CN101516766A - 生产氢气的方法 - Google Patents

生产氢气的方法 Download PDF

Info

Publication number
CN101516766A
CN101516766A CNA2007800356692A CN200780035669A CN101516766A CN 101516766 A CN101516766 A CN 101516766A CN A2007800356692 A CNA2007800356692 A CN A2007800356692A CN 200780035669 A CN200780035669 A CN 200780035669A CN 101516766 A CN101516766 A CN 101516766A
Authority
CN
China
Prior art keywords
gas
volume
tail gas
crude
washing lotion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2007800356692A
Other languages
English (en)
Inventor
霍尔格·施利希廷
托马斯·特尔克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide Global E&C Solutions Germany GmbH
Original Assignee
Lurgi GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lurgi GmbH filed Critical Lurgi GmbH
Publication of CN101516766A publication Critical patent/CN101516766A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0456—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process the hydrogen sulfide-containing gas being a Claus process tail gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/005—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/165—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids at temperatures below zero degrees Celsius
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0877—Methods of cooling by direct injection of fluid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0943—Coke
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0989—Hydrocarbons as additives to gasifying agents to improve caloric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Industrial Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Treating Waste Gases (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

本发明公开了一种用于生产含烃原料的方法。在所述方法中，在添加含氧气体和水蒸气的条件下，在1200至1500℃的温度下和15至100巴abs的压力下，通过非催化性部分氧化，将原材料自热性地转变成原煤气，该原煤气含有作为主要成分的H2和CO，以及成分CO2、H2O、CH4及痕量的H2S、COS、CnHm、N2和Ar，然后通过添加水蒸气使所述原煤气中含有的CO转化成CO2和另外的H2。为了改进所述方法，在变压吸收方法中将所述转化的原合成煤气直接地，即不经除去CO2和H2S的洗涤过程，分离成高纯H2和含有H2S、CO2、H2、CO、CH4、Ar和N2的气体混合物，将所述气体混合物进料到硫回收工艺的尾气洗液中，将分离的H2S进料到所述硫回收工艺的工艺气体中，并使所述尾气洗液的废气燃烧，其中所述废气和所述硫回收工艺的尾气混合。

Description

生产氢气的方法
技术领域
本发明涉及由烃质离析物，例如炼油厂残余物、石油、天然气、石油气、石油焦和煤，生产H2的方法，其中在第一反应阶段，通过在1200至1500℃的温度下和15至100巴abs的压力下添加含氧气体和水蒸气，通过非催化性部分氧化，将原材料自热性地气化，得到原煤气，该原煤气含有作为主要成分的H2和CO以及成分CO2、H2O、CH4及痕量的H2S、COS、CnHm、N2和Ar，并且借助于淬火将所述原煤气中含有的金属灰作为熔渣和烟灰一起除去，以及在第二反应阶段，通过添加水蒸气将所述原煤气中含有的CO转化成CO2和另外的H2。
背景技术
利用Lurgi AG，Frankfurt am Main的公司手册1700e/4.04/15所述的多用途气化法(MPG法)，可以根据下列反应方程式，将很多种烃质液体、气体和固体原材料，例如炼油厂残余物、石油、天然气、石油气、化学废物、煤和石油焦，通过非催化性部分氧化而自热性地转化，得到基本上由H2和CO组成的原煤气：
2CHn+O2→2CO+nH2。
根据原材料的组成和氧气载体例如空气、富氧空气或者纯氧，气化温度是1200至1450℃，气化压力是1至100巴abs并且对于主要生产氢气的情况是30至70巴abs。除了期望的成分H2和CO之外，所得到的原煤气还含有成分CO2、H2O、CH4及痕量的H2S、COS、CnHm、N2和Ar。通过用水淬火，将所述原煤气中含有的金属灰作为熔渣和烟灰一起从该工艺中除去。将与水蒸气混合的氧气载体供应到所述气化装置的燃烧器。在第二反应阶段，根据下列反应方程式用水蒸气使所述原煤气中含有的CO转化，得到CO2和另外的H2：
Figure A20078003566900041
以该方式产生的原合成煤气含有作为期望的成分的50至80体积％的H2和10至40体积％的CO2及作为不期望的成分的H2S、CO、COS、CH4和CnHm，其在两个阶段中借助于作为物理溶剂的负载有CO2的冷甲醇而被吸收。各种成分在甲醇中的溶解度相差很远，由此在20至80巴abs的压力下选择性分离所述成分例如H2S和CO2是可能的。输入的冷却的原合成煤气最初被供应到H2S吸收剂，并且H2S和其它含硫化合物被吸收，以致在所述合成煤气中硫的残余含量低于0.1ppm。为了再生，负载了H2S的甲醇膨胀到中等压力并随后加热到沸沸腾温度，从而使吸收的所有气体被释放。通过克劳斯法从富含H2S的气体中回收纯硫。在第二阶段中，从这种气体中分离CO2，从而使所述气体中的CO2浓度减少到10ppm至3体积％。根据
Figure A20078003566900042
方法，使负载了CO2的溶剂膨胀到低压，并且将释放的无硫CO2排放到大气中或者用于例如生产尿素。相关的方法包括其中采用N-甲基-2-吡咯烷酮(NMP)作为物理溶剂的所谓
Figure A20078003566900043
方法，以及其中利用聚乙二醇醚的混合物作为物理溶剂的
Figure A20078003566900044
方法。采用这两种方法，可以从所述原合成煤气中除去不期望的成分，残余含量低至＜1ppm H2S和0.1至3体积％CO2。还可以借助于胺的水溶液利用胺洗方法例如
Figure A20078003566900045
方法，实现从所述原合成煤气中除去H2S和CO2。
通过采用变压吸收方法(Druckwechsel-Absorptions-Verfahrens)，将除去CO2和H2S剩下的合成煤气分离为由高纯H2组成的部分和可以例如用作燃料气的含有残余成分的小部分。
取决于所述原料，在CO转化成CO2和另外的H2时形成的原合成煤气以高达40体积％含量的CO2的形式含有进料气体的几乎全部碳以及另外≤1体积％的H2S。从所述原合成煤气中选择性分离H2S而不同时分离主要量的CO2，需要相对大的技术努力。对于通过克劳斯法进一步处理富含H2S的相，选择性分离是必须的。通过变压吸收方法来实现剩余H2的最终净化。
发明内容
本发明的目的是，在通过上述方法由烃质离析物生产H2过程中，省略洗涤由转化产生的原合成煤气，其借助用于除去CO2和H2S的物理或者化学溶剂，离开第二反应阶段。
该目的的解决方案在于，在第三阶段通过变压吸收方法，将离开第二反应阶段的转化的原合成煤气分离成高纯H2和含有0.5至10体积％的H2S、50至95体积％的CO2、5至20体积％的H2、0.1至10体积％的CO和0.1至10体积％的CH4、Ar、N2的气体混合物，将该气体混合物供应到克劳斯法的尾气洗液中，将从所述气体混合物中选择性分离的H2S引入克劳斯法的进料气体中，并且将与克劳斯法的尾气混合的尾气洗液的脱硫废气燃烧。
本发明的一个方面在于将在克劳斯法尾气洗液的洗涤剂的再生过程中回收的H2S再循环到所述克劳斯法中，由此增加硫的收率。
对于在所述尾气洗液的脱硫废气的燃烧过程中得到的废气仍然含有痕量的H2S的情况，使所述废气经过二次燃烧。
便利地，为了产生水蒸气、加热等，将在所述克劳斯法尾气洗液的脱硫废气的燃烧过程中获得的热能转移给在热交换器中流动的低温流体。
具体实施方式
实施例
借助于实施方式连同简化的方块流程图，将详细解释本发明的方法。
残余油经导管(2)经布置在反应器顶部的燃烧器供应到连接淬火槽的内衬一层耐火材料的化学反应器(1)中，经导管(3)供应氧气和经导管(4)供应水蒸气。产生的原煤气通过位于反应器(1)底部的出口孔流入淬火槽，并通过侧面布置的排气口离开。刚一离开反应器(1)，热的原煤气就通过将水注入淬火喷嘴直接冷却到饱和水蒸气温度。形成的液体炉渣经反应器壁流出并且在淬火槽中淬火。在玻璃状炉渣小球中，并入了重金属和不溶性化合物，它们经导管(5)排出。在50巴abs的气化压力和1350℃的气化温度下通过非催化性部分氧化产生的原煤气由45体积％的H2、45体积％的CO、5体积％的CO2和＜1体积％的H2S组成，并且从淬火槽经导管(6)流入转化器(7)，在该转化器中，CO和经导管(8)供应的水蒸气反应得到CO2和另外的H2。经导管(9)排出的含有62体积％的H2、35体积％的CO2、2体积％的CO和1体积％的H2S的原合成煤气被进料到变压吸收装置(10)中，在该装置中，原合成煤气在48巴abs的压力下被选择性分离成H2，该H2经导管(11)从变压吸收装置(10)中排出；及吸附在多孔材料上的剩余成分。一旦所述多孔材料完全负载，降低压力，并且回收由2体积％的H2S、78体积％的CO2、13体积％的H2、2体积％的CO、其余的CH4、N2、Ar组成的气体混合物。经导管(12)，将所述气体混合物和克劳斯装置的尾气混合，并一起供应到克劳斯装置的尾气净化阶段(13)，并且借助于经导管(14)流入的洗涤剂从气体混合物中选择性洗脱H2S。作为洗涤剂，典型地采用选择性活性化学洗涤剂，尤其是胺例如甲基二乙醇胺(MDEA)或立体位阻胺(Flexsorb
Figure A20078003566900061
)。在再生器中，洗涤剂从吸收的H2S以及其它气体成分中释放出来，并且所形成的具有相对高的H2S浓度的气体经导管(15)进料到来自其它工艺单元经导管(17)流入刀克劳斯装置(16)中的酸性气流中。剩余气体混合物与从克劳斯装置(16)流出经导管(18)进入到尾气净化阶段(13)的气体成分结合，并且经导管(19)流入燃烧装置(20)。
必定发现用本发明的方法特别取得的优点在于，通过转化产生的第二反应阶段的原合成煤气被直接进料到变压吸收工艺，以分离为高纯H2和含有CO2、H2、H2S、CO、CH4、N2和Ar的气体混合物，并在克劳斯法的尾气洗液中进行H2S从气体混合物中的分离。借助这种方法，可以省略转化的原合成煤气的物理和化学气体洗涤，并且因此用于由烃质离析物回收氢气的全套装置的投资成本可以减少大约20％。此外，通过采用本发明的方法避免了CO2排放。

Claims (4)

1.用于由烃质离析物生产氢气的方法，该烃质离析物例如炼油厂残余物、石油、天然气、石油气、石油焦和煤，其中在第一反应阶段，通过在1200至1500℃的温度下和15至100巴abs的压力下添加含氧气体和水蒸气，通过非催化性部分氧化，使原材料自热性地气化，得到原煤气，该原煤气含有作为主要成分的H2和CO以及成分CO2、H2O、CH4和痕量的H2S、COS、CnHm、N2和Ar，并且借助于淬火将在所述原煤气中含有的金属灰作为熔渣和烟灰一起除去，和在第二反应阶段，通过添加水蒸气将所述原煤气中含有的CO转化成CO2和另外的H2，其特征在于，在第三阶段，通过变压吸收方法将离开所述第二反应阶段的转化的原合成煤气分离成高纯H2和含有0.5至10体积％的H2S、50至95体积％的CO2、5至20体积％的H2、0.1至10体积％的CO和0.1至10体积％的CH4、Ar、N2的气体混合物，将该气体混合物供应到克劳斯法的尾气洗液中，将从所述气体混合物中选择性分离的H2S引入到克劳斯法的进料气体中，并且将与所述克劳斯法的尾气混合的尾气洗液的脱硫废气燃烧。
2.根据权利要求1所述的方法，其特征在于，将在所述克劳斯法的尾气洗液的洗涤剂的再生过程中回收的H2S再循环到所述克劳斯法中。
3.根据权利要求1和2中任一项所述的方法，其特征在于，将在所述尾气洗液的脱硫废气的燃烧过程中获得的热能转移给在热交换器中流动的低温流体。
4.根据权利要求1至3中任一项所述的方法，其特征在于，使在所述尾气洗液的脱硫废气的燃烧过程中获得的废气进行二次燃烧。
CNA2007800356692A 2006-09-26 2007-07-31 生产氢气的方法 Pending CN101516766A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006045379A DE102006045379B4 (de) 2006-09-26 2006-09-26 Verfahren zur Herstellung von Wasserstoff
DE102006045379.4 2006-09-26

Publications (1)

Publication Number Publication Date
CN101516766A true CN101516766A (zh) 2009-08-26

Family

ID=39134132

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007800356692A Pending CN101516766A (zh) 2006-09-26 2007-07-31 生产氢气的方法

Country Status (7)

Country Link
US (1) US8273323B2 (zh)
EP (1) EP2077974A2 (zh)
CN (1) CN101516766A (zh)
CA (1) CA2663238A1 (zh)
DE (1) DE102006045379B4 (zh)
WO (1) WO2008037315A2 (zh)
ZA (1) ZA200901945B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102431971A (zh) * 2010-07-27 2012-05-02 气体产品与化学公司 可调节地处理酸性气体的方法和装置
CN102656112A (zh) * 2009-12-16 2012-09-05 鲁奇有限责任公司 用于操作重整炉的方法和重整设备

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8206669B2 (en) 2010-07-27 2012-06-26 Air Products And Chemicals, Inc. Method and apparatus for treating a sour gas
FR3019830B1 (fr) 2014-04-14 2017-11-24 Gdf Suez Procede et dispositif de traitement d'un gaz de synthese provenant d'une etape de gazeification de biomasse
NL2013759B1 (en) * 2014-11-10 2016-09-07 Stichting Energieonderzoek Centrum Nederland Improved process for removing and recovering H2S from a gas stream.
US11472924B2 (en) * 2018-12-20 2022-10-18 Gas Technology Institute Methods and systems to decarbonize natural gas using sulfur to produce hydrogen and polymers
EP3960728A1 (de) 2020-08-24 2022-03-02 Covestro Deutschland AG Verfahren zur isocyanat-herstellung mit rezyklierender, thermisch oxidativer verwertung

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798316A (en) * 1972-09-08 1974-03-19 Parsons R Co Purification of claus plant tail gas by water washing
DE3047830A1 (de) 1980-12-18 1982-07-15 Linde Ag, 6200 Wiesbaden Verfahren zum reinigen eines gasstromes
DE3208695A1 (de) * 1982-03-11 1983-09-22 Basf Ag, 6700 Ludwigshafen Verfahren zur entschwefelung von h(pfeil abwaerts)2(pfeil abwaerts)s-haltigen gasen
DE3332563A1 (de) * 1983-09-09 1985-03-28 Basf Ag, 6700 Ludwigshafen Verfahren zur entschwefelung von h(pfeil abwaerts)2(pfeil abwaerts)s-haltigen gasen
US4553981A (en) * 1984-02-07 1985-11-19 Union Carbide Corporation Enhanced hydrogen recovery from effluent gas streams
US4801438A (en) * 1987-03-02 1989-01-31 Texaco Inc. Partial oxidation of sulfur-containing solid carbonaceous fuel
US4801440A (en) * 1987-03-02 1989-01-31 Texaco, Inc. Partial oxidation of sulfur-containing solid carbonaceous fuel
US4696680A (en) * 1985-10-03 1987-09-29 The United States Of America As Represented By The United States Department Of Energy Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption
US4889699A (en) * 1987-05-19 1989-12-26 Texaco Inc. Partial oxidation process
US5021232A (en) * 1989-09-29 1991-06-04 Cng Research Company Sulfur recovery process
EP0486174B1 (en) * 1990-11-16 1994-10-05 Texaco Development Corporation Process for producing high purity hydrogen
US5152975A (en) * 1991-03-15 1992-10-06 Texaco Inc. Process for producing high purity hydrogen
WO1993010883A1 (en) * 1991-11-27 1993-06-10 Exxon Research And Engineering Company Lean acid gas enrichment with selective hindered amines
DE4239811A1 (de) * 1992-11-26 1994-06-01 Linde Ag Verfahren zur Entschwefelung eines H¶2¶S-haltigen Rohgases
US6776974B1 (en) * 1999-10-22 2004-08-17 Monsanto Enviro-Chem Systems, Inc. Process for the production of sulfur
EP1142628A3 (en) * 2000-04-05 2001-11-28 The BOC Group plc Treatment of gas streams containing hydrogen sulphide
US7357908B2 (en) * 2000-12-18 2008-04-15 Conocophillips Company Apparatus and catalytic partial oxidation process for recovering sulfur from an H2S-containing gas stream
US6967063B2 (en) * 2001-05-18 2005-11-22 The University Of Chicago Autothermal hydrodesulfurizing reforming method and catalyst
DE50113012D1 (de) * 2001-06-15 2007-10-25 Umicore Ag & Co Kg Verfahren zur Herstellung eines schwefelarmen Reformatgases zur Verwendung in einem Brennstoffzellensystem
FR2845372B1 (fr) * 2002-10-08 2004-12-17 Inst Francais Du Petrole Procede de recuperation d'hydrogene dans un effluent hydrocarbone gazeux par reaction chimique
EP1572324B1 (en) 2002-12-17 2012-08-15 Fluor Corporation Method for acid gas and contaminant removal with near zero emission
RU2343109C2 (ru) * 2003-03-18 2009-01-10 КЕЛЛОГГ БРАУН ЭНД РУТ ЭлЭлСи Способ получения потока, обогащенного водородом, способ генерирования электрического тока, способ гидроочистки, устройство для получения потока, обогащенного водородом
US7399326B2 (en) * 2004-03-04 2008-07-15 General Motors Corporation Carbon monoxide clean-up in a PEM fuel cell system
JP3813969B2 (ja) * 2004-07-15 2006-08-23 ユニ・チャーム株式会社 尿レシーバおよびこれを用いた収尿処理システム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102656112A (zh) * 2009-12-16 2012-09-05 鲁奇有限责任公司 用于操作重整炉的方法和重整设备
CN102656112B (zh) * 2009-12-16 2014-08-27 鲁奇有限责任公司 用于操作重整炉的方法和重整设备
CN102431971A (zh) * 2010-07-27 2012-05-02 气体产品与化学公司 可调节地处理酸性气体的方法和装置
CN102431971B (zh) * 2010-07-27 2014-10-29 气体产品与化学公司 可调节地处理酸性气体的方法和装置

Also Published As

Publication number Publication date
EP2077974A2 (de) 2009-07-15
DE102006045379B4 (de) 2008-07-31
US8273323B2 (en) 2012-09-25
US20100111824A1 (en) 2010-05-06
WO2008037315A2 (de) 2008-04-03
WO2008037315A3 (de) 2008-10-02
DE102006045379A1 (de) 2008-04-03
ZA200901945B (en) 2010-06-30
CA2663238A1 (en) 2008-04-03

Similar Documents

Publication Publication Date Title
US8080232B2 (en) Process for recovering carbon dioxide
TWI291988B (zh)
US4052176A (en) Production of purified synthesis gas H2 -rich gas, and by-product CO2 -rich gas
CN102431971B (zh) 可调节地处理酸性气体的方法和装置
US3976443A (en) Synthesis gas from solid carbonaceous fuel
US6448441B1 (en) Gasification process for ammonia/urea production
CN101516766A (zh) 生产氢气的方法
KR102204443B1 (ko) 메탄화를 포함하는 동력 생산을 위한 시스템 및 방법
US20120094337A1 (en) Process for producing a purified synthesis gas stream
CN101918104B (zh) 用于处理包含co2的工艺气流的方法
MXPA01011573A (es) Recirculacion de hidrogeno y remocion de gas acido utilizando una membrana.
CN102642810B (zh) 一种焦炉气制备费托合成油原料气的组合工艺
CN101239702B (zh) 高温焦炉粗煤气制氢系统装置及工艺
CN102199433A (zh) 一种以co2为燃烧过程控温组分的煤炭化工艺
CN100579896C (zh) 鲁奇炉出口煤气加纯氧非催化部分氧化制取合适氢碳比合成气的方法及系统
TW201529477A (zh) 使用離子輸送膜、氣化器及氨合成單元的氨生產系統及方法
JP2006511433A (ja) Ｈ２ｓリッチ・ストリームからｃｏ２を分離するための化学溶媒の使用法
JP4030846B2 (ja) メタノールの製造方法および装置
CN102320568A (zh) Bgl加压熔渣气化加纯氧非催化部分氧化制取合成气或氢气的方法及装置
WO2016119603A1 (zh) 甲烷合成方法及系统
CN202208705U (zh) Bgl加压熔渣气化加纯氧非催化部分氧化制取合成气或氢气的装置
US8241603B1 (en) Process and system for removing sulfur from sulfur-containing gaseous streams
CN113955716A (zh) 一种焦炉气矿热炉煤气制合成气与cng的工艺
CN117125673B (zh) 一种大规模碳捕集系统
EP2896598A1 (en) System and process for producing ammonia using an ion transport membrane, gasifier, and ammonia synthesis unit

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20090826