Hgu Presentation Rt Course Final 3i2f

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 IOC R&D CENTRE

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 IOC R&D CENTRE

Hydrogen is Everywhere Car

Refinery

Gas Station

Stationary FC

IOC R&D CENTRE

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

S

CONSUMPTION, %

FERTILIZER INDUSTRY (AMMONIA)

57

REFINERIES

27

METHANOL

10

OTHER

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

Nearly all H2 production is based on fossil fuels at present. IOC R&D CENTRE

Different Technologies TECHNOLOGY STEAM REFORMING

STATUS COMMERCIAL

PARTIAL OXIDATION (POX)

R&D / COMMERCIAL

AUTO THERMAL REFOMING (ATR)

R&D / COMMERCIAL

GASIFICATION THERMAL CRACKING WATER GAS SHIFT REACTION (WGS) WATER ELECTROLYSIS

COMMERCIAL R&D COMMERCIAL COMMERCIAL (Small Scale)

THERMOCHEMICAL

R&D

PHOTOCATALYTIC PROCESS

R&D

PHOTO ELECTRIC

R&D

PHOTO BIOLOGICAL

R&D

FERMENTATIVE

R&D

IOC R&D CENTRE

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 IOC R&D CENTRE

Comparison of Purification Systems PSA

MEMBRANE

CRYOGENICS

H2 capacity, mm scfd

1-200

1-50+

10-75+

Feed H2 content, %

>40

>25-50

>10

Feed pressure, psig/Mpa

150-600/ 1.03-4.13

300-2300/ 2.07-15.85

>75-1100/ 0.52-7.58

H2 product pressure

Feed pressure

Much lower than feed pressure

Feed pressure or lower

H2 recovery, %

75-92

85-95

90-98

H2 product purity

99.9+

90-98

90-96

Pretreatment requirement

None

Minimum

CO2, H2O removal

Multiple products

No

No

Liquid hydrocarbons

Capital cost

Medium

Low

High

Scale economics

Moderate

Modular

Good

IOC R&D CENTRE

Economic Analysis

70+

40

20

IOC R&D CENTRE

Hydrogen Generation Statistics

IOC R&D CENTRE

Why Refinery Needs Hydrogen ? HYDRODESULPHURISATION HYDROTREATING HYDROCRACKING HYDRO FINISHING

IOC R&D CENTRE

Typical H2 Usage in Refinery Process Hydrocracking

Hydrogen Requirement (Std. m3/BBL) 40 – 85

Hydrotreating VGO Distillates

20 – 35 10 – 20

Naphtha Aromatics Saturation Isomerization

5 – 15 5 – 15 1–5

Shrinking Refining Margin & Clean Fuel Mandate more H2… H2…

H2... IOC R&D CENTRE

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 IOC R&D CENTRE

HYDROGEN PRODUCTION BY

STEAM REFORMING OF NAPHTHA / NG

IOC R&D CENTRE

Generic Hydrogen Plant Flowsheet

Pressure, kg/cm2 g

35

30

28

23

21

20

IOC R&D CENTRE

Objective of Each Section

IOC R&D CENTRE

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 IOC R&D CENTRE

TYPICAL BLOCK DIAGRAM OF PDS SECTION Sour Naphtha feed

H2 compressor

vaporizer

Sour naphtha super heater

Naphtha

Fuel gas from b.l.

cooler

Naphtha separator

Feed product exchanger

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

CoMoX Reactor I

Sour gas to b.l.

Stripper Overhead overhead separator separator

Overhead condenser

Naphtha stripper

Stripper reboiler

HP Steam IOC R&D CENTRE

Typical Feed for PDS Section

Properties Distillation Range

C5 – 140 0C

Specific Gravity (15 0C)

0.723

Total Sulphur (ppmw)

600

Nitrogen (ppmw)

4

Chlorin (ppmw)

6

Hydrocarbon type (vol%)

Parafins

62.3

Olefins

0.5

Naphthenes

25

Aromatics

12.2

Total Metals ppbw

80

IOC R&D CENTRE

Product and Operating Parameters Of PDS Section Typical Product Specification Properties Sulphur Content (ppmw) max

2

Nitrogen Content (ppmw) max

0.5

Metal Content (ppbw)

Non traceable

Typical Operating Parameters Parameters

Unit

Value

Reactor Inlet/Outlet Temp (SOR/EOR)

0C

290/330 292/333

Weighted Average Bed Temp (WABT)

0C

310

H2 Partial Pressure

kg/cm2g

27

LHSV

h-1

3.2

H2/Oil

Nm3/m3

72 IOC R&D CENTRE

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 IOC R&D CENTRE

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 IOC R&D CENTRE

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 IOC R&D CENTRE

Lead Lag Arrangement

Cl Guard

48-R-02 A R-A

48-R-02 B R-B ZnO beds

From CoMox Desulphurized Feed

IOC R&D CENTRE

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

IOC R&D CENTRE

Pre-Reforming Section

contd..

A typical feed and product composition of a Pre-reformer Component

Feed Composition (mol%)

Product Composition (mol%)

Naphtha

74.62

---

Hydrogen

25.38

23.76

Methane

---

51.01

CO2

---

24.84

CO

---

0.85

C2 +

---

<0.2

Note: Maximum allowable ethane and higher hydrocarbon (C2+) slippage is 0.2 mol% IOC R&D CENTRE

Temperature Profile ∆T across the Pre-reformer catalyst bed for different feed stock Feed Type

∆T over the Cat bed (0C)

Natural Gas

-25 to -30

Naphtha

+15 to +20

Propane / Butane

0

Temperature profile across the Pre-reformer catalyst bed Bed Temperature, deg. C

520 510 500

Naphtha

490

Natural Gas

480

Butane

470 460 0

0.5

1 1.5 Distance from the top the Cat Bed (m)

2

2.5

IOC R&D CENTRE

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

30 – 28

Pre-reformer outlet pressure, Kg/cm2 a

28 – 26

LHSV, Hr-1

2 – 2.5

Steam to Naphtha ratio, (Kmol/Kmol)

22 – 14 IOC R&D CENTRE

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 IOC R&D CENTRE

Pre-reformer Catalyst  Pre-reformer catalyst is typically Ni based  The catalyst is supplied in Oxide form ed 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 IOC R&D CENTRE

Z-90 Curve

Pre Reformer Z 90 Bed Depth, mm

2000

Abnormal 1500 1000 500 0 0

50

100

150

200

Days in operation IOC R&D CENTRE

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

IOC R&D CENTRE

Reforming Section

contd..

A typical feed and product composition of a Reformer Component

Feed Composition (mol%)

Product Composition (mol%)

Hydrogen

23.76

67.91

Methane

51.01

1.97

CO2

24.84

9.65

CO

0.85

20.47

IOC R&D CENTRE

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 + H2O↔CO+ H2 (Exothermic) CO + 3H2 ↔CH4 + H2O

ΔH0298 = +205.9 kJ /mol

ΔH0298 = +164.9 kJ /mol ΔH0298 = +41.0 kJ /mol ΔH0298 = +74.6 kJ /mol ΔH0298 = +131.3 kJ /mol ΔH0298 = -205.9 kJ /mol

 Process parameter affecting the equilibrium position: Process Variables

Changes

Hydrogen Yield Notes

Pressure

Increase

Decrease

Plant economy dictates pressure parameter

Temperature

Increase

Increase

Limited by tube metallurgy

Steam to Carbon Ratio Increase

Increase

Dictates by Plant Design IOC R&D CENTRE

Reformer Operating Range The key operating parameters for a Reformer reactor are: Parameters

Operating range

Reformer inlet temperature, 0C

650 – 665

Reformer outlet temperature, 0C

885 – 890

Reformer inlet pressure, Kg/cm2 a

28 – 26

Reformer outlet pressure, Kg/cm2 a

24 – 23

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

1500 – 1800 2.8 – 3.0 IOC R&D CENTRE

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 Topsøe) IOC R&D CENTRE

Different Reformer Configurations

IOC R&D CENTRE

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 Grid

IOC R&D CENTRE

Reforming Catalyst  Ni–based catalysts dispersed on various s like γ-alumina, α-alumina, magnesium aluminate, calcium aluminate spinels etc.

 In some cases ZrO2 is also used in the 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 of methane slippage in the reactor effluent IOC R&D CENTRE

Catalyst Properties Typical chemical properties of steam reforming catalyst from different vendors Johnson Matthey (46-3Q)

Topsøe

Ni Oxide, wt%

23

>12

Other oxides, wt% (K2O, ZrO2, SiO2)

7

<0.2

Balance

Balance

100

100

(R-67-7H)

Component

Typical average crush strength (kg) (radial) Shape

IOC R&D CENTRE

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 IOC R&D CENTRE

Shift Conversion Section Shift Type

Inlet Temp( 0C)

contd..

Outlet Temp(0C)

HTS

340-350

410-420

MTS

200-205

330-340

LTS

200-205

220-230

 The general configuration for the shift converter section is either HTS followed by LTS (Technip, Linde) or MTS followed by LTS (Topsøe)  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 IOC R&D CENTRE

Shift Conversion Section

contd..

Inlet / Outlet composition of Shift Converter Component

Composition (mol%) HTS inlet

HTS outlet

LTS inlet

LTS outlet

Hydrogen

66.2

69.6

69.6

70.8

Methane

5.5

4.9

4.9

4.7

CO2

11.6

20.6

20.6

23.8

CO

16.7

4.8

4.8

0.7

Component

Composition (mol%) MTS inlet

MTS outlet

LTS inlet

LTS outlet

Hydrogen

67.91

72.47

72.47

73.16

Methane

1.97

1.69

1.69

1.65

CO2

9.56

22.51

22.51

24.44

CO

20.47

3.33

3.33

0.75 IOC R&D CENTRE

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 IOC R&D CENTRE

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 230-250°C may cause catalyst sintering; so H2 is diluted with N2

IOC R&D CENTRE

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

IOC R&D CENTRE

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 IOC R&D CENTRE

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 IOC R&D CENTRE

Hydrogen Quality at PSA outlet Quality Hydrogen

mole%

>99.99

Methane + Carbon dioxide + Carbon monoxide

ppmv

<20

Nitrogen

Mole%

Balance

Chlorides + Chlorine

ppmv

<1

0C

-80

Total sulphur

ppmv

<1 ppmv

Total nitrogen (excl.N2)

ppmv

<1ppmv

Kg/kmol Kg/cm2g 0C

2.02 20.0 40-45

Water (dew point at 1atm.)

Molecular mass O/L Pressure O/L Temp.

IOC R&D CENTRE

Typical PFD of a PSA System

IOC R&D CENTRE

HGUs in Indian Refineries HGU in IndianOil Operated / Subsidiary Refineries S. No. 1

2 3 4 5

6 7 8

Refinery

Unit Licensor

Capacity, MTPA

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

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

* Indian Oil Subsidiary company IOC R&D CENTRE

HGUs in Indian Refineries

contd..

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 Topsøe Haldor Topsøe Haldor Topsøe Technip Haldor Topsøe Linde A G Technip Technip

Capacity, MTPA 18000 14500 14500 45000 18650 38000 165000 20000 23000

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

IOC R&D CENTRE

Different HGU Plant Configurations Units Designed by M/s Haldor Topsøe Refinery

PDS

FDS/HDS Pre-Reformer Reformer

Shift

PSA beds

Gujarat Gujarat

HGU-II HGU-III

Yes Yes

Yes Yes

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

1x5 2x6

Mathura

HGU-I

No

Yes

Single Reactor Side Fired MT only

Panipat

HGU-I

No

Yes

Single Reactor Side Fired MT & LT

1 x 10 1x5 1 x 10

Panipat

HGU-II (A/B)

Yes

Yes

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

Haldia

HGU-I

Yes

Yes

Single Reactor Side Fired MT only

1x5

Barauni

HGU-I

No

Yes

Single Reactor Side Fired MT & LT

1 x 10

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

PDS

FDS/HDS Pre-Reformer Reformer

Shift

PSA beds

Gujarat

HGU-I

No

Yes

No

Top Fired

HT only

1x10

Mathura

HGU-II

Yes

Yes

Two Reactors

Top Fired

HT & LT

1 x 12

Haldia

HGU-II

Yes

Yes

Single Reactor

Top Fired

HT & LT

1 x 10

Guwahati

HGU

No

Yes

Single Reactor

Top Fired

HT & LT

1 x 10

Digboi

HGU

No

Yes

No

Top Fired

HT only

1x5 IOC R&D CENTRE

GENERAL BLOCK DIAGRAM OF HGU BY HTAS Naphtha Vaporiser

Steam Drum

HP Steam

REFORMER

MT shift Converter

Pre-Reformer

BFW Exchanger

Boiler

I D Fan

DMW Preheater

BFW Exchangers

FUEL

Process Con. Vessels

Deaerator

F D Fan

Fin Fan Coolers

LT Shift Converter

CW Exchanger

H2 TO HDT

PSA UNIT

CL guard/ Sulphur guard

H P STEAM FOR PROCESS & EXPORT

H2

H2 Recycle Comp

Hydrogena tor

Preheater

CL guard/ Sulphur guard

Naptha Pump

STACK

NAPTHA(FEED) Surge Vessel

IOC R&D CENTRE

GENERAL BLOCK DIAGRAM OF HGU BY OTHER LICENSORS Naphtha Vaporiser

Hydrogena tor

H P STEAM FOR PROCESS & EXPORT

H2

H2 Recycle Comp

Preheater

F D Fan

Steam Drum

HP Steam

Process Con. Vessels

DMW Preheater

REFORMER

HT shift Converter

Pre-Reformer

Deaerator

BFW Exchangers

BFW Exchanger

Boiler

I D Fan

Fin Fan Coolers

LT Shift Converter

CW Exchanger

H2 TO HDT

PSA UNIT

CL guard/ Sulphur guard CL guard/ Sulphur guard

Naptha Pump

STACK

NAPTHA(FEED) Surge Vessel

IOC R&D CENTRE

HYDROGEN GENERATION UNITS AT

IOC R&D CENTRE

IOC R&D CENTRE

Hydrogen Generation Facility

Hydrogen generation Unit

Water Electrolizer

Supplies Hydrogen for Hydroprocessing Pilot Plants

Pilot Scale Steam Reformer

Catalyst Evaluation and Data generation for different projects

IOC R&D CENTRE

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 IOC R&D CENTRE

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

IOC R&D CENTRE

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 IOC R&D CENTRE

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 IOC R&D CENTRE

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

IOC R&D CENTRE

PFD of HGU Pilot Plant R-300 CO

TO R- 500 & 700

CO2

TO R- 500 & 700

NATURAL GAS

TO R- 400

METHANE

TO R- 300, 400, 500, 700 & 800

NITROGEN

TO R- 300, 400, 500, 700 & 800

HYDROGEN

TO R- 400, 500, 700 & 800

R-400

R-500

R-600

HIGH PRESSURE SEPARATOR

FOR GAS ANALYSIS Cl NAPHTHA HEATER

STEAM GENERATOR NAPHTHA TANK

WATER TANK

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 E F O R M E R

WET GAS METER

WATER PUMP NAPHTHA PUMP CONDENSATE WATER

IOC R&D CENTRE

PFD of HGU Pilot Plant R-700

contd..

HIGH PRESSURE

R-800

SEPARATOR

FROM R-600

FOR GAS ANALYSIS

WATER TANK

STEAM GENERATOR

H T S

L T S

/ M T S

R E A C T O R

R E A C T O R

WET GAS METER

WATER PUMP

CONDENSATE WATER

IOC R&D CENTRE

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

IOC R&D CENTRE

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 IOC R&D CENTRE

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- of HDS section for sulfiding & start-up  6 Reactors in series –Electrical heaters for each reactor. IOC R&D CENTRE

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 IOC R&D CENTRE

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 IOC R&D CENTRE

Tender Catalyst Evaluation • PDS / FDS Catalyst

• Pre-Reformer Catalyst • Reformer Catalyst

• HT – Shift Catalyst • MT – Shift Catalyst • LT – Shift Catalyst IOC R&D CENTRE

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 vendor’s 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 IOC R&D CENTRE

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

   

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

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

IOC R&D CENTRE

Typical Reactor Loading Diagram Thermo-well

QUARTZ WOOL CATALYST BED ALUMINA BALLS

Top Dead end Inlet

Heating zone-1

Internal Thermocouple position

Pre-Heating Zone

Heating zone-2 Heating zone-3

Heating zone-4

Catalyst Bed

Post-Heating Zone Out let

Bottom Dead end

IOC R&D CENTRE

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 refinery’s reactor outlet composition. Steam rate Based on refinery’s Steam/gas ratio Set operating parameters  Temperature (Inlet / Outlet) Pressure (Inlet) Feed rate Gas rate Steam rate  Material Balance: Error limit (± 2 %) IOC R&D CENTRE

Tender Catalyst Evaluation Criteria

CATALYSTS

PERFORMANCE PARAMETERS

HDS

‘S’ Slippage

ZnO

‘H2S’ Slippage

Prereformer

Ethane & higher HC (C2+) Slippage

Reformer

Methane Slippage

Shift (HT / MT / LT)

CO Slippage

IOC R&D CENTRE

Tender Catalyst Evaluation Criteria Typical Tender Evaluation Criteria CATALYSTS

GUARANTY COMPOUND SLIPPAGE

HDS

0.2 ppm wt. Organic sulphur max

Pre-reformer

0.2 vol % C2+ dry basis (max)

Reformer

3 – 4.5 vol % CH4 dry basis (max)

HT Shift

6 vol % CO dry basis (max)

MT Shift

3.9 vol % CO dry basis (max)

LT Shift

1.0 vol % CO dry basis (max)

IOC R&D CENTRE

Pre-Reformer Catalyst Evaluation

COMPOSITION OF EXIT GAS, VOL % COMPONENT

C2+ fraction vol%

H2

CO

CO2

CH4

COMMERCIAL PLANT

Trace

23.7

0.2

17.8

58.3

VENDOR-A

Trace

23.4

0.8

17.69

57.71

VENDOR-B

Trace

23.03

0.79

17.18

57.98

VENDOR- C

Trace

21.9

0.77

17.6

59.73

IOC R&D CENTRE

Reformer Catalyst Evaluation Component

Commercial Plant

Vendor-1

Vendor-2

CH4

4.1

2.79

2.33

H2

66.8

69.32

69.61

CO

18.9

18.51

19.30

CO2

10.1

9.38

8.76

IOC R&D CENTRE

MTS Catalyst Evaluation

CATALYST

COMPOSITION OF EXIT GAS, VOL %

COMPONENT

H2

CO

CO2

COMMERCIAL PLANT

74.6

0.8

19.4

VENDOR- A

75.45

1.82

22.73

VENDOR-B

75.41

1.87

22.72

VENDOR- C

75.49

1.63

22.88

IOC R&D CENTRE

LTS Catalyst Evaluation

CATALYST

COMPOSITION OF EXIT GAS, VOL %

COMPONENT

H2

CO

CO2

COMMERCIAL PLANT

75.4

0.4

18.4

VENDOR-A

73.69

0.72

25.58

VENDOR-B

73.99

0.46

25.55

IOC R&D CENTRE

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 vendor’s procedure  HDS section start-up (In case of sour naphtha )   

Sulphiding as per vendor procedure (use by- 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 IOC R&D CENTRE

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 IOC R&D CENTRE

IOC R&D CENTRE