Hydrogen Recovery & Management in Refineries

1

Hydrogen Recovery & Management in Refineries

ByMadan K. SinhaTechnip KT India Ltd., Noida

2Hydrogen Recovery & Management, Aug'10

CONTENTS

Ø NEED AND OBJECTIVE

Ø ROG UTILIZATION IN REFINERIES

Ø CONTRIBUTION BASED ROG INTEGRATION WITH HYDROGEN GENERATION

Ø CASE STUDIES

Ø CONCLUSIONS

2


THE NEED

Ø ENVIRONMENTAL CONCERNS, DEMANDING REGULATIONS

- SOX, NOX , CO2 EMISSION ETC.

Ø CHANGING PRODUCT QUALITY - ULTRA CLEAN FUELS

Ø CHANGING CRUDE SPECIFICATIONS - SOURER/ HEAVY OPPORTUNITY CRUDE

Ø CHANGING REFINERY PRACTICES - DEEP CONVERSION REFINERIES AND BOTTOM OF

BARREL STRATEGIES

Ø INCREASED HYDROGEN DEMAND


OBJECTIVESØ OPTIMAL UTILIZATION & DISTRIBUTION OF HYDROGEN IN RELATION TO

STRESS ON OPTIMIZING, NOT MINIMIZING THE HYDROGEN NETWORK

Ø COST EFFECTIVE UTILIZATION OF HYDROGEN RESOURCES INSIDE REFINERY

Ø EFFECTIVE ELIMINATION OF CONSTRAINTS ON HYDROGEN AVAILABILITY BY ‘ON-PURPOSE’ HYDROGEN GENERATION

Ø IMPROVING EFFICIENCY, RELIABILITY, OPERATIONAL FLEXIBILITY & RUNTIME

Ø FORMULATING STRATEGIES ON BY-PRODUCTS AND CAPTIVE ENERGY GENERATION

Ø IMPROVING HYDROPROCESSING EFFICIENCY, MAXIMIZE PROFITABILITY

Ø MINIMIZE HYDROGEN LOSS TO FUEL

Ø VARIOUS H2-CONSUMERS & H2-PRODUCERS IN THE REFINERY (TO BRIDGE H2-SHORTFALL EFFECTIVELY

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HYDROGEN DEFICIT MANAGEMENT

Ø SPECIFIC REFINERY SCHEME BASED ON • ESSENTIALITY, • LEVEL OF INVESTMENT,• EXTENT OF MODIFICATIONS, • FEEDSTOCK OPTIONS • MARKET FACTORS

Ø HYDROGEN AVAILABILITY THROUGH• H2 RECOVERY FROM ROG• REVAMPING EXISTING H2 FACILITIES• ON-PURPOSE’ H2 MANUFACTURE

Ø HYDROGEN MANAGEMENT : EFFICIENT & COST-EFFECTIVE UTILIZATION OF OFF-GASES FROM VARIOUS CONSUMERS IN REFINERY AS COMPARED TO ‘ON-PURPOSE’ H2.


TYPICAL CONDITIONS OF ROG

TYPICAL ROG SOURCE PRESSURE (BAR) VOL. % H2

CATALYTIC REFORMING OFF GAS 15 – 30 70 – 90

HYDROCRACKER HP VENT 40 – 140 60 – 85

HYDROTREATER OFF GAS 15 – 50 65 – 80

FCC / DELAYED COKER OFFGAS 5 – 15 15 - 30

4


ROG UTILIZATION ROUTES

COMPRESSION / PRE-TREATMENT

DIRECT

HYDROGEN GENERATION

UNIT

REFINERY OFF-GASES

REF

INER

Y FU

EL N

ET

HIGH PURITY H2 HIGH PURITY

RECOVERY

LOW PURITY RECOVERY

CONSUMER - A

COMPRESSION

CONSUMER - B

CONSUMER - CHIG

H P

UR

ITY

HYD

RO

GEN

NET

WO

RK

BLE

ND

ING

HC FEEDSTOCK

PURITY CASCADING


HYDROGEN RECOVERY FROM ROG

PHYSICAL SEPARATIONSØ PRESSURE SWING ADSORPTION (PSA) SYSTEM

i. Relative Diffusivity Basedii. High Purity / High Pressure Hydrogen

Ø MEMBRANE SYSTEMi. Relative Permeability Basedii. High Feed Pressureiii. Medium Purity / Low Pressure Hydrogen

Ø CRYOGENIC SYSTEMi. Relative Volatilty Basedii. Hydrocarbon Product Creditiii. Economy of Scale

Ø HYBRID SYSTEMSi. Maximum Purity, Recovery, Flexibilty and Capital Returns

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OVERVIEW OF HYDROGEN RECOVERY SYSTEMS

PARAMETER PSA MEMBRANE CRYOGENIC

Min. % of H2 in Feed ~50 15 15

H2 Capacity (KNm3/h) 0.1 – 100 0.5 – 70 5 – 1000

Feed Pressure (Bar) 10 – 65 15 – 120 10 – 80

H2 Prod. Pr. (Bar) Close to Feed P < 1/3 of Feed P ~Feedàlow P

Feed Pretreatment No Yes Yes

H2 Purity (Vol%) ~99.999 ~98 ~97

H2 Recovery (%) ~90 ~95 ~98

Min. turn down (%) 25 15 50

Ease of Expansion ++ +++ +

Flexibility +++ ++ +

Reliability ++ / +++ +++ +

By product Recovery - + +++

Economy of Scale Moderate Small Large


RELATIVE ECONOMICS OF H2 RECOVERY SYSTEM

6


HYBRID SYSTEMS

Ø PSA – CRYOGENIC SYSTEM (including pretreatment)

COLD BOX

PRE-TREATMENT

COMPRESSION

PSA-II

REFINERY COMPLEX

REFORMER +SHIFT PSA-I

COMPRESSION

C2 BY-PRODUCT

H2

LP/Lo-H2HP/Hi-H2

PURGE

HC MU FUEL

PURGE GAS FUEL

HC FEED

FUEL


HYBRID SYSTEMSØMEMBRANE – PSA SYSTEM

HYBRID SYSTEMSCATALYTIC REFORMER

COMPRESSION

PSA-II

REFINERYREFORMER +SHIFT PSA-I

COMPRESSION

H2

LP FLASHHP VENTHC MU

FUEL

PURGE GAS FUEL

HC FEED

OFF-GAS

MEMBRANE

FUEL

7


HYBRID SYSTEMSHYBRID SYSTEMSØMEMBRANE – PSA SYSTEM

HYBRID SYSTEMS

COLD BOX

REFINERY

PRE-TREATMENT

COMPRESSION

LPG

ROG MEMBRANE

FUEL

H2


CRITERIA FOR ROG INTEGRATION

Ø AVAILABLE STREAM(S)i. Quantities, %Hydrogen / Hydrocarbonii. Contaminantsiii. Pressure Regimes

Ø REQUIRED PRODUCT(S)i. Capacity, Purity & Pressureii. Existing Hydrogen Network

Ø REFINERY FUEL GAS NETWORK PRESSURE

Ø OPERATIONAL FLEXIBILITY AND RELIABILITYi. Range of Composition Variation/ Transient Nature of ROG Source(s) :

SOR / EOR Conditions / Regeneration Modes / Refinery Feed stock Variationsii. Turn down requirementsiii. Failure & Fall back modes

……….Continued

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CRITERIA FOR ROG INTEGRATION (….Concld.)

Ø ECONOMIC DRIVERSi. Added Value : Product Credit vs. Fuel valueii. Utility Costs and Availabilityiii. Capital Costs including any Pretreatment Requirediv. Benefit for potential recovery of C2+

Ø IMPLEMENTATIONi. Scheduleii. Available Plot Space & Existing Layout


INTEGRATION BASED ON HYDROGEN CONTRIBUTION

ØPOTENTIAL HYDROGEN CONTRIBUTION = NET EXTRA H2 PRODUCED

ØCLASSIFICATION OF ROG :

• LOW HYDROGEN CONTRIBUTION

• MEDIUM HYDROGEN CONTRIBUTION

• HIGH HYDROGEN CONTRIBUTION

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GUIDELINES FOR ROG INTEGRATION

PROCESS AND OPERATIONAL ASPECTS

COMBINED PSA DIRECT REFORMING RECOVERY PSA

COMPLEXITY MEDIUM LOW HIGH

LOSS OF ROG SUPPLY

LOSS OF ~10% H2 CAPACITY

LOSS OF ~20% -30% OF H2 CAPACITY.

CHANGE OF FEEDSTOCK

LOSS OF LARGE PART OF H 2 CAPACITY.

CHANGE OF FEEDSTO CK

EXCESS PURGE GAS FUEL

TO DEDICATED HEADER TO REFINERY FUEL TO REFINERY FUEL


LOW HYDROGEN CONTRIBUTION

CoMo+

ZnO

SHIFT

HC FEED & HC FEED & FUELFUEL

MAKEMAKE--UP FUELUP FUEL

PSA UNIT

HH2 2 (TOTAL)(TOTAL)

REFINERY OFF GAS (ROG)REFINERY OFF GAS (ROG)

PROCESSPROCESSGAS BOILERGAS BOILER

HEATHEATRECOVERYRECOVERY

REFORMER

PSA PURGE GAS (TOTAL)PSA PURGE GAS (TOTAL)

CONDENSATECONDENSATE

FLUE GASES

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LOW HYDROGEN CONTRIBUTION

FEATURES

ØSIMPLE TO IMPLEMENTØMINOR INVESTMENT, LIMITED TO PSA MODIFICATIONSØENDS UP IN EXCESS PURGE GAS FUELØSENSITIVE TO CAPACITY SWING VARIATIONS : REFORMER TURNDOWN / ROG

AVAILABILTYØSENSITIVE TO VARIATION IN COMPOSITION (EOR/SOR CONDITIONS)ØELABORATE CONTROL REQUIRED TO PROTECT AGAINST HIGHER

HYDROCARBON BREAK THROUGHØDETRIMENTAL TO PSA OPERATION ON LOSS OF REFORMED SHIFT GASØGENERALLY WORTHWHILE TO CONSIDER WHEN ROG / SHIFTED GAS <10 - 15%

BASED ON ITS H2 CONTENTØALSO SCHEME IS FEASIBLE WHEN ENTIRE PURGE GAS IS UTILIZED IN

REFORMER


MEDIUM HYDROGEN CONTRIBUTION

CoMo+

ZnOSHIFT

ROG ROG (PRE(PRE--TREATED)TREATED)

MAKEMAKE--UP FUELUP FUEL

PSA UNIT HH22

PROCESSPROCESSGAS BOILERGAS BOILER

HEATHEATRECOVERYRECOVERY

REFORMER

PSA PURGE GASPSA PURGE GAS

ALTERNATIVEALTERNATIVEHC FEED

CONDENSATE

FLUE GASES

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MEDIUM HYDROGEN CONTRIBUTION

FEATURES

ØROG AS DIRECT FEED TO REFORMER WITH / WITHOUT SUPPLEMENTAL FEEDSTOCKØSUITABLE WHEN LARGE QUANTITIES OF HC RICH ROG IS

AVAILABLE (TOO LARGE FOR COMMON PSA; NOT TOO LARGE FOR DEDICATED PSA)ØPRE-TREATMENT AND COMPRESSION OF ROGØNET REFORMER FUEL IS LOWER COMPARED TO USING

HYDROCARBON FEEDSTOCK (60 - 85%)ØFULL UTILISATION OF OFFGAS TOWARDS PRODUCTION OF H2

ØTHIS SCHEME IS GENERALLY COST EFFECTIVE IF HYDROGEN CONTRIBUTION IS BELOW 50%


HIGH HYDROGEN CONTRIBUTION

HYDROGEN RECOVERY

UNIT

COMPRESSION/ PRE-TREATMENT

REFORMING + SHIFT

MAKE-UP FUEL

OPTIONAL

H2

HIGH-PURITY HYDROGEN

REFINERY OFF GASES

HC-RICH STREAM

ALTERNATE FEED GENERATION PSA

TO REFINERY FUEL NETWORK

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HIGH HYDROGEN CONTRIBUTIONFEATURES

Ø SUITABLE SCHEME WHEN ROG STREAMS HYDROGEN CONTRIBUTION IS HIGH (> 50%).

Ø INDEPENDENT OPERATION OF REFORMER AND OFF-GAS PSA UNITØ POTENTIAL FOR MULTIPLE OFF-GAS STREAMSØ DEDICATED PSA FOR OFF-GAS RECOVERYØ POSSIBLE PSA OFF-GAS USE AS REFORMER FEED AND FUEL (OPEX)Ø PURGE GAS COMPRESSION REQUIRED TO IMPROVE RECOVERYØ OFF-GAS PRE-TREATMENT (FOR CHLORINE, H2S) MAY BE REQUIREDØ ADDITIONAL INVESTMENT FOR PSA AND PURGE GAS COMPRESSION IS

CLOSE TO REDUCTION IN H2 GENERATION UNIT CAPACITY (CAPEX)ØELABORATE CONTROL REQUIRED TO PROTECT AGAINST HIGHER

HYDROCARBON BREAK THROUGH IN ADSORBENTØ SUBSTANTIAL SAVING IN BASE FEED STOCK


CASE STUDY (1) – MEDIUM HYDROGEN CONTRIBUTION

SUMMARY

Ø HYDROGEN DEMAND FOR HDS PROJECT ~36000 NM3/H

i. ROG AVAILABILITY 60-90% H2 AT 34 BARG HAVING ~30%CONTRIBUTION

ii. COMPLEMENTED BY HC CONTENT / BACK-UP LIQUID FEED REFORMING ON ATTAINABLE CAPACITY

Ø RATIO OF ROG / ON-PURPOSE H2 :

i. LARGE FOR COMMON PSA; SMALL FOR DEDICATED PSA

ii. NO INFLUENCE OF ROG FLUCTUATIONS ON PSA PERFORMANCE

Ø PRE-REFORMER NOT FEASIBLE

Ø DIRECT REFORMING OF ROG AND LIQUID FEED

Ø PRODUCT HYDROGEN COMPRESSION; AND NOT FEED COMPRESSION

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CASE STUDY (1) – MEDIUM HYDROGEN CONTRIBUTION

ECONOMIC ANALYSIS

BadGoodPAY-OFF

PSA & COMPRESSOR--ADDITIONAL EQPT

2828REFORMER TUBES

303332$/HOPERATING COST

313134KWh/HPOWER

4.85.8T/HEXPORT STEAM

23862637KG/HTOTAL FEED + FUEL

335197KG/HFUEL ROG

20512440KG/HFEED ROG

RECOVERY PSADIRECT REFORMINGUNIT


CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTION

PROJECT PROFILE

Ø ADDITIONAL HYDROGEN DEMAND FOR HC PROJECT : 55000 NM3/H

Ø ROG CONTRIBUTION : ~35000 NM3/H

i. RATIO OF CONTAINED H2 / GENERATED H2 = ~ 2

ii. LIQ. HC FEED / ROG PRICE RATIO = 1.3

Ø MAXIMUM USE OF ROG & ITS HC CONTENT AS FEED FOR HYDROGEN GENERATION

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BASIS OF DESIGN

Ø COMBINED (TREATED) ROG STREAM SUPPLY :i. 76 – 88% H2 CONTENT ii. 20 ppmv H2S ex-MDEA, WATER SATURATEDiii. 25 barg PRESSURE

Ø PRODUCT H2 PRESSURE : 24 barg

Ø SUPPLEMENTAL AND / OR ALTERNATIVE FEEDSTOCK : i. LPG AND LIGHT NAPHTHA (T85) IN ANY MIX

Ø FALL-BACK MODE : i. UNIT FAILURE (H2 RECOVERY OR GENERATION OR ROG SOURCES) TO

SUSTAIN MIN. 50% H2 FOR HYDROCRACKER



PSA DESIGN CONSIDERATION

Ø RANGE OF FLOW, COMPOSITIONS AND IMPURITIES

Ø H2 RECOVERY > 89% : OPTIMIZATION AGAINST POWER & INVESTMENT

Ø ADSORBENT’S TOLERANCE FOR HEAVIER HCs (worst scenario)

Ø OPTIMIZATION ON NUMBER OF ADSORBERSi. CYCLIC STABILITY OF PURGE GAS(mw) FOR ITS PROPER COMPRESSION

DOWNSTREAMii. AUTOMATIC CYCLE ADJUSTMENT BASED ON VARIATION IN FEED H2 CONTENTiii. REDUCED BED OPERATIONiv. INSTALLED COST

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CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTIONECONOMIC ANALYSIS

Base2.1MM$NET ADDITIONAL INVESTMENT

INCL. COMPRESSION

1932$/HCATALYST COST17671714$/HOPERATING COST

Base0.3MM$/YANNUAL OPEX SAVING

Base6.9YearsPAY-OFF

2.5--MM$RECOVERY PSA INVESTMENT

80104BaseREFORMER TUBES

Base+40%H2 GENERATION UNIT SIZE

1344828KWh/HPOWER

20.730.6T/HEXPORT STEAM

47064777KG/HTOTAL FEED + FUEL

27171295KG/HFUEL19893482KG/HHC FEED

RECOVERY PSADIRECT REFORMINGUNIT


CASE STUDY(3) – ROG AS FEED

LIGHT NAPHTHA FEED PUMPING

FACILITYVAPORI-SATION

FEED TREATMENT

PRE-REFORMER

REFORMERHEAT

RECOVERY & BFW SYSTEM

HT SHIFT & LT SHIFTPSA UNIT

PURGE GAS FUELFUEL

ROG

H2PRODUCT

BFW

HP STEAM

PROCESS STEAM

PROCESS STEAM

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0.0

1.0

2.0

3.0

0.0 10.0 20.0 30.0 40.0

RED

UC

TIO

N I

N N

APH

THA

RA

TE (T

ON

S / H

R)

%H2 CONTRIBUTION FROM ROG



0.0

1.0

2.0

3.0

0.0 10.0 20.0 30.0 40.0

RED

UC

TIO

N I

N T

OTA

L FU

EL

FIR

ING

(MM

Kca

l/Hr)

%H2 CONTRIBUTION FROM ROG

17



HYDROGEN PRODUCTION : 2.25 TONS/HR

NAPHTHA FEED : 7.72 TONS/HR

ROG UTILIZED FOR REFORMING : 1.5 TONS/HR

VOL% OF H2 IN ROG : 70%



SAVINGS IN NAPHTHA FEED : 1.90 TONS/HR

SAVINGS IN FUEL FIRED : 0.20 TONS/HR

REPLACEMENT FUEL EQUIVALENT OF ROG : 1.30 TONS/HR

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CONCLUSIONS

Ø DEMAND FOR HYDROGEN IS INCREASING Ø STRONG NEED FOR HYDROGEN MANAGEMENT Ø HYDROGEN RECOVERY FROM ROG HAS A VITAL ROLEØ SUITABLE SELECTION OF RECOVERY METHOD / INTEGRATION WITH “ON-

PURPOSE HYDROGEN” IS NEEDEDi. PHYSICAL SEPARATIONii. INTEGRATION WITH “ON-PURPOSE” HYDROGEN

Ø INTEGRATION TO BE BASED ON HYDROGEN CONTRIBUTION FROM ROG USING i. COMMON PSA ii. DIRECT REFORMINGiii. RECOVERY PSA

Ø CONFIGUARATION DEPENDS ON PRESENT SYSTEM, ECONOMICS, FEASIBILITY, AND RELIABILITY

Ø METHODOLOGICAL APPROACH STRONGLY DEPEND ON PROJECT TYPOLOGY & ENVIRONMENTAL CONSTRAINTS

Ø NECESSARY FOR EACH PROJECT & CLIENT ENVIRONMENT TO RE-EVALUATE H2ECONOMICS IN LIGHT OF ANY SPECIFIC CONSTRAINT

Contd……


CONCLUSIONS (concl.)

Ø TECHNIP CAN HELP REFINERS TO FIND OUT OPTIMUM SOLUTION USING GROUP TRANSVERSAL COMPETENCE & ADVANCED METHODOLOGIES:

- Knowledge of available option for H2 production, supply & recovery

- Suite of tools based on advanced LP modeling, for planning of all refinery operations

- Expertize on equipment cost estimates with a scaling accuracy

Ø THESE COMPETENCES ARE NOW CONCENTRATED IN TECHNIP’S HYDROGEN NETWORK DESIGN TOOL : HyN.DTTM

Ø SUCCESSFULLY USED TO OPTIMIZE A COMPLEX GRASS-ROOT REFINERY IN TATARSTAN

- (7 MMTPY crude, maximise diesel & jet fuels @EURO V specifications, min. Residue)

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THANKS FOR YOUR KIND ATTENTION

For any clarifications please write to :

[email protected]

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Hydrogen Recovery & Management in Refineries

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