CN102132119A - 通过低温蒸馏产生和分离氢--一氧化碳混合物的方法 - Google Patents

通过低温蒸馏产生和分离氢--一氧化碳混合物的方法 Download PDF

Info

Publication number
CN102132119A
CN102132119A CN2009801300496A CN200980130049A CN102132119A CN 102132119 A CN102132119 A CN 102132119A CN 2009801300496 A CN2009801300496 A CN 2009801300496A CN 200980130049 A CN200980130049 A CN 200980130049A CN 102132119 A CN102132119 A CN 102132119A
Authority
CN
China
Prior art keywords
methane
synthesis gas
gas
transported
rich
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.)
Granted
Application number
CN2009801300496A
Other languages
English (en)
Other versions
CN102132119B (zh
Inventor
N·艾克-贝劳德
A·埃尔南德斯
P·马蒂
B·波尔斯特
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.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of CN102132119A publication Critical patent/CN102132119A/zh
Application granted granted Critical
Publication of CN102132119B publication Critical patent/CN102132119B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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 catalysts
    • C01B3/382Multi-step processes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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 catalysts
    • C01B3/384Production 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 catalysts the catalyst being continuously externally heated
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0242Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 3 carbon atoms or more
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0261Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/502Carbon monoxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702Hydrocarbons
    • B01D2257/7022Aliphatic hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042Purification by adsorption on solids
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046Purification by cryogenic separation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0485Composition of the impurity the impurity being a sulfur compound
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0495Composition of the impurity the impurity being water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258Pre-treatment of the feed
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143Three or more reforming, decomposition or partial oxidation steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/146At least two purification steps in series
    • C01B2203/147Three or more purification steps in series
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/90Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • F25J2200/94Details relating to the withdrawal point
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/02Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/30Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/04Mixing or blending of fluids with the feed stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/06Splitting of the feed stream, e.g. for treating or cooling in different ways
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/60Natural gas or synthetic natural gas [SNG]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/60Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02Recycle of a stream in general, e.g. a by-pass stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2280/00Control of the process or apparatus
    • F25J2280/02Control in general, load changes, different modes ("runs"), measurements

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Gas Separation By Absorption (AREA)
  • Industrial Gases (AREA)

Abstract

本发明涉及一种产生和分离合成气的方法,在该方法中,由给料气体产生含有低于2.3%的甲烷的合成气(15),含有氢和一氧化碳的合成气通过至少一个处理工序净化以便产生净化的合成气,且该合成气在包括至少一个甲烷洗涤塔(29)的装置(25)中通过低温蒸馏分离以便产生富氢气体和/或富含一氧化碳的气体,该合成气在低温蒸馏分离的上游被增浓以便通过将一部分给料气体(11)不经过合成气产生单元地输送到位于合成气产生步骤下游的处理工序而获得包含超过2.3%的甲烷的合成气。

Description

通过低温蒸馏产生和分离氢--一氧化碳混合物的方法
技术领域
本发明涉及用于产生和分离氢和一氧化碳的混合物的方法和设备。
背景技术
用于产生一氧化碳和氢的单元可分成以下两个部分:-产生合成气(主要包含H2、CO、CH4、Ar、H2O和N2的混合物)。在用于产生合成气的各种工业方法中,可以证实基于天然气的部分氧化、自热重整或煤气化的那些方法在H2/CO生产比率低(小于约3)时是有利的。
-净化合成气。包括
利用液体溶剂洗涤/涤气以便去除合成气中存在的大部分酸性气体的单元,
在吸附剂床上进行净化的单元,
称为“冷箱”的低温分离单元,该低温分离单元用于产生CO。
在从部分氧化反应器、自热反应器或用于煤或重烃类原料/给料的气化产生的合成气的情况下,在冷箱的入口处的合成气中的残余甲烷含量对于甲烷型洗涤过程来说过低;CH4含量在煤气化的情况下可为0.1%的量级或在部分氧化或自热反应器的情况下可为0.9%的量级,而在冷箱的入口处的最低含量一般在2%附近。在该情况下,用于净化合成气的常规低温工艺(CO冷箱)为部分冷凝。
本文中的所有百分比均指摩尔百分比。
在加压地组合生产纯氢和CO的情形中,部分冷凝工艺与甲烷洗涤(利用甲烷进行洗涤)相比存在以下缺点:
-部分冷凝不可能在不具备PSA的情况下生产具有低CO含量的纯氢(例如,当通过甲烷洗涤进行生产时氢包含约10ppm的CO,而当通过部分冷凝生产时氢包含从2%至15%的CO);
-部分冷凝的CO产量更低;为了提高部分冷凝的产量,需要购买压缩机以便使来自部分冷凝的废气再循环;
-仅在CO/CH4塔的储罐底部的甲烷清洗物(purge)中部分地发现合成气中存在的甲烷。大量甲烷通过在洗涤塔顶部的温度水平的热动力平衡在洗涤塔的顶部随同富氢气体从冷箱离开,另一部分甲烷通过在汽提塔顶部的温度水平的热动力平衡随同在汽提塔顶部抽取的闪蒸气体离开。为了确保用于CH4的系统的正物料平衡,要求随同合成气进入冷箱的CH4的量大于随同富氢气体和闪蒸气体离开的CH4的量的总和以确保能控制系统的CH4清洗物。
发现在净化出口处的微量CO2(0.3ppm)溶解在CO/CH4塔的储罐液体中。为了避免CO2在系统中(在洗涤环中)的任何积聚,要求进入冷箱的所有CO2经由CH4清洗物离开。
通常,CH4清洗物和洗涤回路在CO/CH4塔的储罐底部被一起抽取。清洗物中的CO2含量因而与洗涤回路中相同。随着洗涤回路被过冷至-180℃以便优化洗涤过程,洗涤回路中以及清洗物中的CO2含量必须低于CO2在-180℃在CH4中的溶解度值以便在交换器的通道中避免CO2在该回路中固化。
考虑到在净化出口处为0.3ppm的CO2含量和CO2在-180℃在℃H4中为42ppm的溶解度值,这限定了CO2的最高浓度水平——其通过进入冷箱的合成气的流速与CH4清洗物的比率表示——为140。
对于一定的合成气流速而言,这限定了在冷箱入口处的CH4含量的最低值以同时确保过量的CH4平衡和用于控制系统的CH4清洗物,并限制CO2的浓度水平以防止CO2在CH4洗涤回路中固化并因而防止堵塞低温交换器。
为了使通过部分氧化或自热反应器或通过用于煤或重原料的气化的反应器产生合成气的过程从甲烷型洗涤过程受益,发明思想是提高在冷箱入口处合成气中的CH4含量,例如以便获得至少1.8%且优选至少2%并且更加有利地2.3%等等的甲烷含量。
有时可以使用包含至少1.8%的甲烷的给料气体执行甲烷洗涤过程,通常可以使用包含至少2%的甲烷的给料气体,并且在任何情况下都可以使用包含至少2.3%的甲烷的给料气体。
显然,根据本发明,可以使包含至多1.8%的甲烷的合成气增浓(使合成气的某一种成分增加,enrich)以获得包含至少2%的甲烷、甚至2.3%的甲烷的气体;同时,该合成气可以是包含最多2%的甲烷的合成气以便获得包含至少2.3%的甲烷的气体。
还存在提出用于处理合成气中可能存在的C2+成分的方案的问题。
发明内容
根据本发明的一个主题,提供一种用于产生和分离合成气的方法,其中合成气从富含甲烷的原料气体例如天然气产生,包含氢和一氧化碳的合成气通过至少一个处理工序净化以产生净化的合成气并且该合成气在包括至少一个甲烷洗涤塔/涤气塔的装置中通过低温蒸馏分离以产生富氢气体和/或富含一氧化碳的气体,产生的合成气包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷,并且通过将原料气体的一部分输送到位于合成气产生级的下游的处理工序而不经过合成气产生级,在低温蒸馏分离的上游使合成气增浓,从而如果所述产生的合成气包含低于2.3%的甲烷,则获得包含超过2.3%的甲烷的合成气,或如果所述产生的合成气包含低于2%的甲烷则获得包含超过2%的甲烷的合成气,或如果所述产生的合成气包含低于1.8%的甲烷,则获得包含超过1.8%的甲烷的合成气。
根据其它可选方面:
-被输送到位于产生级下游的处理工序的原料气体可以源自位于产生级上游的预重整器和/或位于产生级上游的加氢脱硫单元;
-可选地源自外部源的富含甲烷的气体被输送到合成气产生级的下游和低温蒸馏分离级的上游;
-富含甲烷的气体被输送到位于低温蒸馏分离级的上游的处理工序;
-源自低温蒸馏工序的富含甲烷的流可选地在加压之后被输送到合成气产生级的下游;
-源自低温蒸馏工序的富含甲烷的流被输送到用于处理合成气的工序;
-用于处理合成气的工序包括以下工序中的至少一个:去除酸性气体、干燥、吸附二氧化碳;
-富含甲烷的流体在CO/CH4塔的储罐上方的几个理论塔板被抽取(soutirer),可选地以便作为可选地在加压之后被输送到合成气产生级的下游的富含甲烷的气体,且储罐液体从CO/CH4塔被抽取以便作为清洗物;
-富含甲烷的流体在CO/CH4塔的储罐上方的几个理论塔板被抽取,可选地以便在甲烷洗涤塔的顶部进行洗涤,并且储罐液体从CO/CH4塔被抽取以便用作清洗物;
-清洗物液体与通过在低温蒸馏装置中从合成气分离而获得的富含重烃类的液体混合。
根据本发明的另一个主题,提供一种用于分离包含重烃类的合成气的方法,在该方法中,合成气被净化和冷却并被输送到甲烷洗涤塔,源于来自甲烷洗涤塔的储罐液体的流体被输送到CO/CH4塔,富含甲烷的第一液体在CO/CH4塔的储罐上方的几个理论塔板被抽取,所述第一液体的第一部分被输送到甲烷洗涤塔且第一液体的第二部分被蒸发,包含重烃类的第二液体从CO/CH4塔的储罐被取出作为清洗物。
根据本发明的另一主题,提供一种用于产生和分离合成气的设备,该设备包括:合成气产生单元,用于从原料气体产生合成气;合成气净化单元,用于通过至少一个处理工序净化包含氢和一氧化碳的合成气以产生净化的合成气;以及合成气分离单元,用于通过低温蒸馏分离合成气,该合成气分离单元包括至少一个甲烷洗涤塔以产生富氢气体和/或富含一氧化碳的气体,合成气产生单元被调节成产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气,其特征在于,该设备包括增浓装置,该增浓装置用于在低温蒸馏分离单元的上游使合成气增浓,以便如果所述产生的合成气包含低于2.3%的甲烷则获得包含超过2.3%的甲烷的合成气,或如果所述产生的合成气包含低于2%的甲烷则获得包含超过2%的甲烷的合成气,或如果所述产生的合成气包含低于1.8%的甲烷则获得包含超过1.8%的甲烷的合成气,该增浓装置包括输送装置,该输送装置用于将一部分原料气体不经过合成气产生级地输送到位于合成气产生级的下游的处理工序。
根据其它可选方面,该设备包括:
-用于将在预重整器的下游取得的所述一部分原料气体输送到产生级的上游的装置;
-用于将在加氢脱硫单元的下游取得的所述一部分原料气体输送到产生级的上游的装置;
-用于将可选地源自外部源的富含甲烷的气体输送到合成气产生级的下游和低温蒸馏分离级的上游的装置;
-用于将源自低温蒸馏工序的富含甲烷的流输送到合成气的处理工序的装置;
-用于将富含甲烷的气体输送到位于低温蒸馏分离级的上游的处理工序的装置;
-用于将源自低温蒸馏工序的富含甲烷的流可选地在加压之后输送到合成气产生级的下游的装置;
-用于处理合成气的单元,所述单元包括以下单元中的至少一个:酸性气体去除单元、干燥单元、二氧化碳吸附单元;
-用于在CO/CH4塔的储罐上方的几个理论塔板抽取富含甲烷的流体的装置,该富含甲烷的流体可选地以便作为可选地在加压之后被输送到合成气产生级的下游的富含甲烷的气体,以及用于从CO/CH4塔抽取储罐液体以便作为清洗物的装置;
-用于在CO/CH4塔的储罐上方的几个理论塔板抽取富含甲烷的流体的装置,该富含甲烷的流体可选地以便用于在甲烷洗涤塔的顶部进行洗涤,以及用于从CO/CH4塔抽取储罐液体以便用作清洗物的装置;
-用于将清洗物液体与通过在低温蒸馏装置中从合成气分离而获得的富含重烃类的液体混合的装置;
-用于将一部分原料气体不经过合成气产生单元地输送到位于产生级下游的除酸单元的装置;
-用于将一部分原料气体不经过合成气产生单元地输送到位于产生级下游的吸附单元的装置。
根据本发明的另一主题,提供一种用于分离包含重烃类的合成气的设备,该设备包括:用于净化和冷却合成气的装置;用于将净化并冷却的气体输送到甲烷洗涤塔的装置;用于将源自甲烷洗涤塔的储罐液体的流体输送到CO/CH4塔的装置;用于在CO/CH4塔的储罐上方的几个理论塔板抽取富含甲烷的第一液体的装置;用于将所述第一液体的第一部分输送到甲烷洗涤塔的装置;用于使第一液体的第二部分蒸发的装置;以及用于从CO/CH4塔的储罐抽取包含重烃类的第二液体作为清洗物的装置。
根据本发明的方案是在用于产生合成气的反应器之后并在用于使用冷箱的甲烷进行洗涤的塔之前将富含CH4的流喷入合成气。
示例
1.CH 4 在冷箱之前的循环(图1和图2):
本例适用于其中合成气中的CH4含量(在该CH4循环之前)使得冷箱中的正CH4平衡成为可能但呈现过高的CO2水平的情况。为了降低CO2的浓度水平,采取以下措施:
1.提高用于CH4的泵和用于CH4在冷箱与干燥单元上游之间循环的泵的排放压力以便限制从CO/CH4塔的储罐抽取的物料中CO2的浓度水平。
2.使洗涤塔的顶部冷却以便减小富氢气体的CH4含量。
2.具有POX、ATR、SMR的预重整器(图1):在预重整器的出口与反应器的出口之间设置反应器的旁路(以便减小在冷箱入口处的合成气中的C2+成分的含量,供给到预重整器的天然气的所有C2+成分都在预重整器中转化成CH4)实现了甲烷洗涤工序中的正物料平衡,在预重整器出口处一部分原料被直接喷射到反应器的下游。
1.提高用于CH4的泵和用于CH4在冷箱与干燥单元上游之间循环的泵的排放压力使得可以限制从CO/CH4塔的储罐抽取的物料中的CO2的浓度水平。
2.在洗涤塔顶部的冷却使得可以减小富氢气体中的CH4含量。
3.没有预重整器(POX、ATR、SMR)而具有HDS的反应器(图3):
通过在加氢脱硫(HDS)单元的出口与反应器的出口之间设置反应器的旁路,以便提供甲烷洗涤工序中的正物料平衡,在HDS的出口处一部分原料被直接喷射到反应器的下游。
在反应器之后和洗涤塔之前进行旁路流体的喷射:
a)如果旁路流体包含CO2,则规定在反应器的出口与酸性气体去除单元的前面之间喷射该流体,
b)如果旁路流体包含很小量的CO2(<50vpm),则规定在反应器出口与干燥吸附器的前面之间喷射该流体,
c)如果旁路流体完全不包含任何CO2或H2O,则规定在反应器的出口与甲烷洗涤塔的前面之间喷射该流体。
用于CH4的泵和用于CH4在冷箱与干燥单元的上游之间循环的泵的排放压力的提高使得可以限制CH4清洗物中CO2的浓度水平。
用于在约-145℃的温度水平在冷箱内进行两相分离的容器去除C3+成分并防止它们在合成气在交换管路内冷却到更低的温度水平时固化。
有时需要在CO/CH4蒸馏塔的储罐内增设补充区段。CH4清洗物在塔储罐被抽取并且包括C2成分。
在此储罐区段的顶部抽取用于CH4洗涤以及CH4循环的流(包含少量C2成分,洗涤回路中高含量的C2成分可能引起起泡现象或其它现象并导致洗涤塔工作不良)。
在洗涤塔顶部的冷却使得可以减小富氢气体的CH4含量。
4.在合成气产生单元外部喷射富含CH 4 的气体(图5):
1.在反应器的出口之后且在甲烷洗涤塔之前喷射富含甲烷的气体(不包含CO2)(如果含有CO2,则在§3-2喷射)。
2.用于CH4的泵和用于CH4在冷箱与干燥单元上游之间循环的泵的排放压力的提高使得可以限制CH4清洗物中CO2的浓度水平。
3.用于在约-145℃的温度水平在冷箱内进行两相分离的容器去除C3+成分并防止它们在合成气在交换管路内冷却到更低的温度水平时固化(在存在C2+成分的情况下)。
4.在CO/CH4蒸馏塔的储罐内增设补充区段。CH4清洗物在塔储罐被抽取并包含C2成分,洗涤回路中的高C2含量可能引起起泡现象或其它现象并导致洗涤塔工作不良。
5.需要在此储罐区段的顶部抽取用于CH4洗涤以及CH4循环的流(包含少量C2成分)。
6.在洗涤塔顶部的冷却使得可以减小富氢气体的CH4含量。
5.在反应器之后但在脱碳单元中的脱碳及CO 2 和硫的去除之前输入 未脱硫的富含CH 4 的气体(例如天然气)(图6)
附图说明
将参考附图更详细地描述根据本发明的方法和设备,其中图1、图3、图5和图6示出根据本发明的用于产生和分离一氧化碳和氢的混合物的方法,而图2和图4示出适于结合在该方法中的用于分离一氧化碳和氢的混合物的具体工序。
具体实施方式
图1示出这样的方法,在该方法中,可以是富含甲烷的气体(如天然气)的原料气体1被输送到加氢脱硫(HDS)单元3,如Kyte所著的“Desulphuri-zation”(脱硫),IChemE,1995所述。
产生的气体5被输送到预重整器7。在预重整器的出口处,气体主要由CH4组成,C2+成分转化成CH4并且CH4仅极少量地转化成合成气。
从预重整器离开的气体被分离以便形成旁路流/支流11和流9。流9被输送到SMR或ATR型的反应器13以便产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气15,旁路流11与该合成气15混合。该混合物被输送到酸性气体去除单元17以便产生净化的气体19。净化的气体19被输送到吸附单元21以便干燥并净化脱离CO2,从而形成气体23。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元35。该单元在图2中更详细地示出。该单元包括甲烷洗涤塔29、汽提塔31和位于冷箱35内部的CO/CH4分离塔33。液体甲烷在CO/CH4塔33的储罐被抽取,可选地在通过泵27泵送之后被蒸发,并从冷箱被取出作为流43和/或45。泵27也可用于将甲烷37输送到甲烷洗涤塔29。
甲烷的一部分47可用作清洗物,而其余部分49能可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。
这样,流15在到达去除单元17中时的甲烷含量上升到至少1.8%的甲烷、优选至少2%的甲烷、甚至2.3%的甲烷。
富氢气体39、41由洗涤塔29和汽提塔31产生。
在图2中,净化的气体19被输送到图1的吸附单元21以便被干燥并净化脱离CO2,从而形成气体23。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元35。该单元包括甲烷洗涤塔29、汽提塔31和位于冷箱内部的CO/CH4分离塔33。气体23在交换器48内被冷却并被输送到甲烷洗涤塔29的储罐。来自该塔29的储罐液体61被输送到汽提塔31并且来自汽提塔的储罐液体63被输送到CO/CH4塔33的中间部位。液体甲烷在CO/CH4塔33的储罐被抽取,可选地在通过泵27泵送之后在交换器48内被蒸发,并从冷箱被取出作为流49。泵27也可用于将甲烷37输送到甲烷洗涤塔29以及将甲烷65输送到汽提塔31的顶部。
流49可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。
富氢气体39、41由洗涤塔29和汽提塔31产生。
富含一氧化碳的气体或液体55在CO/CH4塔的顶部被抽取、在交换器48内被加热(并可选地被蒸发)并可选地在压缩机57内被压缩以便形成产品。
图3示出这样的方法,在该方法中,合成气由POX、ATR或SMR型的反应器13产生,该反应器没有预重整器并且具有HDS,在该HDS中可为天然气的富含甲烷的原料气体1被输送到加氢脱硫单元3。产生的气体被分成两部分,一部分5被输送到反应器13。气体的其余部分形成旁路流。反应器13产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气15,如果旁路流11包含CO2则该旁路流11与所述合成气混合。混合物被输送到酸性气体去除单元17以便产生净化的气体19。如果旁路流11A包含低于50vpm的CO2,则旁路流11A可与该净化的气体19混合。净化的气体19被输送到吸附单元21以便干燥并净化脱离CO2,从而形成气体23。如果旁路流11B完全不包含任何CO2,则旁路流11B可与该气体23混合。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元35。该单元在图2中更详细地示出。该单元包括用于去除C3+成分的分离容器28、甲烷洗涤塔29、汽提塔31以及位于冷箱35内部的CO/CH4分离塔33。液体甲烷在CO/CH4塔33的储罐上方的几个级被抽取,可选地在通过泵27泵送之后蒸发,并从冷箱被取出作为流45。泵27也可用于将甲烷37输送到甲烷洗涤塔29。
甲烷的一部分47可用作清洗物并且其余部分49能可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。这样,流15在到达去除单元17中时甲烷含量上升到至少1.8%的甲烷、优选至少2%的甲烷、甚至2.3%的甲烷。
富氢气体39、41由洗涤塔29和汽提塔31产生。包含C2成分的富含甲烷的流体从CO/CH4塔33的储罐被抽取并与源自容器28的富含C3+成分的流体30混合,并且混合物43从冷箱被取出。
在图4中,净化的气体19被输送到图3的吸附单元21以便被干燥并净化脱离CO2,从而形成气体23。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元25。该单元包括甲烷洗涤塔29、汽提塔31和位于冷箱内部的CO/CH4分离塔33。气体23在交换器48内被部分冷却并被输送到分离容器28。产生的气体34被输送到甲烷洗涤塔20的储罐。来自该塔29的储罐液体61被输送到汽提塔31并且来自汽提塔的储罐液体63被输送到CO/CH4塔33的中间部位。液体甲烷在CO/CH4塔33的储罐上方的几个级被抽取,可选地在通过泵27泵送之后在交换器48内蒸发,并从冷箱被取出作为流49。泵29也可用于将甲烷37输送到甲烷洗涤塔29以及将甲烷65输送到汽提塔31的顶部。
流体34——其为来自塔33的储罐甲烷——可在与源自容器28的液体30混合之前被泵27泵送并且混合物43被输送到交换器48且随后可被用作燃料。
流的一部分49可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。可选地,由流体47构成的一部分甲烷可被用作燃料。
富含一氧化碳的气体或液体55在CO/CH4塔的顶部被抽取、在交换器48内被加热(并可选地被蒸发)并可选地在压缩机57内被压缩以便形成产品。
富氢气体39、41由洗涤塔29和汽提塔31产生。
图5示出这样的方法,在该方法中,可为天然气的富含甲烷的原料气体1被输送到加氢脱硫单元3(未示出)。产生的气体被输送到反应器13。反应器13产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气15。合成气或合成气与其它气体的混合物被输送到酸性气体去除单元17以便产生净化的气体19。净化的气体19被输送到吸附单元21以便被干燥并净化脱离CO2,从而形成气体23。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元35。该单元在图4中更详细地示出。该单元包括用于去除C3+成分的分离容器28、甲烷洗涤塔29、汽提塔31以及位于冷箱35内部的CO/CH4分离塔33。液体甲烷在CO/CH4塔33的储罐上方的几个级被抽取,可选地在通过泵27泵送之后被蒸发,并从冷箱被取出作为流45。泵27也可用于将甲烷37输送到甲烷洗涤塔29。
源自外部源的富含甲烷的气体71可作为流71A与由反应器13产生的流混合,或作为流71B与源自酸性气体去除单元17的流19混合,或作为流71C与由吸附单元21产生的流23混合。
甲烷的一部分47可被用作产品而其余部分49可以可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。
这样,流15在到达去除单元17中时或在到达吸附单元21中时或在到达冷箱35中时甲烷含量上升到至少1.8%的甲烷、优选至少2%的甲烷、甚至2.3%的甲烷。
富氢气体39、41由洗涤塔29和汽提塔31产生。包含C2成分的富含甲烷的流体从CO/CH4塔33的储罐被抽取并与源自容器28的富含C3+成分的流体30混合,并且混合物43从冷箱被取出作为清洗物。
图6示出这样的方法,在该方法中,可为天然气的富含甲烷的原料气体1被输送到加氢脱硫单元3(未示出)。产生的气体被输送到反应器13。反应器13产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气15。混合物被输送到酸性气体去除单元17以便产生净化的气体19。净化的气体19被输送到吸附单元21以便干燥并净化脱离CO2,从而形成气体23。气体23被冷却并输送到执行甲烷洗涤的低温蒸馏单元35。该单元在图4中更详细地示出。该单元包括用于去除C3+成分的分离容器28、甲烷洗涤塔29、汽提塔31以及位于冷箱35内部的CO/CH4分离塔33。液体甲烷在CO/CH4塔33的储罐上方的几个级被抽取,可选地在通过泵27泵送之后被蒸发,并从冷箱被取出作为流43和/或45。泵27也可用于将甲烷37输送到甲烷洗涤塔29。
甲烷的一部分47可被用作产品而其余部分49可以可选地在压缩之后作为流51或53循环到酸性气体去除单元的上游或下游。
这样,流15在到达去除单元17中时或在到达吸附单元21中时甲烷含量上升到至少1.8%的甲烷、优选至少2%的甲烷、甚至2.3%的甲烷。
富氢气体39、41由洗涤塔29和汽提塔31产生。包含C2成分的富含甲烷的流体从CO/CH4塔33的储罐被抽取并与源自容器28的富含C3+成分的流体30混合,并且混合物43从冷箱被取出作为清洗物。
未脱硫的天然气的流71被输送到反应器13的下游和酸性气体去除单元17的上游。这也使得可以提高甲烷含量并且能够代替其它富甲烷流的输送。

Claims (15)

1.一种用于产生和分离合成气的方法,在该方法中,合成气(15)由富含甲烷的原料气体产生,包含氢和一氧化碳的所述合成气通过至少一个处理工序净化以产生净化的合成气并且所述合成气在包括至少一个甲烷洗涤塔(29)的设施(25)中通过低温蒸馏而分离以产生富含氢的气体和/或富含一氧化碳的气体,产生的合成气(15)包含至少2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷,并且通过将一部分原料气体(11、11A、11B)不经过合成气产生级地输送到位于合成气产生级下游的处理工序而在低温蒸馏分离的上游使所述合成气增浓,从而如果所述产生的合成气包含低于2.3%的甲烷则获得包含超过2.3%的甲烷的合成气,或如果所述产生的合成气包含低于2%的甲烷则获得包含超过2%的甲烷的合成气,或如果所述产生的合成气包含低于1.8%的甲烷则获得包含超过1.8%的甲烷的合成气。
2.如权利要求1所述的方法,其特征在于,可选地源自外部源的富含甲烷的气体(51、53、71、71A、71B、71C)被输送到所述合成气产生级的下游和低温蒸馏分离级的上游。
3.如权利要求3所述的方法,其特征在于,所述富含甲烷的气体(51、53、71、71A、71B、71C)被输送到位于低温蒸馏分离级上游的处理工序。
4.如前述权利要求中任一项所述的方法,其特征在于,用于合成气的所述处理工序包括以下工序中的至少一者:去除酸性气体、干燥、吸附二氧化碳。
5.如前述权利要求中任一项所述的方法,其特征在于,富含甲烷的流体(43、51)在CO/CH4塔(33)的储罐上方的数个理论塔板被抽取,可选地以便作为可选地在加压之后被输送到所述合成气产生级下游的富含甲烷的气体,并且储罐液体(34)从所述CO/CH4塔被抽取以便作为清洗物。
6.如前述权利要求中任一项所述的方法,其特征在于,富含甲烷的流体(37)在CO/CH4塔的储罐上方的数个理论塔板被抽取,可选地以便用来在所述甲烷洗涤塔的顶部进行洗涤,并且储罐液体从所述CO/CH4塔被抽取以便作为清洗物。
7.如权利要求8所述的方法,其特征在于,所述清洗物液体(34)与富含重烃类的液体(30)混合,所述富含重烃类的液体通过在低温蒸馏设施中从所述合成气分离而获得。
8.如前述权利要求中任一项所述的方法,其特征在于,不经过合成气产生级地输送到位于所述产生级下游的处理工序的所述一部分原料气体(11、11A、11B)源自位于所述产生级上游的预重整器(7)。
9.如前述权利要求中任一项所述的方法,其特征在于,不经过合成气产生级地输送到位于所述产生级下游的处理工序的所述一部分原料气体(11、11A、11B)源自位于所述产生级上游的加氢脱硫单元(3)。
10.一种用于分离包含重烃类的合成气的方法,其特征在于,合成气被净化和冷却并被输送到甲烷洗涤塔(29),源于来自所述甲烷洗涤塔的储罐液体的流体被输送到CO/CH4塔(33),富含甲烷的第一液体在所述CO/CH4塔的储罐上方的数个理论塔板被抽取,所述第一液体的第一部分(37)被输送到所述甲烷洗涤塔并且所述第一液体的第二部分被蒸发,包含重烃类的第二液体(34)从所述CO/CH4塔的储罐被取出作为清洗物。
11.一种用于产生和分离合成气的设备,所述设备包括:合成气产生单元,用于从富含甲烷的原料气体例如天然气产生合成气;合成气净化单元,用于通过至少一个处理工序净化包含氢和一氧化碳的合成气以产生净化的合成气;合成气分离单元,用于通过低温蒸馏分离所述合成气,该合成气分离单元包括至少一个甲烷洗涤塔以产生富含氢的气体和/或富含一氧化碳的气体,所述合成气产生单元被调节成产生包含低于2.3%的甲烷、优选低于2%的甲烷、甚至低于1.8%的甲烷的合成气,其特征在于,所述设备包括增浓装置,所述增浓装置用于在通过低温蒸馏进行分离的合成气分离单元的上游使所述合成气增浓,如果产生的合成气包含低于2.3%的甲烷则该增浓装置能够产生包含超过2.3%的甲烷的合成气,或如果产生的合成气包含低于2%的甲烷则该增浓装置能够产生包含超过2%的甲烷的合成气,或如果产生的合成气包含低于1.8%的甲烷则该增浓装置能够产生包含超过1.8%的甲烷的合成气,所述增浓装置包括输送装置,所述输送装置用于将一部分原料气体(11、11A、11B)不经过所述合成气产生单元地输送到位于所述合成气产生单元下游的处理工序。
12.如权利要求11所述的设备,其特征在于,用于将所述一部分原料气体(11、11A、11B)不经过所述合成气产生单元地输送到位于产生级下游的处理工序的所述输送装置与位于所述产生单元(13)上游的预重整器(7)连接。
13.如权利要求11或12所述的设备,其特征在于,用于将所述一部分原料气体(11、11A、11B)不经过所述合成气产生单元地输送到位于产生级下游的处理工序的所述输送装置与位于所述产生单元(13)上游的加氢脱硫单元(3)连接。
14.如权利要求11至13中任一项所述的设备,其特征在于,所述设备包括用于将所述一部分原料气体不经过所述合成气产生单元地输送到位于所述产生单元(13)下游的除酸单元(17)的装置。
15.如权利要求11至14中任一项所述的设备,其特征在于,所述设备包括用于将所述一部分原料气体不经过所述合成气产生单元地输送到位于所述产生单元(13)下游的吸附单元(21)或者直接输送到所述分离单元(35)的装置。
CN200980130049.6A 2008-08-04 2009-07-20 通过低温蒸馏产生和分离氢--一氧化碳混合物的方法 Expired - Fee Related CN102132119B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0855399 2008-08-04
FR0855399 2008-08-04
PCT/FR2009/051438 WO2010015764A2 (fr) 2008-08-04 2009-07-20 Procédé de génération et de séparation d'un mélange d'hydrogène et de monoxyde de carbone par distillation cryogénique

Publications (2)

Publication Number Publication Date
CN102132119A true CN102132119A (zh) 2011-07-20
CN102132119B CN102132119B (zh) 2014-06-04

Family

ID=40577899

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200980130049.6A Expired - Fee Related CN102132119B (zh) 2008-08-04 2009-07-20 通过低温蒸馏产生和分离氢--一氧化碳混合物的方法

Country Status (6)

Country Link
US (1) US8966937B2 (zh)
EP (1) EP2331898B1 (zh)
CN (1) CN102132119B (zh)
HU (1) HUE038198T2 (zh)
PL (1) PL2331898T3 (zh)
WO (1) WO2010015764A2 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104755865A (zh) * 2012-05-07 2015-07-01 乔治洛德方法研究和开发液化空气有限公司 用于通过低温蒸馏分离甲烷、二氧化碳和氢气的混合物的方法和设备
CN108131896A (zh) * 2017-12-28 2018-06-08 上海华林工业气体有限公司 Hyco冷箱双液态co罐切换积液和外供气体的系统和方法
CN108744565A (zh) * 2018-07-31 2018-11-06 中国大唐集团科学技术研究院有限公司西北分公司 一种蒸发结晶换热装置与燃煤厂脱硫废水零排放系统
CN109790019A (zh) * 2016-08-25 2019-05-21 普莱克斯技术有限公司 用于产生一氧化碳的工艺和装置
CN109952482A (zh) * 2016-11-18 2019-06-28 乔治洛德方法研究和开发液化空气有限公司 通过甲烷洗涤对气体混合物进行低温分离的方法和设置
CN112279217A (zh) * 2020-11-03 2021-01-29 北京石油化工工程有限公司 一种合成气的分离装置和方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2881063B1 (fr) * 2005-01-25 2007-04-20 Air Liquide Procede et installation de production de monoxyde de carbone par distillation cryogenique
WO2011104359A2 (en) * 2010-02-26 2011-09-01 Statoil Petroleum As Method for turndown of a liquefied natural gas (lng) plant
EP2592047A1 (en) * 2011-11-14 2013-05-15 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Thermally integrated process and apparatus for purification and separation of components of a synthesis gas
DE102014014168A1 (de) * 2014-09-24 2016-03-24 Linde Aktiengesellschaft Einsatz einer Methanwäsche zur Abtrennung von Kohlenmonoxid aus methanarmem Synthesegas
FR3052159B1 (fr) * 2016-06-06 2018-05-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et installation pour la production combinee d'un melange d'hydrogene et d'azote ainsi que de monoxyde de carbone par distillation et lavage cryogeniques
FR3057056B1 (fr) * 2016-10-03 2020-01-10 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede et appareil de recuperation d’argon dans une unite de separation d’un gaz de purge de synthese d’ammoniac
US10370248B2 (en) * 2017-01-27 2019-08-06 L'air Liquide Societe Anonyme Pour L'etude Maximizing steam methane reformer combustion efficiency by pre-heating pre-reformed fuel gas
US20210071947A1 (en) 2019-09-06 2021-03-11 Joseph M Schwartz Method and apparatus for an improved carbon monoxide cold box operation

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3780534A (en) * 1969-07-22 1973-12-25 Airco Inc Liquefaction of natural gas with product used as absorber purge
US3965253A (en) * 1972-05-01 1976-06-22 Shell Oil Company Process for producing hydrogen
FR2521448A1 (fr) * 1982-02-15 1983-08-19 Inst Francais Du Petrole Procede pour l'hydrodesulfuration de gaz naturel contenant des composes organiques du soufre et de l'oxygene
DE3741906A1 (de) * 1987-12-10 1989-06-22 Linde Ag Verfahren zur gewinnung von h(pfeil abwaerts)2(pfeil abwaerts) und co
US5232467A (en) * 1992-06-18 1993-08-03 Texaco Inc. Process for producing dry, sulfur-free, CH4 -enriched synthesis or fuel gas
WO1999067587A1 (en) * 1998-06-25 1999-12-29 Process Systems International, Inc. Cryogenic and membrane synthesis gas production
US6578377B1 (en) * 2002-03-11 2003-06-17 Air Products And Chemicals, Inc. Recovery of hydrogen and carbon monoxide from mixtures including methane and hydrocarbons heavier than methane
FR2838424B1 (fr) * 2002-04-15 2004-05-28 Air Liquide Procede et installation de separation d'un melange d'hydrogene et de monoxyde de carbone
US7036337B2 (en) 2003-08-29 2006-05-02 Wylie Companies, Inc Recovery of hydrogen from refinery and petrochemical light ends streams
US7427388B2 (en) * 2004-03-19 2008-09-23 Air Products And Chemicals, Inc. Process for improving prereforming and reforming of natural gas containing higher hydrocarbons along with methane
US7617701B2 (en) * 2004-04-07 2009-11-17 L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and installation for providing a fluid mixture containing at least 10% carbon monoxide
EA200800297A1 (ru) * 2005-07-28 2008-08-29 Инеос Ю-Эс-Ей Ллк Выделение потока продукта с высокой концентрацией со из смешанного газа, содержащего тяжёлые углеводороды
WO2007018518A1 (en) * 2005-07-28 2007-02-15 Ineos Usa Llc Recovery of carbon monoxide and hydrogen from hydrocarbon streams
DE102006006281A1 (de) * 2006-02-10 2007-08-16 Linde Ag Verfahren zur Erzeugung von Kohlenmonoxid aus Synthesegas
DE102006023248C5 (de) * 2006-05-18 2018-01-25 Air Liquide Global E&C Solutions Germany Gmbh Verfahren und Anlage zur Herstellung von Synthesegas
JP5269251B2 (ja) * 2009-05-13 2013-08-21 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックの水素添加メタン化のための方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104755865A (zh) * 2012-05-07 2015-07-01 乔治洛德方法研究和开发液化空气有限公司 用于通过低温蒸馏分离甲烷、二氧化碳和氢气的混合物的方法和设备
CN104755865B (zh) * 2012-05-07 2017-02-22 乔治洛德方法研究和开发液化空气有限公司 用于通过低温蒸馏分离甲烷、一氧化碳和氢气的混合物的方法和设备
CN109790019A (zh) * 2016-08-25 2019-05-21 普莱克斯技术有限公司 用于产生一氧化碳的工艺和装置
CN109790019B (zh) * 2016-08-25 2022-08-09 普莱克斯技术有限公司 用于产生一氧化碳的工艺和装置
CN109952482A (zh) * 2016-11-18 2019-06-28 乔治洛德方法研究和开发液化空气有限公司 通过甲烷洗涤对气体混合物进行低温分离的方法和设置
CN109952482B (zh) * 2016-11-18 2021-07-27 乔治洛德方法研究和开发液化空气有限公司 通过甲烷洗涤对气体混合物进行低温分离的方法和设置
CN108131896A (zh) * 2017-12-28 2018-06-08 上海华林工业气体有限公司 Hyco冷箱双液态co罐切换积液和外供气体的系统和方法
CN108744565A (zh) * 2018-07-31 2018-11-06 中国大唐集团科学技术研究院有限公司西北分公司 一种蒸发结晶换热装置与燃煤厂脱硫废水零排放系统
CN108744565B (zh) * 2018-07-31 2023-07-14 中国大唐集团科学技术研究院有限公司西北分公司 一种蒸发结晶换热装置与燃煤厂脱硫废水零排放系统
CN112279217A (zh) * 2020-11-03 2021-01-29 北京石油化工工程有限公司 一种合成气的分离装置和方法
CN112279217B (zh) * 2020-11-03 2022-05-17 北京石油化工工程有限公司 一种合成气的分离装置和方法

Also Published As

Publication number Publication date
CN102132119B (zh) 2014-06-04
WO2010015764A2 (fr) 2010-02-11
US20110138853A1 (en) 2011-06-16
PL2331898T3 (pl) 2018-04-30
WO2010015764A3 (fr) 2011-04-07
EP2331898A2 (fr) 2011-06-15
US8966937B2 (en) 2015-03-03
EP2331898B1 (fr) 2017-12-27
HUE038198T2 (hu) 2018-09-28

Similar Documents

Publication Publication Date Title
CN102132119B (zh) 通过低温蒸馏产生和分离氢--一氧化碳混合物的方法
CN103889546A (zh) 用于酸气去除中h2s浓缩的方法和构造
US20230256387A1 (en) Apparatus for purifying gas
US9216375B2 (en) Method for selectively desulfurizing a crude synthesis gas
CN104023819A (zh) 从含有甲烷的原煤气中分离二氧化碳的方法及设备
JP2005529057A (ja) 天然ガスから合成ガスを生成・分離するための装置および方法
CN101829474A (zh) 在物理洗气中使洗涤剂再生的方法和设备
CA3073036C (en) Integration of cold solvent and acid gas removal
US10695712B2 (en) Process and apparatus for scrubbing medium regeneration in a physical gas scrub
CA2706267C (en) Methods and system for separating carbon dioxide from syngas
US20150203359A1 (en) System and Process for Producing Ammonia Using an Ion Transport Membrane, Gasifier, and Ammonia Synthesis Unit
AU2018322436B2 (en) Integration of cold solvent and acid gas removal
US20150352483A1 (en) Method and device for generating fuel for a gas turbine
CN110615404A (zh) 用于从经变换和未变换的粗合成气生产多种气体产物的方法和设施
US8741971B2 (en) Method for operating a Fischer-Tropsch synthesis
CA2920058C (en) Method and device for sour gas scrubbing
EP2380653B1 (en) System For Gas Purification And Recovery With Multiple Solvents
CN107149854A (zh) 在气体洗涤中生产塔的布置方式
CN110882606A (zh) 用于从合成气去除酸性气体成分的方法及用于产生再循环气体的装置
CN111306892B (zh) 用于纯化富含氢的气体的方法和设备
CN116694370A (zh) 一种处理未变换气的低温甲醇洗系统及方法
EP2896598A1 (en) System and process for producing ammonia using an ion transport membrane, gasifier, and ammonia synthesis unit
CN116803467A (zh) 用于从合成气中去除二氧化碳和水的方法和设备
CN113697771A (zh) 用于通过物理吸收在甲醇中来纯化粗合成气的气体洗涤方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140604

Termination date: 20200720