CN1117693C - 蒸汽重整生产合成煤气 - Google Patents

蒸汽重整生产合成煤气 Download PDF

Info

Publication number
CN1117693C
CN1117693C CN98814142A CN98814142A CN1117693C CN 1117693 C CN1117693 C CN 1117693C CN 98814142 A CN98814142 A CN 98814142A CN 98814142 A CN98814142 A CN 98814142A CN 1117693 C CN1117693 C CN 1117693C
Authority
CN
China
Prior art keywords
reactor
steam reforming
reformer
gas
reforming catalyst
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.)
Expired - Fee Related
Application number
CN98814142A
Other languages
English (en)
Other versions
CN1304380A (zh
Inventor
爱伯·戴伯克杰尔
彼得·西尔·克里斯坦森
维高·卢卡森·汉森
J·R·罗斯楚普－尼尔森
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.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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 Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of CN1304380A publication Critical patent/CN1304380A/zh
Application granted granted Critical
Publication of CN1117693C publication Critical patent/CN1117693C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
    • 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
    • C01B3/38—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 catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/38—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 catalysts
    • C01B3/384—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 catalysts the catalyst being continuously externally heated
    • 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
    • C01B3/38—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 catalysts
    • C01B3/40—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 catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/0009—Coils
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes 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
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/068—Ammonia synthesis
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1619—Measuring the temperature
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1623—Adjusting the temperature
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

本发明涉及一种制备富含氢和一氧化碳气体的方法，该方法是在以薄膜形式负载于反应器壁上的蒸汽重整催化剂的存在下，将烃原料进行蒸汽重整，包括下述步骤：(a)任选使烃原料工艺过程气体通过绝热预重整器，该反应器具有负载于反应器壁上的蒸汽重整催化剂薄膜，反应器壁与热气流处于热传导关系；(b)将绝热预重整器的流出物经过后续的管式反应器，该反应器具有蒸汽重整催化剂薄膜和/或蒸汽重整催化剂颗粒，并通过燃料燃烧来加热，从而获得部分重整的气体物流和热的烟道气流；(c)使管式重整器的流出物经过自热重整器；以及(d)从自热重整器回收富含氢和一氧化碳的产品气体的热气流。

Description

蒸汽重整生产合成煤气
技术领域
本发明涉及烃原料与催化构件相接触，进行蒸汽重整来生产合成煤气。
技术背景
术语催化构件是用来指催化体系，在该体系中，催化剂层被固定在另一种材料的表面，例如金属表面。另一种材料作为支持结构，赋予体系以强度。这样就能把催化剂设计成其形状本身并没有足够机械强度的形状。在本文中，该体系由内壁上涂有重整催化剂薄层的管子组成。
可选择的设计方式还包括，外表涂有催化剂层的管、具有催化剂涂层的板，或其它适当的形状。
烃经过蒸汽重整生产合成煤气是通过反应(1)-(3)来进行的：
(-ΔH°298＜0)    (1)
(-ΔH°298＝41kJ/mole)      (2)
(-ΔH°298＝-206kJ/mole) (3)
生产合成煤气的第二种方法是自热重整(ATR)。在自热重整中，是在燃烧炉的燃烧区，将烃原料和低于化学计量的氧通过燃烧进行火焰反应，随后将部分燃烧的原料在载有蒸汽重整催化剂的固定床上，进行蒸汽重整。氧化剂可以是空气、富氧空气或纯氧。
生产合成煤气的第三种方法是把先将烃原料经过重整催化剂固定床，然后将部分重整的原料经过自热重整器的二个步骤联合起来。固定床可以由许多置于火焰燃烧炉的管子组成。这种联合称作两步重整，或先初级重整接着进行二次重整，特别适合于制造用来生产甲醇和氨的合成煤气。ATR之前，通过定量控制发生在固定床蒸汽重整器中的重整过程，可以生产出用于甲醇的合成的，具有适当化学计量的合成煤气；或生产出具有适当氢氮比例的合成煤气，用于氨的合成。
重整技术的现有技术采用的是各种尺寸和形状的重整催化剂颗粒，催化剂颗粒被置于固定床反应器(重整管)中，重整反应是吸热反应，在传统的重整器中，通常是通过管子外壁的辐射和对流二种方式的结合，从重整管的外部环境提供反应所必须的热量。热量通过管壁的热传导，转移到管子的内壁，再经过对流转移给气相，最后经过对流由气相转移给催化剂。在重整器的同一轴向位置，催化剂比管内壁的温度可低100多℃。
现已发现，在蒸汽重整过程中采用本发明催化构件时，热量传递更为有效，从管子内壁向催化剂的热量传递是通过传导发生的，比起通过气相对流传递，这种传递机制要有效得多，结果，管子内壁和催化剂的温度几乎相等(其差别小于5℃)。此外，还可以减少管的厚度(见下文)，这使得重整管内外壁的温度差更小。因而，在其它条件相同的情况下，用催化构件管代替传统重整管时，就有可能既可使催化剂的温度较高，又可以使管的温度较低。管外壁温度低正是所希望的，因为这样可以延长管的寿命。催化剂温度高是有益的，因为反应速度随温度升高而增加，而且可使反应(3)的平衡向右边移动，使得原料得到更好的利用。
就相同的管径而言，催化重整管的压降比传统情形低得多，这就有可能使用非常规形状的反应器，例如用小直径的管子，而依然保持可允许的压降。管子的直径越小，越能增加其寿命，耐受更高的温度和减少管材的消耗。
最后，和有重整催化剂固定床的传统重整器相比，采用本发明的催化构件重整管可减少催化剂的用量。
催化剂用量少要求使用不含催化剂毒物的原料，这一点，例如可将原料送入并经过预重整器(prereformer)来实现。
附图简述
附图1所示为生产合成气工厂的实例，将原料2进行预热、在单元4脱硫，与生产蒸汽6相混合，并且在进入绝热预重整器8之前进一步加热；从绝热预重整器8出来的物流，经排列在烟道气体通道的热交换盘管12进一步加热，送入管式重整器14，在此甲烷转化为氢、一氧化碳和二氧化碳；流出的气体经过自热重整器16，在那里，与氧化剂物流18进行燃烧，对自热重整器下游物流的流出气体20的加工，依赖于对产物的应用意图。
本发明的催化构件可用于附图1所示的两个单元：
1.在进入管式重整器14之前，用于为了加热预重整器的流出气体的预热盘管10中；
2.在管式重整器14中。
发明内容
本发明提供了制备富含氢和一氧化碳气体的方法，它是在以薄膜形式负载于反应器壁上的包括镍和/或贵金属的蒸汽重整催化剂的存在下，将烃原料进行蒸汽重整。该方法包括以下步骤：
(a)任选使烃原料的工艺过程气体通过绝热预重整器，该反应器具有负载于反应器壁上的包括镍和/或贵金属的蒸汽重整催化剂薄膜，反应器壁与热气流处于热传导关系；
(b)将绝热预重整器的流出物经过后续的管式反应器，该反应器具有包括镍和/或贵金属的蒸汽重整催化剂薄膜和/或蒸汽重整催化剂颗粒，并通过燃料燃烧来加热，从而获得部分重整的气体物流和热的烟道气流；
(c)使管式重整器的流出物经过自热重整器；以及
(d)从自热重整器回收富含氢和一氧化碳的产品气体的热气流。
优选实施方式
实施例1
对催化构件反应器进行了测试，测试单元的组成：对反应器供料的***、反应器本身以及反应器流出气体的后处理设备和分析设备。
反应器由长1050mm的1/4″管子组成，在其中段500mm，于内壁上涂有RKNR镍蒸汽重整催化剂，从Haldor Topsoe A/S得到的RKNR粒状蒸汽重整催化剂具有相同的组成，催化剂的厚度为0.31mm。催化反应器管子置于固体金属制成的套管中，该套管紧贴催化管***有孔。沿孔做了多个打磨的坡槽，其中放入热电偶，其中一个热电偶是可移动的，这样可以获得催化管壁的温度曲线图。此外，还将热电偶置于催化管中的气体通道，测量催化区进口和出口的气体温度。将具有套管的反应器置于电加热炉，其中的温度可以6个不同的区域分别进行控制。
原料气体由氢、甲烷、二氧化碳和水蒸汽组成，原料气体进入反应器之前进行混合和预热，通过反应器后，流出气体进行冷却，冷凝水从气体中分离，气体的组成通过气相色谱测定。
对两组条件进行了测试，一组在较低温度下，模拟在预热盘管中使用催化构件(试验编号1)，另一组在较高温度下，模拟管式反应器(试验编号2)，条件为表1所示。两种情形的压力均为28 bar g，通过移动热电偶测定所给出的反应器壁温度如附图2所示。
                   表1
    用于催化构件反应器试验的条件
试验编号 催化区进口的气体温度 催化区出口的气体温度   氢的流速   甲烷流速   二氧化碳流速  水蒸气流速
    ℃     C   Nl/h   Nl/h    Nl/h   Nl/h
    1     605     633   62.0   310.0    16.1   781.4
    2     679     795   240.5   152.0    63.1   425.0
所测定的流出气体的组成如表2所示。该气体组成是以干组分为基准的。
                             表2
    以干组分为基准的气体组成
  试验编号     氢   一氧化碳   二氧化碳     甲烷
  mole％     Mole％     mole％     mole％
    1    49.6     2.48     11.4     36.5
    2    67.8     10.8     9.80     11.7
在两种情况下，于出口气体温度，在实验条件的不确定度范围内，流出气体处于重整反应平衡的，这表明在催化构件反应器中可以获得与固定床反应器相似的转化。

Claims (1)

1.一种制备富含氢和一氧化碳气体的方法，该方法是在以薄膜形式负载于反应器壁上的包括镍和/或贵金属的蒸汽重整催化剂的存在下，将烃原料进行蒸汽重整，包括下述步骤：
(a)使烃原料工艺过程气体通过绝热预重整器(8)，该反应器具有负载于反应器壁上的包括镍和/或贵金属的蒸汽重整催化剂薄膜，预热盘管(10)与热的烟道气流处于热传导关系；
(b)将绝热预重整器(8)的流出物经过后续的管式重整器(14)，该反应器具有包括镍和/或贵金属的蒸汽重整催化剂薄膜和/或蒸汽重整催化剂颗粒，并通过燃料燃烧来加热，从而获得部分重整的气体物流和热的烟道气流；
(c)使管式重整器(14)的流出物经过自热重整器(16)；以及
(d)从自热重整器(16)回收富含氢和一氧化碳的产品气体(20)的热气流。
CN98814142A 1998-07-21 1998-07-21 蒸汽重整生产合成煤气 Expired - Fee Related CN1117693C (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1998/004563 WO2000005168A1 (en) 1998-07-21 1998-07-21 Synthesis gas production by steam reforming

Publications (2)

Publication Number Publication Date
CN1304380A CN1304380A (zh) 2001-07-18
CN1117693C true CN1117693C (zh) 2003-08-13

Family

ID=8167013

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98814142A Expired - Fee Related CN1117693C (zh) 1998-07-21 1998-07-21 蒸汽重整生产合成煤气

Country Status (19)

Country Link
US (1) US7060118B1 (zh)
EP (1) EP1097105B1 (zh)
JP (1) JP2002521295A (zh)
KR (1) KR100401369B1 (zh)
CN (1) CN1117693C (zh)
AT (1) ATE225314T1 (zh)
AU (1) AU752109B2 (zh)
BR (1) BR9815937A (zh)
CA (1) CA2337937C (zh)
CZ (1) CZ294907B6 (zh)
DE (1) DE69808521T2 (zh)
EA (1) EA002517B1 (zh)
ES (1) ES2185209T3 (zh)
MX (1) MXPA01000735A (zh)
NO (1) NO328552B1 (zh)
NZ (1) NZ509100A (zh)
PL (1) PL192266B1 (zh)
SK (1) SK285118B6 (zh)
WO (1) WO2000005168A1 (zh)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE535495T1 (de) * 1999-07-15 2011-12-15 Haldor Topsoe As Verfahren zur katalytischen dampfreformierung eines kohlenwasserstoffeinsatzes
JP2005263618A (ja) * 2004-02-16 2005-09-29 Fuji Electric Holdings Co Ltd 燃料改質器
US7320778B2 (en) 2004-07-21 2008-01-22 Catacel Corp. High-performance catalyst support
US7472936B2 (en) 2005-04-14 2009-01-06 Catacel Corp. Tool for insertion and removal of a catalytic reactor cartridge
US7565743B2 (en) 2005-04-14 2009-07-28 Catacel Corp. Method for insertion and removal of a catalytic reactor cartridge
US7682580B2 (en) 2005-05-19 2010-03-23 Catacel Corp. Catalytic reactor having radial leaves
US7501102B2 (en) 2005-07-28 2009-03-10 Catacel Corp. Reactor having improved heat transfer
US20070104641A1 (en) * 2005-11-08 2007-05-10 Ahmed M M Method of controlling oxygen addition to a steam methane reformer
CN101370733B (zh) * 2006-01-13 2012-09-26 松下电器产业株式会社 氢生成装置、燃料电池***及其运转方法
US7829035B2 (en) 2006-01-19 2010-11-09 Massachusetts Institute Of Technology Oxidation catalyst
EP2008968B1 (en) * 2006-04-05 2017-08-30 Kao Corporation Method for producing water gas
DE102006023248C5 (de) 2006-05-18 2018-01-25 Air Liquide Global E&C Solutions Germany Gmbh Verfahren und Anlage zur Herstellung von Synthesegas
EP1985580A1 (en) * 2007-04-27 2008-10-29 Methanol Casale S.A. Process for producing methanol synthesis gas
JP5174411B2 (ja) * 2007-09-28 2013-04-03 独立行政法人石油天然ガス・金属鉱物資源機構 管式リフォーマーの有効熱利用方法
US20090184293A1 (en) * 2008-01-18 2009-07-23 Han Pat A Process for reforming hydrocarbons
US7850944B2 (en) * 2008-03-17 2010-12-14 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming method with limited steam export
DE102010007916B4 (de) * 2010-02-12 2013-11-28 Centrotherm Sitec Gmbh Verfahren zur Hydrierung von Chlorsilanen und Verwendung eines Konverters zur Durchführung des Verfahrens
TWI412172B (zh) * 2010-11-05 2013-10-11 Ind Tech Res Inst 燃料重組裝置及其方法
CN103508418B (zh) * 2012-06-18 2015-08-12 中国石油化工集团公司 水蒸气制氢工艺中的开工气加热***及加热方法
CN102977914B (zh) * 2012-10-31 2015-01-07 成都易态科技有限公司 催化重整工艺及催化重整反应器
CN103149837B (zh) * 2013-03-01 2015-10-14 浙江大学 甲醇自热重整制氢过程的滑模控制方法
AU2015243290B2 (en) * 2014-04-08 2018-11-01 Haldor Topsoe A/S A process for heating an ATR
WO2016016257A1 (en) 2014-07-29 2016-02-04 Eni S.P.A. Integrated sct-cpo/pox process for producing synthesis gas
WO2016016251A1 (en) 2014-07-29 2016-02-04 Eni S.P.A. Integrated sct-cpo/sr process for producing synthesis gas
CN109071216B (zh) 2016-04-26 2022-04-26 托普索公司 一种甲醇裂解生产氢气或合成气的方法
KR20210132671A (ko) * 2019-02-28 2021-11-04 할도르 토프쉐 에이/에스 개질 구역을 가진 화학 플랜트 및 화학 생성물을 생성하는 과정
US11472700B2 (en) * 2019-12-27 2022-10-18 Saudi Arabian Oil Company Catalyst and process for thermo-neutral reforming of petroleum-based liquid hydrocarbons
CN112265962B (zh) * 2020-10-30 2022-03-04 庄焱法 一种电气协同供热重整反应***
IT202100012551A1 (it) 2021-05-14 2022-11-14 Rosetti Marino S P A Processo per la conversione della co2
IT202100015473A1 (it) 2021-06-14 2022-12-14 Nextchem S P A Metodo di produzione di catalizzatori per processi chimici ad alta temperatura e catalizzatori cosi' ottenuti

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400309A (en) * 1972-06-30 1983-08-23 Foster Wheeler Energy Corporation Process for activating a steam reforming catalyst and the catalyst produced by the process
US4985230A (en) * 1987-08-27 1991-01-15 Haldor Topsoe A/S Method of carrying out heterogeneous catalytic chemical processes
CN1056850A (zh) * 1990-02-02 1991-12-11 赫多特普索化工设备公司 热交换转化方法和反应器***
EP0583211A2 (en) * 1992-08-13 1994-02-16 Haldor Topsoe A/S Process and reactor for the preparation of hydrogen and carbon monoxide rich gas

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2169961A1 (en) 1972-02-05 1973-09-14 Inst Nawozow Sztucznych Steam reforming of hydrocarbons - using surfaces of reactor heating tubes as catalyst
US4019969A (en) 1975-11-17 1977-04-26 Instytut Nawozow Sztucznych Method of manufacturing catalytic tubes with wall-supported catalyst, particularly for steam reforming of hydrocarbons and methanation
JPS5382690A (en) 1976-12-29 1978-07-21 Chiyoda Chem Eng & Constr Co Ltd Improved preparation of synthetic gas for ammonia
JPH0657601B2 (ja) 1984-10-17 1994-08-03 日揮株式会社 炭化水素の水蒸気改質法
JPH0722694B2 (ja) 1986-03-18 1995-03-15 株式会社日立製作所 燃料改質器
JP2662529B2 (ja) * 1989-10-02 1997-10-15 三菱化学エンジニアリング株式会社 無電解めっきによる改質ガス製造装置および方法
JPH05155602A (ja) 1991-12-09 1993-06-22 Sekiyu Sangyo Kasseika Center 薄型水蒸気改質反応器
DE19534433C1 (de) 1995-09-16 1996-10-10 Daimler Benz Ag Katalysatorschichtstruktur für einen Methanolreformierungsreaktor und Verfahren zu ihrer Herstellung
DE69800734T2 (de) * 1997-01-22 2001-08-09 Haldor Topsoee As Lyngby Erzeugung eines Synthesegases durch Dampfreformierung unter Verwendung eines katalysierten Hardware
DE19754013C2 (de) * 1997-12-05 2000-10-26 Dbb Fuel Cell Engines Gmbh Vorrichtung und Verfahren zur Wasserdampfreformierung eines Kohlenwasserstoffs
DK173496B1 (da) * 1998-07-16 2001-01-02 Topsoe Haldor As Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400309A (en) * 1972-06-30 1983-08-23 Foster Wheeler Energy Corporation Process for activating a steam reforming catalyst and the catalyst produced by the process
US4985230A (en) * 1987-08-27 1991-01-15 Haldor Topsoe A/S Method of carrying out heterogeneous catalytic chemical processes
CN1056850A (zh) * 1990-02-02 1991-12-11 赫多特普索化工设备公司 热交换转化方法和反应器***
EP0583211A2 (en) * 1992-08-13 1994-02-16 Haldor Topsoe A/S Process and reactor for the preparation of hydrogen and carbon monoxide rich gas

Also Published As

Publication number Publication date
CZ294907B6 (cs) 2005-04-13
PL192266B1 (pl) 2006-09-29
MXPA01000735A (es) 2002-04-08
CN1304380A (zh) 2001-07-18
US7060118B1 (en) 2006-06-13
NO20006711L (no) 2001-03-21
EP1097105A1 (en) 2001-05-09
ES2185209T3 (es) 2003-04-16
AU752109B2 (en) 2002-09-05
WO2000005168A1 (en) 2000-02-03
CA2337937A1 (en) 2000-02-03
KR20010106413A (ko) 2001-11-29
EA002517B1 (ru) 2002-06-27
EP1097105B1 (en) 2002-10-02
NO328552B1 (no) 2010-03-15
SK285118B6 (sk) 2006-06-01
KR100401369B1 (ko) 2003-10-17
DE69808521D1 (de) 2002-11-07
SK342001A3 (en) 2001-09-11
NZ509100A (en) 2002-09-27
ATE225314T1 (de) 2002-10-15
CZ20004929A3 (en) 2001-05-16
DE69808521T2 (de) 2003-01-30
NO20006711D0 (no) 2000-12-29
PL345848A1 (en) 2002-01-14
EA200100134A1 (ru) 2001-08-27
CA2337937C (en) 2004-10-26
JP2002521295A (ja) 2002-07-16
BR9815937A (pt) 2001-02-28
AU9067298A (en) 2000-02-14

Similar Documents

Publication Publication Date Title
CN1117693C (zh) 蒸汽重整生产合成煤气
US6506359B1 (en) Auto-oxidation and internal heating type reforming method and apparatus for hydrogen production
CA2550062C (en) Axial convective reformer
CN1124226C (zh) 制备合成气的方法和反应器***
EP2812278B1 (en) Heat integrated reformer with catalytic combustion for hydrogen production
CN103648972A (zh) 用于产生合成气的方法及设备
US7919057B2 (en) Method and apparatus for producing a hydrogen-containing gas
CN102844267A (zh) 重整烃的方法
US11607657B2 (en) Heat integrated reformer with catalytic combustion for hydrogen production
EP0199878A2 (en) Apparatus for hydrocarbon fuel processing
JP2006511783A (ja) 蒸気発生時の窒素酸化物生成を減少させる方法
EA000777B1 (ru) Способ и технологический блок для получения синтез-газа для дальнейшего производства аммиака
AU2018330243B2 (en) Conversion reactor and management of method
US20070051041A1 (en) Plant capacity expansion and dynamic production control
KR20230004843A (ko) 역수성 가스 전이 촉매 반응기 시스템
Venkataraman et al. Millisecond catalytic wall reactors: dehydrogenation of ethane
US20060242902A1 (en) High-temperature reforming
Kelling et al. Ceramic Counterflow Reactor for Efficient Conversion of CO2 to Carbon‐Rich Syngas
Tavan A note on use of the CO2-ethane azeotrope as new feed of reforming process using mathematical modeling
CA2341124A1 (en) Process for obtaining a heating fluid as indirect heat source for carrying out endothermic reactions
RU191712U1 (ru) Устройство получения синтез-газа
RU2664138C1 (ru) Компактный реактор для получения синтез-газа из природного/попутного газа в процессе автотермического риформинга
CN1854064A (zh) 高温转化
EP3241805A1 (en) Method and apparatus for producing a hydrogen-containing product
SA93140127B1 (ar) عملية تفاعل ماص للحرارة

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: 20030813

Termination date: 20160721