KR950008346A - 일산화탄소 및 수소의 제조방법(Process for the preparation of carbon monoxide and hydrogen) - Google Patents

일산화탄소 및 수소의 제조방법(Process for the preparation of carbon monoxide and hydrogen) Download PDF

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KR950008346A
KR950008346A KR1019940023872A KR19940023872A KR950008346A KR 950008346 A KR950008346 A KR 950008346A KR 1019940023872 A KR1019940023872 A KR 1019940023872A KR 19940023872 A KR19940023872 A KR 19940023872A KR 950008346 A KR950008346 A KR 950008346A
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catalyst
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hydrocarbon
oxygen
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레오나르두스 게라르두스 야곱스 루도비쿠스
얀 슈우네비이크 로날드
야코부스 아드리아누스 티옘 페트루스
알렉산더 본 케만 코에르트
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알베르투스 빌헬무스·요아네스 쩨스트 라텐
셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이
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    • 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
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    • 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
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    • 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
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    • 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
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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    • 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
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    • 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
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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    • 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
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    • C01B2203/1005—Arrangement or shape of catalyst
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    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
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    • 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
    • C01B2203/1241—Natural gas or methane
    • 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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

탄화수소를 부분 산화함으로써 일산화탄소 및 수소를 제조하는 방법은 탄화수소, 이산화탄소 및 산소-함유 기체로 구성되는 공급물을 원소 주기율표의 Ⅷ족으로부터 선택된 금속으로 구성되는 촉매와 적어도 500,000N1/㎏/시의 시간당 기체 공간 속도에서 접촉시키는 것으로 구성된다.

Description

일산화탄소 및 수소의 제조방법(Process for the preparation of carbon monoxide and hydrogen)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (14)

  1. 탄화수소, 이산화탄소 및 산소-함유 기체로 구성되는 공급물을 원소 주기율표의 Ⅷ족으로부터 선택된 금속으로 구성되는 촉매와 적어도 500,000N1/㎏/시의 시간당 기체 공간 속도에서 접촉시키는 것으로 구성되는 탄화수소를 부분 산화함으로써 일산화탄소 및 수소를 제거하는 방법.
  2. 제1항에 있어서, 탄화수소가 메탄이거나 또는 천연 가스, 혼합 기체, 또는 다른 저급 탄화수소 원료로서 존재하는 것을 특징으로 하는 방법.
  3. 제1또는 2항에 있어서, 이산화탄소가 50부피% 이하, 바람직하게 30 부피%이하, 보다 바람직하게 25 부피%이하, 특별히 10부피%이하의 농도로 공급물내 존재하는 것을 특징으로 하는 방법.
  4. 제1-3항중 임의의 한 항에 있어서, 산소-함유 기체가 실질적으로 순수한 산소인 것을 특징으로 하는 방법.
  5. 제1-4항중 임의의 한 항에 있어서, 공급물이 0.9-1.6, 바람직하게 0.9-1.5, 보다 바람직하게 0.9-1.4, 특별히 0.9-1.3범위내의 산소-대-탄소 비율을 얻는데 충분한 농도로 탄화수소, 이산화탄소 및 산소-함유 기체를 포함하는 것을 특징으로 하는 방법.
  6. 제1-5항중 임의의 한 항에 있어서, 공급물이 150bara이하, 바람직하게 2-125bara범위내, 보다 바람직하게 2-100bara범위내 압력에서 촉매와 접촉하는 것을 특징으로 하는 방법.
  7. 제1-6항중 임의의 한 항에 있어서, 공급물이 800℃이상 온도에서, 바람직하게 900-1400℃범위내, 보다 바람직하게 1000-1300℃범위내 온도에서, 촉매와 접촉하는 것을 특징으로 하는 방법.
  8. 제1-7항중 임의의 한 항에 있어서, 공급물이 500,000-50,000,000N1/㎏/시, 바람직하게는 750,000-30,000,000N1/㎏/시, 보다 바람직하게 1,000,000-20,000,000N1/㎏/시의 범위내 시간당 기체 공간 속도에서 촉매와 접촉하는 것을 특징으로 하는 방법.
  9. 제1-8항중 임의의 한 항에 있어서, 촉매가 루테늄, 로듐, 팔라듐, 오스뮴, 이리듐 및 백금으로부터 선택되는 금속, 바람직하게는 루테늄, 로듐 또는 이리듐으로 부터 선택되는 금속으로 구성되는 것을 특징으로 하는 방법.
  10. 제1-9항중 임의의 한 항에 있어서, 촉매가 고정 배열내 유지되는 것을 특징으로 하는 방법.
  11. 제10항에 있어서, 촉매가 바람직하게 1.1-10.0, 보다 바람직하게 1.1-5.0, 특별히 1.3-4.0범위내의 높은 만곡률을 갖는 고정 배열내 유지되는 것을 특징으로 하는 방법.
  12. 제10 또는 11항에 있어서, 촉매가 입자 또는 세라믹 포움 형태인 것을 특징으로 하는 방법.
  13. 제1-12항중 임의의 한 항에 있어서, 공급물이 단열 조건하에 촉매와 접촉하는 것을 특징으로 하는 방법.
  14. 제1-13항중 임의의 한 항에서 청구된 바와 같은 방법에 의해 제조되는 일산화탄소 또는 수소.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019940023872A 1993-09-23 1994-09-22 일산화탄소 및 수소의 제조방법(Process for the preparation of carbon monoxide and hydrogen) KR950008346A (ko)

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JP (1) JPH0789701A (ko)
KR (1) KR950008346A (ko)
CN (1) CN1040526C (ko)
AT (1) ATE168969T1 (ko)
AU (1) AU680286B2 (ko)
BR (1) BR9403803A (ko)
CA (1) CA2132586A1 (ko)
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DE (1) DE69412019T2 (ko)
DZ (1) DZ1813A1 (ko)
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US6254807B1 (en) * 1998-01-12 2001-07-03 Regents Of The University Of Minnesota Control of H2 and CO produced in partial oxidation process
US6540975B2 (en) * 1998-07-27 2003-04-01 Battelle Memorial Institute Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
EP1156026A1 (en) 2000-05-19 2001-11-21 Shell Internationale Researchmaatschappij B.V. Process for the production of liquid hydrocarbons
FR2823192B1 (fr) * 2001-04-09 2004-02-13 Air Liquide Procede d'oxydation partielle catalytique d'hydrocarbures pour la production de gaz de synthese a faible rapport h2/co
US7544342B2 (en) 2004-08-25 2009-06-09 The Boc Group, Inc. Hydrogen production process
RU2475302C2 (ru) * 2007-10-11 2013-02-20 Джапан Петролеум Эксплорейшн Ко., Лтд. Катализатор риформинга углеводородов и способ получения синтез-газа с использованием такового
JP4639247B2 (ja) 2008-07-23 2011-02-23 石油資源開発株式会社 炭化水素リフォーミング用触媒およびその製造方法ならびにこれを用いた合成ガスの製法
US8128902B2 (en) * 2011-04-12 2012-03-06 Midwest Refrigerants, Llc Method for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
KR101903791B1 (ko) * 2012-06-25 2018-10-02 에스케이이노베이션 주식회사 카본 블랙 촉매를 이용한 이산화탄소 개질 방법
RU2603662C2 (ru) * 2015-04-24 2016-11-27 федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский государственный университет нефти и газа имени И.М. Губкина" Способ получения синтез-газа высокотемпературным каталитическим окислительным превращением метана
FI127925B (en) * 2018-03-13 2019-05-31 Teknologian Tutkimuskeskus Vtt Oy Method and apparatus for producing carbon monoxide
JP7327929B2 (ja) * 2018-12-03 2023-08-16 古河電気工業株式会社 合成ガスの製造装置および合成ガスの製造方法
EP4313853A1 (de) * 2021-03-26 2024-02-07 Basf Se Verfahren zur herstellung eines synthesegasgemischs
CN115716781A (zh) * 2022-10-27 2023-02-28 万华化学集团股份有限公司 一种丙烷脱氢耦合羰基合成制备丁醛的工艺

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Publication number Priority date Publication date Assignee Title
GB9028034D0 (en) * 1990-12-24 1991-02-13 Isis Innovation Improved processes for the conversion of methane to synthesis gas
ATE173449T1 (de) * 1992-06-24 1998-12-15 Shell Int Research Verfahren zur katalytischen kohlenwasserstoffteiloxidation
US5411927A (en) * 1992-08-14 1995-05-02 Council Of Scientific & Industrial Research Process of preparing composite catalysts for production of synthesis gas by oxidative conversion of methane or natural gas

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ZA947334B (en) 1995-05-10
CA2132586A1 (en) 1995-03-24
CN1104173A (zh) 1995-06-28
RU94034103A (ru) 1996-07-27
EP0645344B1 (en) 1998-07-29
JPH0789701A (ja) 1995-04-04
NO943512D0 (no) 1994-09-21
DZ1813A1 (fr) 2002-02-17
DE69412019D1 (de) 1998-09-03
ES2119065T3 (es) 1998-10-01
NO943512L (no) 1995-03-24
DE69412019T2 (de) 1999-01-21
SG49079A1 (en) 1998-05-18
EP0645344A1 (en) 1995-03-29
ATE168969T1 (de) 1998-08-15
NZ264499A (en) 1995-12-21
BR9403803A (pt) 1995-05-23
CN1040526C (zh) 1998-11-04
MY131617A (en) 2007-08-30
AU7414294A (en) 1995-04-06
AU680286B2 (en) 1997-07-24
CO4180614A1 (es) 1995-06-07
RU2136581C1 (ru) 1999-09-10

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