HGU Fundamentals and R&D Technical Services

Mainak Sarkar & I. R. Choudhury

COURSE ON PETROLEUM REFINING TECHNOLOGY Jan 31 Feb 3 , 2011 IOC R&D Centre
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Presentation Outline
Overview
Hydrogen demand and supply sources Refinery Hydrogen Management

Steam Reforming of Naphtha / NG

Process Fundamentals & Catalysts Poisoning of Catalyst

PSA Purification HGUs in Indian Refineries HGU Facility at IOC R&D Centre
Features of HGU Pilot Plant

Tender Catalyst Evaluation

Evaluation Methodology Performance Criteria
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Hydrogen is Everywhere
Car

Refinery

Gas Station

Stationary FC

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Demand for Hydrogen

H2 is essential in industrial process World wide H2 consumption : 50 Million Tonnes per year

USERS

CONSUMPTION, %

FERTILIZER INDUSTRY (AMMONIA)

REFINERIES

57
27

METHANOL
OTHER

10
6
Shell, 2004 IOC R&D CENTRE

Hydrogen Production Routes

Raw material
Natural Gas Refinery off-gases 48% LPG Naphtha 30% Kerosene, gas oil Methanol DME Ammonia 18% Coal Biomass 4% Water

Process
Steam Reforming

Reforming Cracking Gasification Electrolysis

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Nearly all H2 production is based on fossil fuels at present.

Different Technologies
TECHNOLOGY
STEAM REFORMING PARTIAL OXIDATION (POX) AUTO THERMAL REFOMING (ATR) GASIFICATION THERMAL CRACKING WATER GAS SHIFT REACTION (WGS) WATER ELECTROLYSIS THERMOCHEMICAL

STATUS
COMMERCIAL
R&D / COMMERCIAL R&D / COMMERCIAL COMMERCIAL R&D COMMERCIAL COMMERCIAL (Small Scale) R&D

PHOTOCATALYTIC PROCESS PHOTO ELECTRIC

PHOTO BIOLOGICAL FERMENTATIVE

R&D R&D
R&D R&D

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Purification Techniques
PRESSURE SWING ADSORPTION (PSA) Based on differences in adsorption and diffusion of different components MEMBRANE SEPARATION Based on selective permeation through membrane CRYOGENIC SYSTEM Based on differences in relative volatility of hydrogen and other impurities METAL HYDRIDE Based on metal alloys; Used in semiconductor industry
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Comparison of Purification Systems

PSA MEMBRANE CRYOGENICS

H2 capacity, mm scfd
Feed H2 content, % Feed pressure, psig/Mpa H2 product pressure H2 recovery, % H2 product purity

1-200
>40 150-600/ 1.03-4.13 Feed pressure 75-92 99.9+

1-50+
>25-50 300-2300/ 2.07-15.85 Much lower than feed pressure 85-95 90-98

10-75+
>10 >75-1100/ 0.52-7.58 Feed pressure or lower 90-98 90-96

Pretreatment requirement
Multiple products Capital cost Scale economics

None
No Medium Moderate

Minimum
No Low Modular

CO2, H2O removal

Liquid hydrocarbons High Good

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Economic Analysis

70+

40

20

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Hydrogen Generation Statistics

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Why Refinery Needs Hydrogen ? HYDRODESULPHURISATION HYDROTREATING HYDROCRACKING HYDRO FINISHING

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Typical H2 Usage in Refinery

Process Hydrocracking Hydrotreating VGO Distillates Naphtha Aromatics Saturation Isomerization Hydrogen Requirement (Std. m3/BBL) 40 85 20 35 10 20 5 15 5 15 15

Shrinking Refining Margin & Clean Fuel Mandate

more H2 H2

H2...
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Sources of H2 in Refinery
Purification of
Hydrotreater Vents Hydrocracker Vents / Purges FCC Off Gas

Catalytic Reformer Off Gas

Production by
Steam Reforming of o Natural Gas

o Naphtha
Partial Oxidation of o Fuel Oil
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HYDROGEN PRODUCTION BY

STEAM REFORMING OF NAPHTHA / NG

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Generic Hydrogen Plant Flowsheet

Pressure, kg/cm2 g

35

30

28

23

21

20

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Objective of Each Section

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Pre-desulphurisation section (PDS)

The main objective of pre-desulphurisation plant is to reduce the sulphur content in the sour naphtha feedstock for the hydrogen generation plant since sulphur is a poison for reformer catalyst .

The sour naphtha from the battery limit may contain up to 600 ppm wt Sulphur.
The sour naphtha is desulphurized in the PDS where the sulphur is converted to H2S which subsequently is removed in the Stripper. The pre-desulphurisation unit is designed for removing the bulk sulphur in the naphtha feed in order to minimise the desulphuriser (ZnO) catalyst consumption in FDS section

RSH + H2 RH + H2S RCI + H2 RH + HCI RNH2 + H2 RH + NH3 R=R + H2 R-R

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TYPICAL BLOCK DIAGRAM OF PDS SECTION

Sour Naphtha feed

vaporizer

Sour naphtha super heater

CoMoX Reactor I

Sour gas to b.l.

H2 compressor

Naphtha
cooler

Fuel gas from b.l.

Overhead condenser

Stripper Overhead overhead separator separator

Naphtha separator

Feed product exchanger

Naphtha stripper

Make up H2 from b.l. Sour water to b.l. Sweet naphtha to b.l.

Stripper reboiler

HP Steam
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Typical Feed for PDS Section

Properties Distillation Range Specific Gravity (15 0C) Total Sulphur (ppmw) Nitrogen (ppmw) Chlorin (ppmw) Hydrocarbon type (vol%) C5 140 0C 0.723 600 4 6

Parafins
Olefins Naphthenes Aromatics Total Metals ppbw

62.3
0.5 25 12.2 80

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Product and Operating Parameters Of PDS Section

Typical Product Specification
Properties Sulphur Content (ppmw) max Nitrogen Content (ppmw) max Metal Content (ppbw) 2 0.5 Non traceable

Typical Operating Parameters

Parameters Reactor Inlet/Outlet Temp (SOR/EOR) Weighted Average Bed Temp (WABT) H2 Partial Pressure LHSV Unit
0C

Value 290/330 292/333 310 27 3.2

0C

kg/cm2g h-1

H2/Oil

Nm3/m3

72
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Feed Desulphurisation Section (FDS)

This section consists of two reactors in series HDS Reactor Desulphurizer Reactor HDS Reactor contains CoMoX type of catalyst and converts all type of organic sulphur and chlorine compounds to H2S and HCl Desulphurizer Reactor contains Chlorine guard and Sulphure guard beds. Cl-guard removes HCl and S-guard removes H2S from the desulphurized naphtha stream Allowable Sulphur and Chlorine slippage from FDS section is <0.2ppmw and < 0.1 ppmw respectively
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HDS Reactor
Operates at 350-400oC (WABT 392oC ) Temperature and 35 bar pressure LHSV is very high i.e. In the range of 7-8 h-1 Major S compounds present in Light Naphtha are COS, mercaptans, organic sulphides, disulphides, thiophenes and react as follows RSH + H2 RH + H2S Other impurities such as chlorine, nitrogens and olefins also get removed because of the side reactions RCI + H2 RH + HCI RNH2 + H2 RH + NH3 R=R + H2 R-R
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Desulphurizer Reactor (Guard Bed)

ZnO acts as S-guard and absorbs H2S
ZnO + H2S ZnS + H2O

HCl reacts with Cl-guard which may contain Al2O3, NaAlO2 or Na2O
Al2O3 + 6HCl 2AlCl3 + 3H2O Na2O + 2HCl 2NaCl + H2O HCl + NaAlO2 AlOOH + NaCl HCl + 2NaAlO2 Al2O3 + 2NaCl + H2O K2CO3+HCL 2KCL+H20+CO2

Since HCl reacts with the Zinc Oxide to mobile ZnCl2, the chlorine guard bed is installed before the ZnO bed The Desulphurizer Reactor acts as lead lag arrangement In lead lag arrangement, the lag bed acts as a guard bed and lead bed takes the high sulphur loading. Once the lead bed gets exhausted the lag bed takes the load Allowable H2S slippage limit for Lead bed is 10 ppmv; S slip may increase with low operating temperature, high carbon dioxide or water content in the feed
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Lead Lag Arrangement

Cl Guard

48-R-02 A R-A
ZnO beds

48-R-02 B R-B

From CoMox Desulphurized Feed

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Pre-Reforming Section
The main objective of Pre-reformer reactor is to convert higher hydrocarbons (C5-90) into lighter gaseous mixture containing primarily CH4, H2, CO and CO2

The main reactions occurring inside a pre-reformer are: CnHm + nH2O -----> nCO + (n +m/2)H2 (Endothermic)
H0298= 1175 kJ/mole (for n=7)

CO + 3H2 CH4 + H2O (Exothermic)

H0298= -206 kJ/mole

CO + H2O CO2 + H2

(Exothermic)
H0298 = - 41 kJ/mole

Pre-reformer is an adiabatic fixed-bed reactor Pre-reforming is typically carried out at 480 -520 0C and steam to carbon ratio 1.8 3.0

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Pre-Reforming Section
A typical feed and product composition of a Pre-reformer
Component Feed Composition (mol%)

contd..

Product Composition (mol%)

Naphtha Hydrogen Methane CO2 CO C2 +

74.62 25.38 ---------

--23.76 51.01 24.84 0.85 <0.2

Note: Maximum allowable ethane and higher hydrocarbon (C2+) slippage is 0.2 mol%
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Temperature Profile
T across the Pre-reformer catalyst bed for different feed stock
Feed Type Natural Gas Naphtha Propane / Butane T over the Cat bed (0C) -25 to -30 +15 to +20 0

Temperature profile across the Pre-reformer catalyst bed

520 Bed Temperature, deg. C 510 500 490 480 470 460 0 0.5 1 1.5 Distance from the top the Cat Bed (m) 2 2.5

Naphtha Natural Gas Butane

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Pre-Reformer Operating Range

The key operating parameters for a pre-reformer reactor are:

Parameters
Pre-reformer inlet temperature, 0C

Operating range
470 490

Pre-reformer inlet pressure, Kg/cm2 a

Pre-reformer outlet pressure, Kg/cm2 a

30 28
28 26

LHSV, Hr-1
Steam to Naphtha ratio, (Kmol/Kmol)

2 2.5
22 14
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Advantages of Pre-Reformer
Advantages of incorporating Pre-reforming step prior to Reforming are: Removal of Higher Hydrocarbons & larger Feedstock Flexibility Flexibility in operation of Tubular Reformer w.r.t lower S/C ratio and higher feed preheat temperature Protection of Downstream catalysts from poisoning of S and other impurities

Capacity Increase
Overall Energy Savings
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Pre-reformer Catalyst
Pre-reformer catalyst is typically Ni based The catalyst is supplied in Oxide form supported on some refractory material such as Alumina (Al2O3), Magnesium Oxide (MgO) etc The catalyst is active in reduced form Ni crystal NiO + H2 Ni + H2O Normal expected life of pre-reforming catalyst is 1.5 to 2 yrs

Life assessment of pre-reformer catalyst is done by plotting Z- 90 curve with days of operation
Z-90 = (Prereformer max. Temp. - Prereformer min. Temp.) x 0.90 + Prereformer min. Temp The bed height corresponding to this temperature is called the Z-90 of prereformer catalyst

In case of NG feed, Z-90 is measured when the temperature becomes steady after endotherm
Z- 90 = Prereformer Max. Temperature - (Prereformer Max. temperature - Prereformer mini. Temp.) x 0.90
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Z-90 Curve

Pre Reformer Z 90
2000 Bed Depth, mm

Abnormal
1500 1000 500 0 0 50 100 150 200 IOC R&D CENTRE Days in operation

Reforming Section
Reforming section is the heart of the Hydrogen generation unit The main objective is to produce Synthesis gas (CO + H2) from CH4 The reforming is highly endothermic and require external heat supply Reformer reactor is a large furnace with multiple tube rows filled with catalyst running vertically along the furnace box

The normal inlet and outlet temperature of a typical reformer is 650-665 0C and 880-890 0C respectively

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Reforming Section
A typical feed and product composition of a Reformer Component Hydrogen Methane Feed Composition (mol%) 23.76 51.01

contd..

Product Composition (mol%) 67.91 1.97

CO2
CO

24.84
0.85

9.65
20.47

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Reforming Reaction and Thermodynamics

The main reaction occuring in Reformer is : CH4 + H2O CO + 3H2 (Endothermic) with side reactions CH4 + 2H2O CO2 + 4H2 (Endothermic) (Endothermic) CO2 + H2 CO + H2O (Endothermic) CH4 C + 2H2 (Endothermic) C + H2OCO+ H2 (Exothermic) CO + 3H2 CH4 + H2O
Process Variables Changes H0298 = +205.9 kJ /mol

H0298 = +164.9 kJ /mol H0298 = +41.0 kJ /mol H0298 = +74.6 kJ /mol H0298 = +131.3 kJ /mol H0298 = -205.9 kJ /mol

Process parameter affecting the equilibrium position:

Hydrogen Yield Notes

Pressure Temperature

Increase Increase

Decrease Increase Increase

Plant economy dictates pressure parameter Limited by tube metallurgy Dictates by Plant Design
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Steam to Carbon Ratio Increase

Reformer Operating Range

The key operating parameters for a Reformer reactor are:
Parameters Reformer inlet temperature, 0C Reformer outlet temperature, 0C Reformer inlet pressure, Kg/cm2 a Reformer outlet pressure, Kg/cm2 a Operating range 650 665 885 890 28 26 24 23

GHSV, Hr-1
Steam to Methane ratio, (Kmol/Kmol)

1500 1800
2.8 3.0
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Reformer Furnace
Reformer furnaces are available in various geometry, tubes arrangement and burner arrangements

The most common types are: Top fired Box furnace (M/s Technip & Linde) Side fired Box furnace (M/s Haldor Topse)
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Different Reformer Configurations

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Schematic Diagram of a Reformer Tube

Top Flange Feed Inlet Pigtail Catalyst

11.6 m Reformer Tube

Tube metallurgy 35 Ni 25 Cr & Niobium

Catalyst Support Grid

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Reforming Catalyst
Nibased catalysts dispersed on various supports like -alumina, -alumina, magnesium aluminate, calcium aluminate spinels etc.

In some cases ZrO2 is also used in the support for increase in stability
Promoters such as K2O, MgO, CaO, and SrO are used to minimize carbon formation; small amount of SiO2 prevents the evaporation of K2O and other alkali oxides 4-hole or 7-hole structure of reformer catalyst ensures high mechanical strength, thermal stability and low pressure drop The performance of the Reforming catalyst is measured in terms of methane slippage in the reactor effluent
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Catalyst Properties
Typical chemical properties of steam reforming catalyst from different vendors
Johnson Matthey (46-3Q)
Component Ni Oxide, wt% Other oxides, wt% (K2O, ZrO2, SiO2) Support Typical average crush strength (kg) (radial) Shape 23 7 Balance 100 >12 <0.2 Balance 100

Topse
(R-67-7H)

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Shift Conversion Section

Shift conversion stands for Water Gas shift reaction CO+ H2O CO2 + H2 H0298 = - 41 kJ/mol The main objective of this section is to enhance the hydrogen yield and at the same time reduces the emission of CO Thermodynamics: Slightly Exothermic Pressure has no effect on the equilibrium At high temperature, this is equilibrium controlled reaction Depending up on the reaction temperature and catalyst type, shift reactors can be further classified as High temperature shift reactor HTS Medium temperature shift reactor MTS Low temperature shift reactor LTS
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Shift Conversion Section

Shift Type Inlet Temp( 0C) Outlet Temp(0C)

contd..

HTS
MTS LTS

340-350
200-205 200-205

410-420
330-340 220-230

The general configuration for the shift converter section is either HTS followed by LTS (Technip, Linde) or MTS followed by LTS (Topse) Some time only HTS or only MTS may also present In the HTS reactor because of the unfavorable equilibrium, the CO conversion is low compared to MTS reactor. On the other hand, HTS catalyst is more resistance to sulphur poison CO slippage is the controlling criterion for the shift reactor performance
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Shift Conversion Section

Inlet / Outlet composition of Shift Converter
Component HTS inlet Hydrogen Methane CO2 CO 66.2 5.5 11.6 16.7 Composition (mol%) HTS outlet 69.6 4.9 20.6 4.8 LTS inlet 69.6 4.9 20.6 4.8

contd..

LTS outlet 70.8 4.7 23.8 0.7

Component MTS inlet Hydrogen Methane CO2 CO 67.91 1.97 9.56 20.47

Composition (mol%) MTS outlet 72.47 1.69 22.51 3.33 LTS inlet 72.47 1.69 22.51 3.33 LTS outlet 73.16 1.65 24.44 0.75
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HT Shift Catalyst
HT shift catalyst is based on Fe3O4 promoted with Cr2O3 to prevent sintering

The typical composition of HT catalyst is 90 wt% Fe3O4 & 10 wt% Cr2O3

For activation the catalyst is reduced in situ in a controlled atmosphere of H2 & CO The active form is a spinel with composition FeIIFeIII2-xCrxO4 Excess steam is used during activation to avoid the formation of metal carbide This catalyst is tolerant to sulfur and chlorine compounds
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MT / LT Shift Catalyst
A typical composition of MT Shift catalyst includes ZnO:Cr2O3:CuO= 1:0.24:0.24 with 2% 5% MnOx, Al2O3 and MgO promoters The typical composition of LTS catalyst is 32-33 wt% CuO, 34-53 wt% ZnO and 15-33 wt% Al2O3

MTS and LTS catalysts are sensitive to sulphur and chlorine in feed
Both MT/LT shift catalysts need to be reduced with H2 to form the active species Cu Reduction reaction is exothermic and temperature excursions above 230-250C may cause catalyst sintering; so H2 is diluted with N2

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Poisoning of Catalyst
Sulphur - Ni is good sulphur absorbent (One atomic layer) Detected by hot spots on the surface of reformer tubes hot bands, hot patches, giraffe necking and increase of methane slippage at exit of reactor

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Poisoning of Catalyst

contd..

Chlorine - usually present as organic Cl or HCl - is similar to sulphur - accelerates the sintering of the metal crystallites - serious poison for Cu shift catalyst (MTS/LTS) Arsenic - found in naphtha feedstock - severe and irreversible catalyst poison - also contaminates metal of pipework and reformer tubes

Si, P & Alkali - found in liquid feedstock - poison the reforming catalyst Olefins - Highly exothermic; 1.0 % ethylene in NG leads to increase of 29 0C - carbon formation
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Purification Section: PSA Unit

The objective of this section is to enrich Hydrogen in the HGU effluent Pressure Swing Adsorption (PSA) route is used in general Principle: Desired component is adsorbed at high pressure while impurities are rejected at low pressure Adsorbents used: Na- Silicates: for H2O adsorption Activated charcoal for CO2 removal Molecular sieves for CO/CH4 removal Multi vessel systems. One vessel is in adsorption while the others are in various stages of regeneration. Waste stream from the PSA (Purge Gas) is burnt in the Reformer as fuel
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Hydrogen Quality at PSA outlet

Quality
Hydrogen Methane + Carbon dioxide + Carbon monoxide Nitrogen Chlorides + Chlorine mole% ppmv Mole% ppmv
0C

>99.99 <20 Balance <1

Water (dew point at 1atm.)

Total sulphur Total nitrogen (excl.N2) Molecular mass O/L Pressure O/L Temp.

-80
<1 ppmv <1ppmv 2.02 20.0 40-45

ppmv ppmv Kg/kmol Kg/cm2g 0C

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Typical PFD of a PSA System

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HGUs in Indian Refineries

HGU in IndianOil Operated / Subsidiary Refineries
S. No. 1 Refinery Unit Licensor Capacity, MTPA 38000 11000 72500 38000 70000 (2 Chains) 34000 60000 15000 75000 34000 --10000 7000 16064 56000 Year of Commissioning 1993 1999 2010 1999 2005 1999 2005 1999 2010 2002 Under construction 2002 2003 1999 2004
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2 3 4 5

6 7 8

HGU-I Linde A G Gujarat HGU-II Haldor Topse HGU-III Haldor Topse HGU-I Haldor Topse Panipat HGU-II (A/B) Haldor Topse HGU-I Haldor Topse Mathura HGU-II Technip HGU-I Haldor Topse Haldia HGU-II Technip HGU-I Haldor Topse Barauni HGU-II Linde A G Technip Guwahati HGU Digboi HGU Technip Technip HGU-I CPCL* HGU-II Technip

* Indian Oil Subsidiary company

HGUs in Indian Refineries

HGU in Other Indian Refineries
S. Own Refinery No. er 1 HPCL Vishak Refinery Mumbai Refinery 2 BPCL Mumbai Refinery (HGU-I) Mumbai Refinery (HGU-II) Kochi Refinery (KRL) 3 NRL Numaligarh Refinery 4 RPL Jamnagar Refinery 5 MRPL HGU-I HGU-II Unit Licensor Technip Haldor Topse Haldor Topse Haldor Topse Technip Haldor Topse Linde A G Technip Technip Capacity, MTPA 18000 14500 14500 45000 18650 38000 165000 20000 23000

contd..

Year of Commissioning 2000 2000 1999 2005 2000 2000 2005 1996 1999

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Different HGU Plant Configurations

Units Designed by M/s Haldor Topse
Refinery
Gujarat Gujarat HGU-II HGU-III

PDS
Yes Yes

FDS/HDS Pre-Reformer Reformer

Yes Yes

Shift

PSA beds
1x5 2x6

Single Reactor Side Fired MT only Single Reactor Side Fired MT & LT

Mathura
Panipat Panipat Haldia

HGU-I
HGU-I HGU-II (A/B) HGU-I

No
No Yes Yes

Yes
Yes Yes Yes

Single Reactor Side Fired MT only

Single Reactor Side Fired MT & LT Single Reactor Side Fired MT only

1 x 10 1x5 1 x 10
1x5

Single Reactor Side Fired MT & LT 1x12(2 chains)

Barauni

HGU-I

No

Yes

Single Reactor Side Fired MT & LT

1 x 10

Units Designed by M/s Technip & M/s Linde

Refinery
Gujarat Mathura Haldia Guwahati Digboi HGU-I HGU-II HGU-II HGU HGU

PDS
No Yes Yes No No

FDS/HDS Pre-Reformer Reformer

Yes Yes Yes Yes Yes No Two Reactors Single Reactor Single Reactor No Top Fired Top Fired Top Fired Top Fired Top Fired

Shift
HT only HT & LT HT & LT HT & LT HT only

PSA beds
1x10 1 x 12 1 x 10 1 x 10 1x5
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GENERAL BLOCK DIAGRAM OF HGU BY HTAS

NAPTHA(FEED) Surge Vessel Naptha Pump H2 Naphtha Vaporiser Preheater Hydrogena tor CL guard/ Sulphur guard CL guard/ Sulphur guard Pre-Reformer BFW Exchangers STACK IOC R&D CENTRE F D Fan Boiler

H P STEAM FOR PROCESS & EXPORT

H2 Recycle Comp
H2 TO HDT

Steam Drum

HP Steam

CW Exchanger

PSA UNIT

Fin Fan Coolers

Deaerator

LT Shift Converter

MT shift Converter

REFORMER

Process Con. Vessels

DMW Preheater

BFW Exchanger

I D Fan

FUEL

GENERAL BLOCK DIAGRAM OF HGU BY OTHER LICENSORS

NAPTHA(FEED) Surge Vessel Naptha Pump H2 Naphtha Vaporiser Preheater Hydrogena tor CL guard/ Sulphur guard CL guard/ Sulphur guard Pre-Reformer BFW Exchangers STACK IOC R&D CENTRE Boiler I D Fan F D Fan HP Steam

H P STEAM FOR PROCESS & EXPORT Steam Drum

H2 Recycle Comp H2 TO HDT

CW Exchanger

PSA UNIT

Fin Fan Coolers

Deaerator

Process Con. Vessels

DMW Preheater

LT Shift Converter

BFW Exchanger

HT shift Converter

REFORMER

HYDROGEN GENERATION UNITS AT

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Hydrogen Generation Facility

Water Electrolizer Hydrogen generation Unit

Supplies Hydrogen for Hydroprocessing Pilot Plants Catalyst Evaluation and Data generation for different projects

Pilot Scale Steam Reformer

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HGU Pilot Plant Facility

HGU PILOT PLANT HGU Pilot plant is the 1st of its kind in India Indigenously designed by R&D centre and fabricated by M/s Xytel India Miniature Steam Reformer It can exactly simulate the operating parameters of any commercial unit
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Objectives of HGU Pilot Plant

Catalyst selection & evaluation from different vendor and recommendation of the same to refineries Kinetic data generation for in-house model development Optimization Studies Trouble shooting Feed and product evaluation Catalyst health monitoring / deactivation studies Competitors technology assessment Development of new technologies
With model application

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Different Sections of Pilot Plant

Liquid feed section

Naphtha Tank + Weighing Balance DM water tank + Weighing Balance Feed Pump for Naphtha Pumps for DM water Naphtha Vaporizer Steam generator

Gas Feed Section

H2, N2, CH4, CO2, CO & Natural gas (NG) Mass flow controllers for each gas Drier for each gas
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Different Sections of Pilot Plant

contd ..

Reactor Section FDS Section

Hydrogenation Desulfurization (Sulfur and Chlorine guard beds)

REFORMER Section
Pre-Reformer Reformer

SHIFT Section
High/Medium Temperature Shift (HTS/MTS) Low Temperature Shift (LTS)

Or a combination of these
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Different Sections of Pilot Plant

contd ..

Gas/Liquid separation section

High pressure Separator (HPS) Pressure control valve Level control valve Condensate collection tank + Weighing balance Wet Gas meter (WGM) Off gas sampling arrangement

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PFD of HGU Pilot Plant

R-300 CO CO2 NATURAL GAS METHANE NITROGEN HYDROGEN TO R- 500 & 700 TO R- 500 & 700 TO R- 400 TO R- 300, 400, 500, 700 & 800 TO R- 300, 400, 500, 700 & 800 TO R- 400, 500, 700 & 800 FOR GAS ANALYSIS Cl STEAM GENERATOR NAPHTHA HEATER S U L P H U R R E M O V A L G A U R D S G A U R D P R E R E F O R M E R R-400 R-500 R-600 HIGH PRESSURE
SEPARATOR

WATER TANK

NAPHTHA TANK

R E F O R M E R

WET GAS METER

WATER PUMP NAPHTHA PUMP CONDENSATE WATER

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PFD of HGU Pilot Plant

R-700

contd..

R-800

HIGH PRESSURE
SEPARATOR

FROM R-600

FOR GAS ANALYSIS

H T S WATER TANK / M T S R E A C T O R

L T S R E A C T O R

WET GAS METER

STEAM GENERATOR

WATER PUMP

CONDENSATE WATER

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Operating Range
REACTOR CAPACITY :
Cat volume: 50 - 100 cc

OPERATING TEMPERATURES :
450oC max for HDS & Guard Bed Reactor

600oC max for Pre reformer

950oC max for Reformer 550oC max for HTS/MTS 350oC max for LTS Reactor

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Operating Range

contd..

PRESSURE : 50 bar max for HDS/ Pre reformer/ Reformer 35 bar max for HTS/ LTS Reactor NAPHTHA FEED RATE : 20 - 450 ml/h (C5 - 1000C)

WATER FLOW RATE : 60-600 ml/h

FEED GAS FLOWRATE : 10-500 SLPH for NG, CH4, CO, CO2 16-800 SLPH for H2
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Additional Features of HGU Pilot Plant

PLC system for remote control State of the art instrumentation for measuring all major operating parameters during start-up, shutdown and normal operation Five internal Thermocouples in each reactor for adjusting catalyst bed temperature Flexible operation All 6 reactors in series Any one reactor or reactors in combination Separate sampling arrangement for each reactor By-pass of HDS section for sulfiding & start-up 6 Reactors in series Electrical heaters for each reactor.
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Additional Features of HGU Pilot Plant

Off gas sampling arrangements
GC for online/off line off gas analysis

Provision of steam startup line to check steam quality

Provision for slop tank

Water de-aeration facility Emergency pump for water

Comprehensive safety features

Temperature safety switch for each reactor Pressure safety valve & Rupture disc in each reactor UPS for bake up power supply
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Additional Features of HGU Pilot Plant

Feed / Product Characterization Facilities
Feed/product N, S, Cl Analyzer Feed naphtha ASTM, SIMTBP, sp. gr and detailed component analysis DM water quality analysis (TDS etc)

Catalyst Characterization
Surface area, pore volume analyzer XRD & XRF for catalyst chemical composition

Crushing strength measurement

(Side Crush Strength for Reformer Catalyst) Apparatus for Bulk Density measurement
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Tender Catalyst Evaluation

PDS / FDS Catalyst

Pre-Reformer Catalyst
Reformer Catalyst

HT Shift Catalyst
MT Shift Catalyst LT Shift Catalyst
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Steps involved in Tender Cat Evaluation

Catalyst ex-situ drying (if

recommended by vendor)

Sizing of catalyst (only for Reformer catalyst) Catalyst Loading Catalyst reduction by vendors recommended procedure Determination of the operating parameter

Steam start-up through start-up line

Start Feed Set operating parameters Stabilization Product gas analysis& Material Balance
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Step Details
Sizing of catalyst (Only for Reformer Catalyst)

Reformer catalyst size is bigger than reactor annular space The catalyst are broken. Then the broken catalyst are sieved. Catalyst of particular size range are taken for loading Bulk Density (BD) is determined

Catalyst Loading: Following parameters need to be considered for determining the loading volume

LHSV / GHSV Maximum Feed pump capacity Maximum Water pump capacity Minimum and maximum limit of MFC

Feedrate(m 3 / h) Gasrate (m 3 / h) LHSV , GHSV CatalystVolume (m 3 ) CatalystVolume (m 3 )

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Typical Reactor Loading Diagram

Thermo-well Top Dead end Inlet QUARTZ WOOL CATALYST BED ALUMINA BALLS

Internal Thermocouple position

Heating zone-1

Pre-Heating Zone

Heating zone-2 Heating zone-3 Catalyst Bed

Heating zone-4

Post-Heating Zone Out let

Bottom Dead end

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Operating Parameters
Determination of the operating parameter Feed rate Naphtha rate (Pre-reformer catalyst) LHSV Gas rate (Reformer, HTS, MTS & LTS catalyst) GHSV In case of synthetic feed Synthetic feed composition Based on refinerys reactor outlet composition. Steam rate Based on refinerys Steam/gas ratio Set operating parameters Temperature (Inlet / Outlet) Pressure (Inlet) Feed rate Gas rate Steam rate Material Balance: Error limit ( 2 %)
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Tender Catalyst Evaluation Criteria

CATALYSTS HDS ZnO

Prereformer Reformer Shift (HT / MT / LT)

PERFORMANCE PARAMETERS S Slippage H2S Slippage

Ethane & higher HC (C2+) Slippage Methane Slippage CO Slippage

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Tender Catalyst Evaluation Criteria

Typical Tender Evaluation Criteria
CATALYSTS HDS Pre-reformer
Reformer HT Shift MT Shift LT Shift

GUARANTY COMPOUND SLIPPAGE 0.2 ppm wt. Organic sulphur max 0.2 vol % C2+ dry basis (max)
3 4.5 vol % CH4 dry basis (max) 6 vol % CO dry basis (max) 3.9 vol % CO dry basis (max) 1.0 vol % CO dry basis (max)

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Pre-Reformer Catalyst Evaluation

COMPOSITION OF EXIT GAS, VOL %

COMPONENT COMMERCIAL PLANT VENDOR-A VENDOR-B VENDOR- C C2+ fraction vol% Trace Trace Trace Trace H2 23.7 23.4 23.03 21.9 CO 0.2 0.8 0.79 0.77 CO2 17.8 17.69 17.18 17.6 CH4 58.3 57.71 57.98 59.73

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Reformer Catalyst Evaluation

Component Commercial Plant 4.1 Vendor-1 Vendor-2

CH4

2.79

2.33

H2
CO CO2

66.8
18.9 10.1

69.32
18.51 9.38

69.61
19.30 8.76

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MTS Catalyst Evaluation

CATALYST
COMPONENT COMMERCIAL PLANT VENDOR- A VENDOR-B VENDOR- C

COMPOSITION OF EXIT GAS, VOL % H2 74.6 75.45 75.41 75.49 CO 0.8 1.82 1.87 1.63 CO2 19.4 22.73 22.72 22.88

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LTS Catalyst Evaluation

CATALYST
COMPONENT COMMERCIAL PLANT VENDOR-A VENDOR-B

COMPOSITION OF EXIT GAS, VOL % H2 75.4 73.69 73.99 CO 0.4 0.72 0.46 CO2 18.4 25.58 25.55

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Steps involved in running Pilot Plant

All the reactors in series
Catalyst ex-situ drying (if required) Catalyst Loading Catalyst reduction (Pre-reformer, Reformer, HTS/MTS & LTS) as per vendors procedure HDS section start-up (In case of sour naphtha ) Sulphiding as per vendor procedure (use by-pass line) Normal HDS operation till product sulfur < 1 ppm Divert HDS outlet to Sulfur guard bed

Steam start-up through start-up line

Feed start-up / Divert Sulphur guard (R-400) outlet to Pre-reformer

Stabilization Product gas analysis , Material Balance and Yield calculation
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Conclusions Hydrogen Generation Unit is an integral part of todays Refinery configuration Understanding of different sections of HGU plant is essential for better monitoring/ troubleshooting, optimization and revamp studies

IOC R&D Centre offers the state-of-the-art HGU catalyst evaluation facility for tender catalyst evaluation
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