PT1106570E - Processo e reactor para realizar reacções catalíticas não adiabáticas - Google Patents

Processo e reactor para realizar reacções catalíticas não adiabáticas Download PDF

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PT1106570E
PT1106570E PT125077T PT00125077T PT1106570E PT 1106570 E PT1106570 E PT 1106570E PT 125077 T PT125077 T PT 125077T PT 00125077 T PT00125077 T PT 00125077T PT 1106570 E PT1106570 E PT 1106570E
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heat exchange
reaction space
catalyst
stream
space
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PT125077T
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English (en)
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Soren Gyde Thomsen
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Haldor Topsoe As
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    • 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
    • B01J8/0285—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
    • 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
    • B01J8/0242—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 the fluid flow within the bed being predominantly vertical
    • B01J8/0257—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 the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped 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
    • 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
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/021—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles comprising a plurality of beds with flow of reactants in parallel
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • 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
    • C01B2203/025—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]
    • 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
    • C01B2203/0838—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
    • C01B2203/0866—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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Description

DESCRIÇÃO
PROCESSO E REACTOR PARA REALIZAR REACÇÕES CATALÍTICAS MÃO ADIABÁTICAS A presente invenção tem por objecto um processo para a realização de reacções não adiabáticas tendo lugar exotermicamente ou endotermicamente, num processo gasoso, na presença de um catalisador, numa permutai indirecta de calor com um. meio apropriado de permuta de calor. A patente US 4 079 017 descreve um processo de reformação em que três equipamentos de reformação funcionam em paralelo. invenção consiste assim a realização de reacções as etapas definidas na
Um objecto geral da present· em providenciar um processo para não adiabáticas, compreendendo reivindicação 1. Ά presente invenção, em particular, é ut ir para a realiz ação de reacções de reformação a vapor numa carga de b id.ro c arbonetos, oor meio do calor fornecido a pa rtir dos efluentes gasosos quentes que saem de um reactor auto-térmico de reformação a vapor e o produto gasoso reformado a vapor resultante do processo. reacc teor uma r A fig. 1 mostra, esquematicamente, um sistema ional utilizado na produção de um gás com um elevado de hidrogénio e/ou de monóxido de carbono, a partir de eformação a vapor de uma carga de bidrocarbonetos, que az ρarte da presente invençâo. l A reformação a vapor é uma reacçáo quimica endotérmica, em que os hidrocarbonetos e o vapor reagem num catalisador de reformação a vapor e, se necessário, fornece-se calor ao local da reacçáo, 0 sistema do reactor que se utiliza nesta modalidade consiste em três reactores, onde se realiza o processo de reformação a vapor. Os três reactores Rl, R2 e R3 funcionam, em paralelo.
Rl é um. reactor adia.bático. Os reagentes para o processo em Rl consistem em hidrocarbonetos, vapor e um gás rico em oxigénio que são introduzidos no reactor a uma temperatura apropriada e são misturados, 0 oxigénio e o hid.roca.rbon.eto irão reagir por combustão o que resulta num gás quente de bidrocarboneto residual e vapor, resultando nos produtos da combustão. Em sequida, o gás quente passa através de um leito de catalisador de reformação e é convertido, cataliticamente, numa. mistura. quente de hidrogénio, monóxido de carbono e d.ióxido d.e carbono. R2 e R3 são dois reactores de fluxo contínuo. Os reagentes para o processo em R2 e R3 são uma. mistura de hidrocarbonetos e vapor que é aquecida até a uma temperatura apropriada antes de fluir através de um leito de catalisador de reformação. R2 e R.3 são circundados por paredes que envolvem os leitos de catalisador. Um gás quente flui por fora destas paredes, em contra-corrente com os gases de reacção nos leitos de catalisador. 0 calor é conduzido através das paredes, do gás quente, para os gases de reacção, enquanto os gases são convertidos numa mistura quente de hidrogénio, monóxido de carbono e dióxido de carbono. 2
Os gases produzidos a partir de RI, R2 e R3 misturam- se e formam o gás quente que flui para fora das paredes de R2 e r3, onde constituem a fonte de calor c ias reacções em R2 e κ3. Este gás é chamado o gás de aquecimento,
Corno uma vantagem geral da presente invenção, as paredes de R2 e R.3 podem ser concebidas com uma configuração de modo a formar um ópt imo canal para o gás d.e aquecimento.
Em geral, o sistema rea.cci.onaI, útil para o processo da presente invenção, compreende, ligados em paralelo, um primeiro e um segundo compartimentos de reacção adaptados para suportar um catalisador e para receber ama corrente de reagente, tendo o primeiro compartimento a forma de um tubo de reactor, em que os reactores R2 e R3 combinados contêm nm certo número de tubagens duplas, em que os tubos internos estão cheios com catalisador (R2) e as tubagens duplas, além disso, são configurarias num modelo que permite que o volume entre as tubagens duplas esteja também cheio com catalisador, isto é, o reactor R3. 0 calor sensível dos produtos gasosos combinados dos reactores RI, R2 e R3 é reciclado de volta para os reactores R2 e R3. 0 produto gasoso flui nos canais anelares originados pelas tubagens duplas, em contra-corrente com o fluxo dos reactores R2 e R3. 0 calor é fornecido ao reactor R2 por via da parede interior das tubagens duplas e o reactor R3 é abastecido com o calor da parede exterior das tubagens duplas, A vantagem dos reactores combinados, como se mostra na fíg. 2 , consiste no facto de o s canais de permuta de calor serem utilizados de uma. forma optimizada, r s t o e f tanto a parede interna como a parede externa são utilizadas como superfícies de permuta de calor fazendo assim uma 3 utilização óptima de material caro. Isto também leva a um desenho muito compacto do equipamentof em comparação com outros tipos de reformadores de permuta de calor e, ao mesmo tempo, providencia uma baixa quede de pressão. um certo n SCO cr a van tacem. d 0 -f s t r 11 o r .1. S C 0
Ao arrefecer o produto gasoso, existe de corrosão causada por metal em. pó. Uma ou desenho dos reactores combinados consiste no de ρό de metal numa superfície limitada.
Normalmente, as dimensões das tubagens duplas são as seguintes: tubo interno com um DO de 50 a 110 mm e o tubo externo com um DO de 80 a 170 mm. A configuração pode ser tal < 3ue a prop orção de permuti a de cai -or/area/volume de catai isador •S p ja. igual para. O s tub os interiores e exter rores, ΓΠ8 8 não é necessário que : seja 3. S S η-ΐΠ „
Lisboa, 8 de Outubro de 2013. 4

Claims (1)

  1. REIVIMDICAÇOES Processo para realizar a reformação a vapor endotérmica, não adiabática, de uma carga de bidrocarbonetos, caracterizado pelo facto de compreender as etapas de: introdução, em paralelo, de uma primeira corrente de carga de bidrocarbonetos num primeiro espaço de reacção e uma segunda corrente de carga de bidrocarbonetos num segundo espaço de reacção; em condições de reacção em que se faz contactar a primeira corrente com um catalisador no primeiro espaço oe reacção e se faz contactar a segunda corrente com um catalisador, no segundo espaço de reacção e a reformação endotérmica a vapor, não adiabática, da primeira e da segunda correntes numa permuta de calor indirecta com um meio de permuta de calor e retirando um primeiro e um segundo produto gasoso, reformado a vapor de forma endotérmica. não adiabática, em que o catalisador no primeiro espaço de reacção está disposto dentro de um reactor tubular (R3), numa relação de permuta indirecta de calor com o meio de permuta de calor, sendo o meio de permuta de calor introduzido num espaço tubular de permuta de calor que rodeia coneentricamente o reactor tubular (R3) com o primeiro espaço de reacção, sendo o catalisador, no segundo espaço de reacção (R2), disposto no lado exterior do espaço tubular de permuta, de calor, numa relação indirecta de permuta de calor com o meio de permuta de calor e em que o meio de permuta de calor compreende uma corrente de efluente da reformação a 1 vapor autotérmica cie um. misturada com o primeiro resultantes da reiormacao carga de hidrocarboneto o segundo produtos gasosos vapor endotérmica. Lisboa, 8 de ubro de 2013. 2
PT125077T 1999-12-02 2000-11-17 Processo e reactor para realizar reacções catalíticas não adiabáticas PT1106570E (pt)

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US (1) US6726851B1 (pt)
EP (1) EP1106570B1 (pt)
JP (1) JP5190162B2 (pt)
CN (2) CN1314203A (pt)
CA (1) CA2326950C (pt)
ES (1) ES2427927T3 (pt)
NO (1) NO324482B1 (pt)
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JP3202440B2 (ja) * 1993-10-08 2001-08-27 東京瓦斯株式会社 水素製造装置
ATE194816T1 (de) * 1996-10-04 2000-08-15 Haldor Topsoe As Dampfreformierungsverfahren
ATE200884T1 (de) * 1997-01-22 2001-05-15 Haldor Topsoe As Erzeugung eines synthesegases durch dampfreformierung unter verwendung eines katalysierten hardware
DK173052B1 (da) * 1997-05-05 1999-12-06 Topsoe Haldor As Fremgangsmåde til fremstilling af ammoniak syntesegas
EP0936182A3 (en) * 1998-02-13 2000-02-23 Haldor Topsoe A/S Method of soot-free start-up of autothermal reformers
DK173742B1 (da) * 1998-09-01 2001-08-27 Topsoe Haldor As Fremgangsmåde og reaktorsystem til fremstilling af syntesegas

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RU2261756C2 (ru) 2005-10-10
NO20006105D0 (no) 2000-12-01
NO20006105L (no) 2001-06-05
US6726851B1 (en) 2004-04-27
JP5190162B2 (ja) 2013-04-24
CA2326950C (en) 2008-07-29
CA2326950A1 (en) 2001-06-02
CN101015784B (zh) 2010-06-16
EP1106570B1 (en) 2013-08-28
NO324482B1 (no) 2007-10-29
CN1314203A (zh) 2001-09-26
CN101015784A (zh) 2007-08-15
EP1106570A3 (en) 2003-04-02
EP1106570A2 (en) 2001-06-13
ES2427927T3 (es) 2013-11-04
JP2001190946A (ja) 2001-07-17

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