% CO2 Max (v/v) – 4%
H2 – 0.01% N2 – 1-25% CO2 + N2 + O2 Max (v/v) – 10%
N2 – 0.11% O2 – 0.1-5 % O2 Max (v/v) – 0.5 %
C2H6 – 4.05% H2S – 10- 3000 ppm H2S mg/m3 Max – 30.3
C3H8 – 0.83% Moisture mg/m3Max -16
Iso-C4H10 – 0.28%
Neo-C4H10 – 0.66%
Iso-C5H12 – 0.09%
Neo-C5H12 – 0.28%
C6H14 -0.17%
Lower Heating Value 44.39 MJ/kg 20.5 MJ/kg 42.62 MJ/kg

Relative Density 0.765 1.014 0.714

Flame speed (cm/sec) 34 25 –

Stoichiometric A/F 17.03 17.16 17.16

(kg of Air/ kg of Fuel)
Auto-ignition 540 650 –
Temperature (⁰C)
 Raw Biogas
Biogas Upgrading: The Gas Separation Problem
• A low Grade fuel (CH4 55-65 % & • A high grade fuel (CH4 > 90 % and
CO2 35-45 %) with lower
percentage of methane.
• Mode of utilisation
• The presence of CO2 besides
being non combustible,
restrains its compressibility
there by making biogas
difficult to be stored in
containers.
Cleaned/Upgraded
Biogas
< 10 % other gases) with high
percentage of methane.
• Mode of utilisation
• Onsite/ Remote applications
• Methane burns faster hence
yields a higher specific output
and thermal efficiency
compared to raw biogas when
used as engine fuel.
• Upgrading , compression and
bottling facilitates easy storage
and transportation as a vehicle
fuel
Utilization of Upgraded Biogas

First Biomethane bus in India Biomethane Bus in Sweden

Biogas car in Sweden Biogas Train in Sweden

 Upgraded & Bottled Biogas for Cooking and Vehicular Applications

Cascades of Upgraded biogas being Biogas Motorcycle in Thailand Biogas Car in India
transported

Bottled biomethane used for power

generation
Upgraded and bottled biogas for use as a cooking fuel http://www.pluginindia.com/advantagesusesofbiogas.html
 Techniques for Biogas Cleaning/Upgrading

Absorption Adsorption Membrane Cryogenic

Pressure High Pressure

Water
Swing Gas – Gas
Scrubbing
Adsorption separation

Low Pressure
Physical Gas – Liquid
Scrubbing separation

Chemical
Scrubbing

• Decide for suitable technology primarily NOT by investment costs

• Select suitable technology according to:
 All Technologies are Not Equal.
• Upgrading capacity
 The current biogas technologies have different strengths and weaknesses.
 The •established
CH4 recovery
technologies for the removal of CO2 from biogas are based on the differences in molecular,
thermodynamic
• andratio
Turn down transport properties of the gaseous components in biogas.
• Shut down / start up performance and ease of operation
• Product quality required
• Chemicals and energy consumption
 • Simple process
• Based on high solubility of CO2 and H2S
in water
• H2S pre-removal is not mandatory
• Can tolerate 300–2500 ppmv
• Low investment and operational cost
• Low methane slip
• High energy efficiency >96%
• Best in Medium and Large Applications
• Proven technology
• Robust system
• Regeneration is simple with
depressurisation of water
• Water is recycled

Water Scrubbing Process for Biogas Upgradation

 • Chemical absorption of CO2 into chemicals
• MEA/DMEA
• High selectivity for CO2
• Low methane loss
• Regeneration by heating spent chemical at high
temperatures
• H2S pre-removal is mandatory
• Otherwise H2S will also be absorbed in the
solvent leading to higher heating requirements
for regeneration

Chemical Scrubbing Process for Biogas Upgradation

 • Adsorption on activated carbon or zeolite under pressure
• Adsorbent is regenerated by sequential decrease in pressu
• Pre-removal of H2S is mandatory
• Low biomethane recovery

Pressure Swing Adsorption Process for Biogas Upgradation

 • Low investment and
operational cost
• Low methane slip 98% with
multi stage systems
• Compact
• Simple on/off Simple on/off
• Best for low and Medium
Flows

Membrane Cascade Separation System For Biogas Upgradation

i) General Design, Ii) Single Stage Configuration, Iii) Two-stage Configuration With A Recirculation Loop, Iv) Two-stage Configuration With Sweep And V) Three-stage Configuration With Sweep
 • Liquefied CO2
• Complex Technique
• High energy requirement for
• High pressure
• low temperatures

Cryo-technology for Biogas Upgradation

 Summary of Biogas Upgrading Technologies
Parameter Basis of Gas Pre Working Methane Solvent/ Fate of Heat % Purity N2, O2 Invest Ease of
Water scrubbing technology
Operation Cleaning is one of Loss
Pressur the most widelySplit
Adsorbent implemented and
Biogas Require of CH4 mature technology
in separation Cost operation
Requirement e during ment Upgraded €/Nm3
with over 41% plants out of 503(bar)
Method
biogas upgrading plants installed worldwide
Upgradatio Gas
(IEA, 2017).
biogas
n

• Based on
Water Scrubbing
physical
Physical
Absorption
absorption
Not required,
H S removed
2
6-10
of<Medium
gases
2%,
inWater
water- no chemical No
reaction
95-98
involved.
No Cheapest, Simplest
0.13 -15
• No pre-cleaningalong of with
H2CO2
S required, since solubility of H2S is higher than CO2, it will also get
Physical dissolved in water
Physical at high4-7pressures.
Not required < 4%, Organic Medium,7 > 96, < 93- No 0.25 Difficult in
Absorption Absorption High solvents, 0-80C 98% operation
• Water is used as a solvent – cheap, easily and abundantly available.
CH rich (above
• Regeneration
Chemical Chemical ofRequired
water & is simple
1 – release
<0.1%, of Alkali
Amines, pressure. 4
90%) Too high > 98 No 0.28 Difficult in
Absorption Absorption Recommended Low solutions biomethane gas 120-160 C operation
• No heat requirement during absorption or regeneration stream and CO process.
2
rich (80-90%)
• No
Pressure Swing complicated
Adsorption and complex
Required & 4-8 bar equipment
<2, 6 -10%, required.
Molecular
off gas stream
No > 96, > 98 Yes 0.26 Extensive
with some CH
Adsorption
• Easy operation and Highly Medium Sieves 4 process
maintenance.
recommended
as loss
control
needed
•
Membrane
No use of chemicals.
Gas – Permeation Required & >10-20, High Membranes No 90-92%, Partly Cheap, Easy
Separation Gas Recommended 20-36 0.22
• Cheap,
Gas - Investment cost is1 less. High 96%
Liquid

Cryogenic Multistage Recommended 40 Lowest Not required CH4 rich (above No 99 No 0.40 - Complex,
Separation Compression 98%) 0.44, Most multifaceted
and biomethane gas expensive
condensation stream and
solid CO2 rich
(99%) off
stream
 State of the Art

Water Scrubbing based BioCH4 and BioCO2

Production Technology Developed at IIT
Delhi, India

Awarded: Patent No. 284588 is granted on 27/06/2017 for “A Device and a Process for Conversion of Biogas to a Fuel Gas
with enhanced Thermal Efficiency. V.K.Vijay, P.M.V. Subbarao, R.R. Gaur and S.S. Kapdi. Patent Application No.
161/DEL/2006 dated 20.1.2006
Applied:
V .K. Vijay, Rimika Kapoor, P.M.V. Subbarao, “A System for Biomethane and Bio Carbon Dioxide Production from
Biogas and a Method Thereof”. (Indian) – Patent Application No.: 201811018965, Dated: May 21, 2018.
Water Scrubbing based BioCH4 and BioCO2 Production System at IIT Delhi
 WS1 (BioCH4 WS2 (BioCO2
Production) Production)
Capacity 10Nm3/h 5 Nm3/h
Gas Flow Rate
WS1
Quality of Gas 95% BioCH4 99.9% BioCO2
Obtained
Recovery of 91% 88.5%
WS2 Gas
 Upgraded Biogas Dispensing System at IIT Delhi

High Pressure Compressor Two cylinder cascade for Dispensing Nozzle -

bottling of upgraded NZ type
biogas
BioCH4 Application as Vehicular Fuel
 BioCO2 Application

• Algae Cultivation
• Grain Fumigation
• Greenhouses
• Chemical Manufacturing
Mobile Biogas Upgradation System developed at IIT Delhi
THANK YOU
 Biogas
Biogas as Upgrading:
an AlternateThe Gas Separation
to Natural Gas! Problem
Properties Natural Gas Raw Biogas Upgraded Biogas(Biomethane)

Composition% (v/v) CH4 – 89.14% CH4 – 50- 65% CH4 Min - 90%
CO2 – 4.38% CO2 – 35-45% CO2 Max (v/v) – 4%
H2 – 0.01% N2 – 1-25% CO2 + N2 + O2 Max (v/v) – 10%
N2 – 0.11% O2 – 0.1-5 % O2 Max (v/v) – 0.5 %
C2H6 – 4.05% H2S – 10- 3000 ppm H2S mg/m3 Max – 30.3
C3H8 – 0.83% Moisture mg/m3Max -16
Iso-C4H10 – 0.28%
Neo-C4H10 – 0.66%
Iso-C5H12 – 0.09%
Neo-C5H12 – 0.28%
C6H14 -0.17%
Lower Heating Value 44.39 MJ/kg 20.5 MJ/kg 42.62 MJ/kg

Relative Density 0.765 1.014 0.714

Flame speed (cm/sec) 34 25 –

Stoichiometric A/F 17.03 17.16 17.16

(kg of Air/ kg of Fuel)

Auto-ignition Temperature 540 650 –

(⁰C)
Techniques for Carbon Dioxide Removal

Absorption Adsorption Membrane Cryogenic

Pressure High Pressure

Water
Swing Gas – Gas
Scrubbing
Adsorption separation

Low Pressure
Physical Gas – Liquid
Scrubbing separation

Chemical
Scrubbing

 The established technologies for the removal of CO2 from biogas are based on the differences in molecular,
thermodynamic and transport properties of the gaseous components in biogas.
 Parameter Basis of Gas Pre Workin Methane Solvent/ Fate of Heat % Purity N2, O2 Invest Ease of
Operation Cleaning g Loss Adsorben Split Requir of CH4 in separatio Cost operation
Requireme Pressu t Biogas ement Upgrade n €/Nm3
Method nt re during d Gas biogas
(bar) Upgradati
In view of the above, the need of the hour is on
Water Scrubbing Physical Not required, 6-10 < 2%, Water No 95-98 No Cheapest, Simplest
Water
Absorption scrubbing
H S removed
2
technology
Medium is one of the most widely implemented with
0.13 -15 over
Optimize 135 the plants
along out
water of 400 biogas
with CO2
scrubbing upgrading
technology to plants
produce installed worldwide
high quality (IEA, 2013).
biomethane along
Physical Physical Not required 4-7 < 4%, Organic Medium, > 96, < 93- No 0.25 Difficult in
with, Absorption
Absorption High solvents, 70-80C 98% operation

Chemical Chemical • Based on

Required & physical
1 absorption
<0.1%, Amines,of gases CH rich
(above in 90%)water-
4
Too high no
> 98chemical
No reaction
0.28 Difficult in
 Minimisation
Absorption and
Absorption involved.Recovery CH
Recommended Low lossAlkali
4 and CO 2 from the off gas stream of the plant
biomethane 120-160 operation
solutions gas stream C
• No pre-cleaning of H2S required, since and CO solubility
rich
2 of H2S is higher than CO2, it
to reduce
Pressure Swing Adsorption will greenhouse
also
Required &get 4-8 bar gas
dissolved
<2, inemissions
6 -10%, water
Molecularat high into
gas
the environment
(80-90%) off No
pressures.
stream
> 96, > 98 Yesand 0.26 Extensive
Adsorption Highly Medium Sieves process
• Water is used as a solvent – cheap,CHeasily
recommended with some
as loss
and abundantly available. control
 to
Membrane Gas – Permeation
increase
• Regenerationthe
Required &
economic
of water viability
is simple
>10-20, High
of the 4

Membranes– release of
biogas upgrading
No pressure.
90-92%,
setup
Partly Cheap,
needed
Easy
Separation Gas Recommended 20-36 0.22
Gas - • No heat requirement
1 High during absorption or regeneration
96% process.
 make the complete process carbon negative.
Liquid
• No complicated and complex equipment required.
Cryogenic
Separation
•
Multistage
Compression
Easy operation
Recommended 40 and maintenance.
Lowest Not required CH4 rich
(above 98%)
No 99 No 0.40 -
0.44,
Complex,
multifaceted
and • No
condensation
use of chemicals. biomethane
gas stream
Most
expensiv
• Cheap, Investment cost is less. and solid CO2
rich (99%) off
e
Water Scrubbing Process
Methane Loss during Water Scrubbing Process

• Key parameter defining the economic and environmental performance of the process.

• CH4 is approximately 21 times stronger greenhouse gas than CO2 and high CH4 losses
negate the plant economy.

• CH4 losses are an integral part of the upgrading process, because a high CH4 level in the
upgraded gas stands in contradiction to low CH4 losses.

• Dependent on operating parameters (pressure, water flow rate, flash pressure, etc) and
conditions.

• CH4 losses cannot be avoided during the upgradation process but they can only be
minimised by maximum recovery of CH4 from off gas stream.
Treatment Methods for Off Gas (Methane Loss Minimization) from
Biogas Upgrading Plant
Treatment Methods Conclusion
Combustion in Lean  Off gas is captured and mixed with Natural Gas or  Complex and separate gas treatment
Burner / Torch Biogas facilities
 Flared as a torch/ Used for combustion in the boiler  Requires another energy source for
Thermal Oxidation  Oxidation at high temperatures combustion/ treatment
 Natural gas/biogas used for attaining high  Requires sophisticated design and
temperatures careful sizing of the system
Thermal Catalytic  Platinum, palladium or cobalt as catalyst  Costly
Oxidation  Catalytically oxidize CH4 to CO2 and water vapour at the  Unfeasible
surface of the catalyst  Oxidize CH4
 Catalyst lowers the energy required for oxidation  Does not recover CH4
Regenerative Thermal  Heat transfer bed filled with porous ceramic media
Oxidation  Oxidation takes place over the heated media
Flash Tank  Off gas is depressurized in a flash tank at 2-4 bar and  Simple equipment
CH4 is recovered and recirculated back into the raw gas  CH4 recovery is dependent on pressure
inlet. and retention time of water in the
flash tank
 Most preferable method of CH4 loss
minimization and recovery
CO2 Recovery and Utilisation from Off Gas Stream

••Conventionally,
Literature and data related
Carbon to CO
capture 2 recovery
and from biogas
storage (CCS) is oftenupgrading
associatedplants is rare
with flue gas
mixtures, it can also be combined with bio-energy conversion.
• This important area is yet to be explored.
• Off gas stream of the water scrubbing process can also be processed to recover CO2 as
•bioCO
Need2totodevelop
be used sophisticated
in different applications
method forlike
CO2manufacturing
separation andand synthesis
recovery of the
from salicyclic
off gas
acid, methanol,
stream of watercarbonates, polycarbonates etc. or can be used for algae production, in
scrubbing plant.
greenhouses and anaerobic digesters to provide CO2 rich environment and in warehouses
as a fumigant.

• The main feature of upgradation process is that separation of CO2 is already an intrinsic
step.
Factors Affecting CO2 Removal in Packed Bed Scrubber

1. Solubility of Gaseous Components in Water

2. Operating & Design Parameters

• Pressure
• Temperature
• Water and Gas Flow Rates
• Packing
• Packed Bed Diameter and Height
Solubility of Biogas Components in Water
Comparison of Solubility of Gases in Water [Lems,2009]
Biogas Solubility
Component (mole fraction)

Pressure

Temp⁰ 1 2.75 5
C
25 2.0*10-3 -
H2S
30 1.55*10-3 - 7.92*10-3 • At STP, the solubility for H2S is
25 0.609*10-3 3.02*10-3 approximately 2.5 and 73 times
CO2 higher than CO2 and CH4.
30 0.531*10-3 - 2.66*10-3

25 0.277*10-4 -
CH4
30 0.6*10-4 1.15*10-4
Effects of Operating and Design Factors on CO2 removal from
a Gas Mixture in Water Scrubbing Column

Packing
•Gas TheFlow
size of Rate
packing used influences the height and diameter of a column, the pressure drop and cost of
Pressure
packing.
• The solubility of a gas in water increases with increases in pressure. High pressures also decrease the quantity of
•• Sizing
As the packing size is increased, the cost per unit volume of packing and the pressure drop per unit height
solventParameter
required.
of packing
• Too low  the are driving
reducedforce
which reduces
inside the mass
the tower is nottransfer efficiency.
high enough This efficient
to cause results inmass
a requirement
transfer. of taller
column height to achieve the required purity and separation.
Temperature
• As the gas flow rates are increased  it causes better spreading capacity and enhanced mixing of the gas and
• Lowerwater causing mass in
temperature transfer
the to increase.
absorption tower is beneficial for the enhancement of CO2 absorption (solubility
Column Diameter
•• To increases
Very
avoid  gas
with decrease
highchannelling
pressureindrop
in the temperature).
increases
column packed rapidly
with and water
random starts accumulating
packings, the diameter in of
thethe
upper part ofpacking
individual the column
preventing the flow of gas  flooding condition.
pieces should be smaller than at least 1/8th the tower diameter.
• Too high
Water Flow Rate
gas flow rates can cause flooding in the column, however with high liquid flow rates flooding can occur
•Columneven- at lower
areagas
forflow
massrates.
Low Height
less transfer for gas molecules.
•• High - increase
Determines theineffectiveness
absorption ofofgasgasdue to the continuous
separation renewal
and the level of theofgas
of purity gasliquid boundary  increase in the
required.
• concentration
Conventionally,ofawater molecules reacting
height-to-diameter with- 20:1
of 10:1 carbon dioxide
is used formolecules.
water scrubbing plants.
•• Too high -column
A higher reducedcancross sectional
separate area
more COavailable for flow of gas  gas pressure drop increases  flooding
2 from biogas with lower incoming biogas flow rates, whereas a
wider column can treat a larger volume of biogas.
 Designing the Packed Bed Scrubber for CO2 removal from Biogas

• Aim 99 % removal of carbon dioxide from biogas.

• Diameter and Height - main determinants of designing the packed bed.
• In conventional packed bed design calculations, L/G is calculated by using the equilibrium line
and operating line based on Henry's law (applicable to only dilute solutions).
• Whereas, in our case, (biogas), the concentration of CO2 in the gas mixture is quite high,
therefore, making Henry’s law inappropriate for calculating the packed bed dimensions.
• A GUI MATLAB based on a recent law given by Duan and Sun (2003) is used to calculate the
design of the packed bed for high concentration of solute in gaseous phase .
• Input values
 diameter of the column,
 inlet gas flow rate,
 water flow rate,
 pressure inside the column and
 packing characteristics.
• The software calculates the height of the packed bed, loading and flooding conditions.