OVERVIEW

HYDROGEN & DHT

UNITS

DHT BLOCK REFRESHER COURSE– JAN 2018

AGENDA

➢ Process Description - PDS / FDS / Reformer/PSA

➢ Process Chemistry - PDS / FDS / Reformer/PSA

➢ Process Description - DHT / Amine Section

➢ Process Chemistry – DHT / Amine Section

DHT BLOCK REFRESHER COURSE – JAN 2018 2

HGU & DHT Block Diagram

Purge Gas

Naphtha
Lean Amine
PDS FDS Reformer PSA from SRU

H2
Hydrogen

H2S rich H2
DHT Amine Section
Sour Diesel Rich Amine to SRU

Sweet Diesel to Tanks

Sour Water

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Hydrogen Production

Hydrogen Plant is designed to produce 4500 Kg/hr (36000 Tons /

Annum) of pure hydrogen (99.9%) using Steam Reforming of
Naphtha with further enrichment in shift converters & purification
in PSA.

Process Steps
➢ Feed (Naphtha) Pre-desulphurisation

➢ Final desulphurisation

➢ Steam Naphtha Reforming (Pre-Reforming + Reforming +

Steam Generation)
➢ CO HT & LT shift conversion

➢ H2 purification (PSA)

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PDS Section PFD

Sour
Sour Gas
Naphtha Diene Rx Hydrogenator -I
270o/320o 97o
160o/200o
7.8 kg/cm2
1.3kg/cm2g
Surge
Ni-Mo
Drum
Ni-Mo

Stripper
Co-Mo
Sour
water

Quench
175o/211o 271o/321o

28.7 kg/cm2
Sour Gas

Seperator
RGC Make 21 Kg/cm2g 163o
up
H2 Sour
water
Sweet
DHT BLOCK REFRESHER COURSE – JAN 2018 Naphtha 5
Pre - Desulphurization Section (PDS)

➢ To remove Sulphur from Naphtha which is poison to Pre-reformer and

Reformer catalyst (Sulphur reduction to < 10PPM).

➢ Naphtha and recycle H2 are heated and sent to Diene Reactor (91-R-
01) and Hydrogenator-I (90-R-02) where Olefins are saturated and
Sulphur compounds are converted to H2S over Ni-Mo catalyst HR 945
and HR 406 Cobalt-Molybdenum based catalyst
CnH2n + H2 → CnH2n+2
CnH2n-2 + H2 → CnH2n
RSH + H2 → RH + H2S (Exothermic Reaction)

➢ Other Side Reactions

O2+H2 →2H2O ( Exothermic Reaction)
CnH2n+H2 →CO+H2O (Exothermic Reaction)
CO2+H2→ CO+H2O (Endothermic Reaction)
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FDS Section PFD

H2 from PSA

H2 Comp
36.4 kg/cm2
Surge Drum
2.5 kg/cm2g
386o 385o

Al2O3 Al2O3
CoMox
ZnO ZnO

Cu Cu
Preheat in 366o
•LT Shift Efflnt
•HT Shift Efflnt
•Reformer Coil Desulfurizer A/B
Hydrogenator - II
Desul
Naphtha
Pre-reformer

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Final De-sulphurisation Section (FDS)

➢ To reduce the Sulphur content of Naphtha from 10 ppm to < 0.1 ppm.

➢ Naphtha and H2 are heated and processed in Hydrogenator-II (R-20) to

convert S compounds to H2S over Cobalt-Molybdenum based catalyst.
R - SH + H2 → R - H + H2S
R-Cl + H2 → R-H + HCl
T=380 – 400 oC & P= 36.4 Kg/cm2g

➢ Chloride removal in R21A/B by alumina based Chloride adsorbent.

6HCl+Al2O3 → 2 AlCl3 + 3H2O

➢ The H2S generated in R20 is absorbed in ZnO reactor(R21A/B)

ZnO + H2S → ZnS + H2O

● Deep desulphurization copper based adsorbent reduces the sulphur content in

the feed to very low level (<0.5 ppb).

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Reformer Section
Export Steam
From Process
Cond Degasser
Process Steam
Drum PSA Purge Gas
To Stack
M / U Fuel
630o
Steam
From DM Water
Desulfurizers
PRE-REFORMER

REFORMER
Reformax-330
Reformax-210
455o/499o
Reformax-100

DM WATER
DEGASSER Preheat

Export Steam
503o/541o Drum
900o PROCESS GAS
Steam BOILER

To HT SHIFT
REACTOR

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Steam Pre-reforming & Reforming

● The desulphurized vaporized feed reacts with steam over a nickel based
catalyst to form a mixture of methane, carbon dioxide, carbon monoxide and
hydrogen in both the Pre-reformer (91-R-22) and the Reformer (91-F-20).

● In the adiabatic pre-reformer the conversion of higher hydrocarbons results in

a temperature rise over the reactor.

● Process gas is further mixed with steam and passed through a Nickel catalyst
packed in vertical narrow 136 tubes (in 4 equal rows) mounted in the reformer
at high temperature.

● Due to pre-reformer, carbon formation in the Reformer due to cracking of C2+

is negligible.

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Steam Pre-reforming & Reforming

➢ CnHm + nH2O ←→ nCO + (n+ m/2)H2 (endothermic)

CH4 + H2O ← → CO + 3H2 (endothermic)
C + H2O ←→ CO + H2 (endothermic)

➢ Pre-reformer : Inlet / Outlet T= 455-499 / 545 oC & P=34.4 kg/cm2g

➢ Reformer : Inlet / Outlet T= 630 / 870-900 oC & P=33.2 kg/cm2g

➢ Reforming Process is endothermic and heat is supplied by vaporised

Naptha make –up fuel and purge gas firing with 50 top fired burners.

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Steam Reforming

Parameters influencing design and operation

➢ Pressure - favored by low pressure.
➢ Steam carbon ratio:
Defined as moles of steam per atom of carbon in the HC feed.
➢ Carbon formation
2CO → C + CO2
Sufficient steam is required to avoid carbon lay down in the
catalyst
➢ Temperature : Conversion favored by high temperature.

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CO Conversion Section

From Process LT Shift

Gas Boiler 330o/350o
190o/220o

PSA
Shiftmax-120

HT Shiftmax-210
Shift 113o/115o 40o
COLD COND
SEPARATOR

423o/436o 229o/260o HOT COND

SEPARATOR

Heat exchange with Heat exchange with

•Feed+H2 •Feed+H2 To Process
•Satd steam •DM Water Steam Drum
•Process BFW •Process BFW PROCESS COND
Preheat
•Clean BFW •Clean BFW DEGASSER

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CO Shift Conversion

➢ HT & LT shift reaction converts the carbon monoxide present in

the reformer gas to Carbon dioxide producing additional H2.
CO + H2 ←→ CO2 +H2 (exothermic)
➢ SOR & EOR inlet temperatures:
HT Shift : 330 – 350 oC & LT Shift : 190 – 220 oC
➢ Improve PSA performance by reducing CO load.
➢ The Catalyst should be operated at the minimum practical inlet
temperature giving the desired conversion of CO.
➢ As the Catalyst ages it is necessary to increase the converter inlet
temperature in order to maintain a satisfactory exit CO level.

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Importance of Recycle Hydrogen

H2 molecules
Predominantly Reforming Reactions
Recycle H2 of FDS section keeps this thus generation of H2
portion of catalyst in reduced state.

Predominantly Catalytic
Cracking Reactions &
Olefin Saturation
Generated Hydrogen Keeps the
catalyst of this portion in
reduced state.

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PSA (Pressure Swing Adsorption)

➢ PSA unit works on the principle that the adsorbent attracts and retains
the impurities at higher pressure and releases them at lower pressure.
➢ Designed to produce 51496.2 Nm3/h hydrogen with a purity of 99.97
mol% out of 79229.2 Nm3/h feed gas with a hydrogen recovery rate of
89.5 %.
➢ Designed for continuous operation at all loads between 100% and 27
%.
➢ PSA Unit can be operated with 10, 9, 8, 7, 6 or 5 adsorbers.
➢ 4 Basic steps carried out by automatic PLC controlled control valves.
1. Adsorption
2. Expansion or Depressurization
3. Purging & Dumping
4. Re-Pressurisation

DHT BLOCK REFRESHER COURSE – JAN 2018 16

PSA(Pressure Swing Adsorption)

Flare

Purge Gas to
Flare Burners
Process Gas from 91-V-28 H2 to PDS/FDS
H2 to B.L

DHT BLOCK REFRESHER COURSE – JAN 2018 17

Adsorption

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DHT Unit

● The DHDT unit is designed to hydro treat a feed blend containing

➢ Kerosene
➢ Heavy Gas oil (HGO)
➢ Vacuum Diesel
➢ Light Coker Gas Oil (LCGO)
➢ Light Cycle Oil (LCO)
➢ Coker Naphtha and Disulfide Oil (DSO)

● Sulphur reduction from 2.1-2.2 wt% to less than 8 wt ppm

● Design : 1.32 MMTPA (Initial –Non-coker case) & 2.2 MMTPA

(Future case with Delayed Coker Unit)

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SPECIFICATIONS OF DIESEL

Specification BS-I BS-II Euro-III Euro-IV

Sulfur, ppmw max 2500 500 350 50
Cetane number, min 48 48 51 51

Polyaromatics % max No spec No spec 11 11

Density, kg/m3 820 - 860 820 - 860 820 – 845 820 – 845
Distillation
T 85 max 350 350 No spec No spec

T 95 max 370 370 360 360

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DHT Unit

DHT Major Sections:

➢ DHDS Feed section – Feed filter, Coalescer and Surge drum.

● DHDS Reaction Section - Charge pumps, Heater, Reactors, Effluent

exchangers, Wash water system, separator, flash drum, Lean Amine
system, off gas scrubber, recycle gas amine scrubber, RGC and MGC’s.

● The fractionation section includes stripper, stripper receiver, product

fractionator, product fractionator re-boiler, product fractionator
receiver, kerosene stripper, over head pumps, product pumps and
product exchangers. In future the fractionator section will include
debutanizer and its receiver also.

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DHT Unit : Product Specifications

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Reaction Section

T: 88

Make up H2
P: 65.7
T:315 T: 349 MGC
P: 75 P:73.1

T: 49
Single KF 848- KF 848- P: 65.7
pass 1.3Q Quench
1.3Q
T: 268 Lean
Reactor-1
P: 79.3 Amine
KF 848- Reactor-2
1.3Q Recycle
Combined RGC gas
Feed Scrubber
Heater T: 81
T: 355 T: 371 P: 84
P: 73.1 T:347 P:71.5
P: 81.9 Rich
Amine
Sour
T: 42
Diesel Feed
Surge P: 65.9
Drum T: 237
P: 81
Separator T:55 To
Seperator P: 66.3 Flash
Drum
To Flash Drum

DHT BLOCK REFRESHER COURSE – JAN 2018 To Flash Drum 23

Fractionation Section
Sour Fuel
Fuel Gas
Gas T: 153 Naphtha
P: 9.9 T: 135
P: 0.77
Lean T: 293
Amine P: 9.8
St

Product Fractionator
Off Gas ri

Stripper
Scrubber T: 181
p
P: 0.98
T: 42 pe T: 177
Rich P: 27.2
Amine
r P: 0.94
Kerosene
Stripper
Steam
T: 340
P: 33

T: 189
T: 237 Kerosene
P: 1.3
P: 1.1
T:59
P: 27.2
T: 57 Flash
T: 282
P: 1.1

P: 27.5 Drum
P: 15.2
T: 59

Sour Prod. Fract- Reboiler

Water T: 283 T:45 Product
P: 10.3 P: 5 Diesel 24
DHT Block Relatives

H2 to VRCFP
Sour Water to
H2 from VRCFP D-SRU/ VRCFP
Fuel Gas

Cold Feed from Tanks

CDUs LD/HD/VD/VBN Sweet Diesel to
DHT Tanks
FCCUs LCO/HCO

AAG to SRU / D-SRU DHT Naphtha to

MS Blend / Storage

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Diesel Composition

Diesel composition : ( 9-23 Carbon atoms )

➢ Paraffin ( straight chain Hydrocarbons) -- Olefins

➢ Naphthenes (Cyclic Hydrocarbons)

➢ Aromatic Compounds ( benzene Rings like structures)

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DHT Reactions

➢ Desirable Reactions
➢ Elimination of Sulphur
➢ Elimination of Nitrogen and oxygen
➢ Elimination of metals
➢ Saturation of olefins/ di-olefin & Aromatics

➢ Undesirable Reactions
➢ Hydro cracking
➢ coking

DHT BLOCK REFRESHER COURSE – JAN 2018 27

DHT Reactions

Desulphurisation
➢ Mercaptans , sulfides and disulfides react easily leading to saturated and
aromatic compounds.
➢ Sulphur combined into cycles of aromatic structure is difficult to eliminate.
➢ Desulphurization reaction is exothermic, consume hydrogen and produce
H2S.
➢ 2 to 3 molecules of hydrogen are consumed for every atom of sulphur
removal.

+ 6H2 H 2S + + Heat
S

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DHT Reactions

Elimination of Nitrogen
C
C C
+ 5H2 C5H12 + NH3 + Heat
C C
N

➢ Nitrogen removal is desired to improve feed stock color & color stability.

➢ De-nitrification rate is lower than the desulphurization rate.

➢ Reactions are exothermic.

➢ On average 4 molecules of H2 are consumed per atom of nitrogen

DHT BLOCK REFRESHER COURSE – JAN 2018 29

DHT Reactions

Hydrogenation
➢ Hydrogenation occurs of olefinic and aromatic compounds.
➢ The reactions are highly exothermic and decreases the number of reacting
molecules.
C-C=C-C-C-C + H2 → C-C-C-C-C-C
Demetalization:
The organo metal compounds ( As, Pb, Cu, Ni, V) are cracked and the metals are
trapped on the catalyst.
Undesirable Reactions : Hydro cracking
Cracking of Hydrocarbon in presence of hydrogen
* Consumes hydrogen * Reduces product yield * Hydrogen purity of recycle gas.

DHT BLOCK REFRESHER COURSE – JAN 2018 30

DHT Reactions

Undesirable Reactions :Coking

Heavy molecules are adsorbed on the active sites of the catalyst, it may get
condensed and polymerize on the catalyst and form coke.

Catalyst Active Sites Catalyst Pores

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Effect of Temperature

Hydrodesulphurization
De-nitrification
Rate of Reaction

Aromatic/Olefin Saturation

Coking

Temperature

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Effect of Pressure

Aromatic/Olefin Saturation
Hydrodesulphurization
Rate of Reaction

Coking

Pressure

DHT BLOCK REFRESHER COURSE – JAN 2018 33

Chemistry of Amine Section

H2S is a weak acid & ionizes in water to form hydrogen ion & sulfide ion.
H2S + H2O ←→ H3O+ + HS-
Mono Di ethanolamine is a weak base and ionizes in water to form amine ion and
hydroxyl ion
(HOCH2CH2)2NH + H2O ←→ (HOCH2CH2)2NH2+ + OH-
When H2S dissolves into the solution containing the amine ion, it reacts to form a
weakly bonded salt of the acid & the base
(HOCH2CH2)2NH2+ + HS- ←→ (HOCH2CH2)2NH2SH

The sulphide ion is thus absorbed by the amine solution.

(HOCH2CH2)2NH + H2S ←→ (HOCH2CH2)2NH2SH

DHT BLOCK REFRESHER COURSE – JAN 2018 34

Absorption independent variables

➢Temperature
Lower Temperature favors the absorption. However lean amine temperature should
be maintained 7 to 13oC higher than the gas temperature to avoid the condensation.

➢Acid gas loading

Absorption depends on restricting the H2S loading in the rich amine to
favour the forward direction of the reaction given in equation. The H2S loading of the
amine solution is controlled by adjustment of the amine circulation rate.

➢Amine concentration
Practical and economical considerations, confirmed by field experience, have
generally shown that the optimum amine concentration for this unit is 25% wt DEA.
This is based on the lowest heat requirement for the desired H2S removal, the lowest
chemical losses, and the fewest operational problems.

DHT BLOCK REFRESHER COURSE – JAN 2018 35

Thank You

DHT BLOCK 36