Hydrogen Production in Refineries December 2013 Report Contents

Hydrogen Production in
Refineries
Table of Contents
A Report by Nexant
Process Evaluation/Research Planning (PERP) Program
PERP Report 2013S3 – Published December 2013
www.nexantthinking.com

Section Page

1 Executive Summary ................................................................................................. 1

1.1 ON-PURPOSE HYDROGEN PRODUCTION ............................................. 1
1.1.1 Natural Gas Feedstocks...................................................................... 1
1.1.2 Naphtha Feedstocks ........................................................................... 5
1.1.3 Adiabatic Pre-reforming .................................................................... 5
1.1.4 Partial Oxidation/Gasification of Residual Oil .................................. 7
1.1.5 Hydrogen from Refinery Off Gas ...................................................... 8
1.2 HYDROGEN RECOVERY AND PURIFICATION .................................... 10
1.2.1 Pressure Swing Adsorption ................................................................ 10
1.2.2 Membrane Separation ........................................................................ 11
1.3 PROCESS ECONOMICS .............................................................................. 11
1.3.1 Natural Gas Steam Reforming ........................................................... 11
1.3.2 Naphtha Steam Reforming ................................................................. 12
1.3.3 Partial Oxidation/Gasification of Residual Oil .................................. 13
1.3.4 Purification Using Pressure Swing Adsorption ................................. 13
1.3.5 Membrane Purification ...................................................................... 14
1.4 COMMERCIAL STATUS ............................................................................ 15
2 Introduction .............................................................................................................. 17
3 Hydrogen Production and Purification ................................................................. 19
3.1 HYDROGEN PRODUCTION ...................................................................... 19

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3.1.1 Reforming-Based Hydrogen Production............................................ 19

3.1.2 Partial Oxidation/Gasification of Residual Oil .................................. 27
3.1.3 Hydrogen from Refinery Off-Gases .................................................. 32
3.2 HYDROGEN RECOVERY AND PURIFICATION .................................... 33
3.2.1 Introduction ........................................................................................ 33
3.2.2 Pressure Swing Adsorption ................................................................ 33
3.2.3 Membrane Separation ........................................................................ 37
3.2.4 Cryogenic Systems............................................................................. 37
4 Hydrogen Technology Licensors ............................................................................ 40
4.1 REFORMING-BASED HYDROGEN PRODUCTION LICENSORS......... 40
4.1.1 Foster Wheeler ................................................................................... 40
4.1.2 Haldor Topsoe .................................................................................... 44
4.1.3 Technip .............................................................................................. 50
4.1.4 ICI Gas Heated Reformer .................................................................. 57
4.1.5 Uhde ................................................................................................... 57
4.1.6 KBR ................................................................................................... 60
4.1.7 The Linde Group ................................................................................ 62
4.1.8 CB&I .................................................................................................. 63
4.1.9 Air Liquide-Lurgi............................................................................... 63
4.1.10 Small-Scale Reformers ...................................................................... 63
4.1.11 JGC .................................................................................................... 66
4.2 PROCESS CATALYST LICENSORS FOR HYDROGEN
PRODUCTION .............................................................................................. 67
4.2.1 Haldor Topsoe .................................................................................... 67
4.2.2 BASF.................................................................................................. 68
4.2.3 Johnson Matthey ................................................................................ 68
4.2.4 Clariant ............................................................................................... 69
4.2.5 Matros Technologies .......................................................................... 69
4.3 PARTIAL OXIDATION/GASIFICATION BASED HYDROGEN
PRODUCTION LICENSORS ....................................................................... 69
4.3.1 Review of Experience ........................................................................ 69
4.4 POLYMER MEMBRANE HYDROGEN RECOVERY LICENSORS ....... 71

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4.4.1 Air Products ....................................................................................... 71

4.4.2 UOP.................................................................................................... 74
4.4.3 Membrane Technology and Research (MTR) ................................... 75
4.5 PSA BASED HYDROGEN RECOVERY LICENSORS ............................. 76
4.5.1 UOP.................................................................................................... 76
4.5.2 Air Liquide ......................................................................................... 80
4.5.3 Linde .................................................................................................. 81
5 Recent Developments ............................................................................................... 82
5.1 NEW REFORMER TECHNOLOGIES ........................................................ 82
5.1.1 CO2 Reforming (or Dry Reforming) .................................................. 82
5.1.2 Membrane Reforming Reactors ......................................................... 82
5.1.3 Sorbent-Enhanced Reforming ............................................................ 84
5.1.4 Plasma Reforming .............................................................................. 84
5.2 NEW PURIFICATION TECHNOLOGIES .................................................. 85
5.2.1 Solid Membranes ............................................................................... 85
5.2.2 Carbon Molecular Sieves (CMS) ....................................................... 86
5.2.3 Palladium Alloy Composite Membrane............................................. 87
5.2.4 Mixed Matrix Membranes ................................................................. 87
5.2.5 Fast Cycle PSA .................................................................................. 88
6 Economic Analysis ................................................................................................... 90
6.1 METHODOLOGY ........................................................................................ 90
6.2 FEEDSTOCK AND UTILITY PRICING ..................................................... 91
6.3 PROCESS ECONOMICS FOR STEAM REFORMING OF METHANE
TO HYDROGEN ........................................................................................... 91
6.3.1 Process Economics............................................................................. 91
6.3.2 Sensitivity to Changes in Plant Capacity ........................................... 94
6.3.3 Sensitivity to Changes in Capital Cost............................................... 94
6.3.4 Sensitivity to Changes in Feedstock Price ......................................... 95
6.4 PROCESS ECONOMICS FOR NAPHTHA STEAM REFORMING.......... 96
6.4.1 Process Economics............................................................................. 96
6.4.2 Sensitivity to Changes in Capacity .................................................... 98
6.4.3 Sensitivity to Changes in Capital Cost............................................... 99
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6.4.4 Sensitivity to Changes in Feedstock Price ......................................... 100

6.5 PROCESS ECONOMICS FOR PARTIAL OXIDATION OF
RESIDUAL OIL ............................................................................................ 101
6.5.1 Process Economics............................................................................. 101
6.5.2 Sensitivity to Changes in Plant Capacity ........................................... 103
6.5.3 Sensitivity to Changes in Capital Cost............................................... 104
6.5.4 Sensitivity to Changes in Feedstock Price ......................................... 105
6.6 PROCESS ECONOMICS FOR PURIFICATION USING PRESSURE
SWING ADSORPTION ................................................................................ 106
6.6.1 Process Economics............................................................................. 106
6.6.2 Sensitivity to Changes in Plant Capacity ........................................... 108
6.6.3 Sensitivity to Changes in Capital Cost............................................... 109
6.6.4 Sensitivity to Changes in Feedstock Price ......................................... 110
6.7 PROCESS ECONOMICS FOR MEMBRANE PURIFICATION ................ 111
6.7.1 Process Economics............................................................................. 111
6.7.2 Sensitivity to Changes in Capacity .................................................... 113
6.7.3 Sensitivity to Changes in Capital Cost............................................... 114
6.7.4 Sensitivity to Changes in Feedstock Price ......................................... 115
6.8 CONCLUSIONS............................................................................................ 116
7 Commercial Analysis ............................................................................................... 118
7.1 COMMERCIAL STATUS ............................................................................ 118
7.1.1 Hydrotreating ..................................................................................... 118
7.1.2 Hydrocracking.................................................................................... 119
7.2 REFINERY HYDROGEN OPTIONS ........................................................... 119
7.2.1 The Traditional Refinery Model ........................................................ 119
7.2.2 Third Party Supply Schemes .............................................................. 120
7.3 CAPACITY STATUS ................................................................................... 120
7.3.1 Global Capacity ................................................................................. 120
7.3.2 United States ...................................................................................... 121
7.3.3 Other North America ......................................................................... 124
7.3.4 Western Europe .................................................................................. 124
7.3.5 Asia .................................................................................................... 126

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7.3.6 Eastern Europe/CIS ............................................................................ 128

7.3.7 Middle East ........................................................................................ 129
7.3.8 Africa ................................................................................................. 130
7.3.9 Central and South America ................................................................ 131
8 Glossary .................................................................................................................... 132
9 References ................................................................................................................. 133

Appendix Page

A Cost of Production Tables ....................................................................................... A-1

B Definitions of Capital Cost Terms Used in Process Economics ........................... B-1
C Definitions of Operating Cost Terms Used in Process Economics ...................... C-1
D PERP Program Title Index (2004 - 2013) .............................................................. D-1

Figure Page

1.1 Hydrogen Balance in Refineries ................................................................................ 10

1.2 Cost of Production + ROCE for Hydrogen Production Processes ............................. 15
2.1 Global Crude Quality ................................................................................................. 18
3.1 Steam-Methane Reforming ........................................................................................ 20
3.2 Gasification Process Flow Diagram........................................................................... 30
3.3 Hydrogen Balance in Refineries ................................................................................ 33
3.4 PSA Unit .................................................................................................................... 36
3.5 Partial Condensation Process ..................................................................................... 39
4.1 Typical Downfired Reformer Furnace ....................................................................... 42
4.2 Terrace Wall Reformer Furnace ................................................................................ 42
4.3 Haldor Topsoe Convective Reformer (HTCR) .......................................................... 48
4.4 HTCR Operating Principle ........................................................................................ 49
4.5 Haldor Topsoe Exchange Reformer (HTER) ............................................................ 50
4.6 Process Flow Diagram of Technip Hydrogen Plant ................................................. 56
4.7 Uhde’s Steam Reformer ............................................................................................. 59
4.8 Uhde CARTM .............................................................................................................. 60
4.9 KRESTM ..................................................................................................................... 62
4.10 Catacel SSR ............................................................................................................... 66

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4.11 JGC MRG Process ..................................................................................................... 67

4.12 PRISM Membrane Applications ................................................................................ 72
4.13 Air Products PRISM Membrane ................................................................................ 73
4.14 MTR VaporSep-H2TM Operation ............................................................................... 76
4.15 Pressure Swing Adsorption - Overview...................................................................... 79
4.16 PSA Process Flow Diagram ....................................................................................... 80
5.1 Tokyo Gas Hydrogen Membrane Reformer .............................................................. 84
5.2 Pall Pd-Alloy Composite Membrane for Hydrogen Separation ................................ 87
5.3 Xebec’s Rapid-Cycle PSA Technology ..................................................................... 89
6.1 Sensitivity to Changes in Plant Capacity (USGC SMR) .......................................... 94
6.2 Sensitivity to Changes in Capital Cost (USGC SMR) ............................................... 95
6.3 Sensitivity to Changes in Feedstock Price (USGC SMR) ......................................... 96
6.4 Sensitivity to Changes in Plant Capacity (USGC NAP-Reforming) ......................... 99
6.5 Sensitivity to Changes in Capital Cost (USGC NAP-Reforming) ............................ 100
6.6 Sensitivity to Changes in Feedstock Price (USGC SMR) ......................................... 101
6.7 Sensitivity to Changes in Plant Capacity (USGC POX-Resid) ................................. 104
6.8 Sensitivity to Changes in Capital Cost (USGC POX-Resid) ..................................... 105
6.9 Sensitivity to Changes in Feedstock Price (USGC POX-Resid) ............................... 106
6.10 Sensitivity to Changes in Operating Rate (PSA) ...................................................... 109
6.11 Sensitivity to Changes in Capital Cost (PSA)........................................................... 110
6.12 Sensitivity to Changes in Feedstock Price (PSA) ..................................................... 111
6.13 Sensitivity to Changes in Plant Capacity (Membrane) .............................................. 114
6.14 Sensitivity to Changes in Capital Cost (Membrane)................................................. 115
6.15 Sensitivity to Changes in Feedstock Price (Membrane) ........................................... 116
6.16 Cost of Production + ROCE for Hydrogen Production Processes ............................. 117
7.1 Hydrogen Consumption for Hydrotreating of Various Refinery Products ................ 119

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Table Page

1.1 Major Refinery Gasification/POX Units ................................................................... 8

1.2 Typical Hydrogen Content in Refinery Off Gas Streams .......................................... 9
1.3 Cost of Hydrogen Production from Natural Gas Reforming ..................................... 12
1.4 Cost of Hydrogen Production from Naphtha Steam Reforming ................................ 12
1.5 Cost of Hydrogen Production from Partial Oxidation of Residual Oil ...................... 13
1.6 Regional Cost of Hydrogen Purification by Pressure Swing Adsorption .................. 14
1.7 Regional Cost of Hydrogen Purification by Membrane Separation .......................... 14
1.8 Global Hydrogen Plant Capacity ............................................................................... 16
3.1 Major Refinery Gasification/POX Units ................................................................... 28
3.2 Raw Syngas Characteristics ....................................................................................... 31
3.3 Typical Hydrogen Content in Refinery Off Gas Streams .......................................... 32
3.4 List of Common Adsorbents and Adsorbates ............................................................ 35
4.1 Natural Gas Quality ................................................................................................... 51
4.2 Catalyst Requirements ............................................................................................... 54
4.3 Examples of Shell Gasification Process Refinery and Heavy Oil Applications ........ 71
6.1 Assumptions for Cost of Production Analyses .......................................................... 90
6.2 Regional COP Production Assumptions .................................................................... 91
6.3 Summary of Raw Material and Utility Prices ............................................................ 91
6.4 Cost of Production Estimate for: Hydrogen
Process: Steam Reforming of Natural Gas ................................................................ 92
6.5 Cost of Hydrogen Production from Natural Gas Reforming ..................................... 93
6.6 Cost of Hydrogen Production from Steam Reforming of Naphtha USGC Q1
2013............................................................................................................................ 97
6.7 Cost of Hydrogen Production from Naphtha Steam Reforming ................................ 98
6.8 Cost of Hydrogen Production from Partial Oxidation of Residual Oil (USGC Q1
2013) .......................................................................................................................... 102
6.9 Cost of Hydrogen Production from Partial Oxidation of Residual Oil ...................... 103
6.10 Cost of Production Estimate for: Hydrogen
Process: PSA Purification of Hydrogen ..................................................................... 107
6.11 Regional Cost of Hydrogen Purification by Pressure Swing Adsorption .................. 108
6.12 Cost of Production Estimate for: Hydrogen Process: Membrane Purification of
Hydrogen.................................................................................................................... 112
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6.13 Regional Cost of Hydrogen Purification by Membrane Separation .......................... 113

7.1 EU Gasoline and Diesel Requirements ...................................................................... 118
7.2 Global Hydrogen Plant Capacity ............................................................................... 121
7.3 U.S. Existing Hydrogen Capacity .............................................................................. 122
7.4 Other North American Hydrogen Capacities............................................................. 124
7.5 Western Europe Existing Capacity ............................................................................ 125

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