hydrogen recovery & management in refineries
TRANSCRIPT
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Hydrogen Recovery & Management in Refineries
ByMadan K. SinhaTechnip KT India Ltd., Noida
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CONTENTS
Ø NEED AND OBJECTIVE
Ø ROG UTILIZATION IN REFINERIES
Ø CONTRIBUTION BASED ROG INTEGRATION WITH HYDROGEN GENERATION
Ø CASE STUDIES
Ø CONCLUSIONS
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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
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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.
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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
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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
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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
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RELATIVE ECONOMICS OF H2 RECOVERY SYSTEM
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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
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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
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HYBRID SYSTEMSHYBRID SYSTEMSØMEMBRANE – PSA SYSTEM
HYBRID SYSTEMS
COLD BOX
REFINERY
PRE-TREATMENT
COMPRESSION
LPG
ROG MEMBRANE
FUEL
H2
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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
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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
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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
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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%
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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
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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$/HOPERATING COST
313134KWh/HPOWER
4.85.8T/HEXPORT STEAM
23862637KG/HTOTAL FEED + FUEL
335197KG/HFUEL ROG
20512440KG/HFEED ROG
RECOVERY PSADIRECT REFORMINGUNIT
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CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTION
PROJECT PROFILE
Ø ADDITIONAL HYDROGEN DEMAND FOR HC PROJECT : 55000 NM3/H
Ø ROG CONTRIBUTION : ~35000 NM3/H
i. RATIO OF CONTAINED H2 / GENERATED H2 = ~ 2
ii. LIQ. HC FEED / ROG PRICE RATIO = 1.3
Ø MAXIMUM USE OF ROG & ITS HC CONTENT AS FEED FOR HYDROGEN GENERATION
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CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTION
BASIS OF DESIGN
Ø COMBINED (TREATED) ROG STREAM SUPPLY :i. 76 – 88% H2 CONTENT ii. 20 ppmv H2S ex-MDEA, WATER SATURATEDiii. 25 barg PRESSURE
Ø PRODUCT H2 PRESSURE : 24 barg
Ø SUPPLEMENTAL AND / OR ALTERNATIVE FEEDSTOCK : i. LPG AND LIGHT NAPHTHA (T85) IN ANY MIX
Ø FALL-BACK MODE : i. UNIT FAILURE (H2 RECOVERY OR GENERATION OR ROG SOURCES) TO
SUSTAIN MIN. 50% H2 FOR HYDROCRACKER
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CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTION
PSA DESIGN CONSIDERATION
Ø RANGE OF FLOW, COMPOSITIONS AND IMPURITIES
Ø H2 RECOVERY > 89% : OPTIMIZATION AGAINST POWER & INVESTMENT
Ø ADSORBENT’S TOLERANCE FOR HEAVIER HCs (worst scenario)
Ø OPTIMIZATION ON NUMBER OF ADSORBERSi. CYCLIC STABILITY OF PURGE GAS(mw) FOR ITS PROPER COMPRESSION
DOWNSTREAMii. AUTOMATIC CYCLE ADJUSTMENT BASED ON VARIATION IN FEED H2 CONTENTiii. REDUCED BED OPERATIONiv. INSTALLED COST
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CASE STUDY (2) – HIGH HYDROGEN CONTRIBUTIONECONOMIC ANALYSIS
Base2.1MM$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
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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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CASE STUDY(3) – ROG AS FEED
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
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CASE STUDY(3) – ROG AS FEED
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
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CASE STUDY(3) – ROG AS FEED
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%
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CASE STUDY(3) – ROG AS FEED
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……
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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 :