EP0629176A1 - Procede pour fabriquer un produit gazeux - Google Patents

Procede pour fabriquer un produit gazeux

Info

Publication number
EP0629176A1
EP0629176A1 EP93905114A EP93905114A EP0629176A1 EP 0629176 A1 EP0629176 A1 EP 0629176A1 EP 93905114 A EP93905114 A EP 93905114A EP 93905114 A EP93905114 A EP 93905114A EP 0629176 A1 EP0629176 A1 EP 0629176A1
Authority
EP
European Patent Office
Prior art keywords
particles
fluidized bed
gaseous product
process according
separated
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.)
Withdrawn
Application number
EP93905114A
Other languages
German (de)
English (en)
Other versions
EP0629176A4 (fr
Inventor
Rodney James Dry
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.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
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 Commonwealth Scientific and Industrial Research Organization CSIRO filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Publication of EP0629176A1 publication Critical patent/EP0629176A1/fr
Publication of EP0629176A4 publication Critical patent/EP0629176A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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
    • C01B3/42—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 using moving solid particles
    • C01B3/44—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 using moving solid particles using the fluidised bed technique
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/384—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
    • B01J8/388—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only externally, i.e. the particles leaving the vessel and subsequently re-entering it

Definitions

  • the present invention relates to processes for producing a gaseous product.
  • the invention relates to a process for the steam reforming of hydrocarbons.
  • Steam reforming of hydrocarbons such as natural gas or naphtha involves reaction with steam to produce a mixture of carbon oxides, hydrogen and water vapour.
  • This gas mixture commonly referred to as "syngas” in the petrochemical industry, is the starting point for numerous catalytic synthesis products such as methanol, gasoline and wax. It is also useful for metallurgical reduction processes, production of eleptrical energy from fuel cells and production of hydrogen for use in, for example, ammonia synthesis.
  • the reforming reaction is strongly endothermic and is conventionally performed at around 800-900°C, at pressures of 10 to 30 bar in catalyst-filled, high-alloy tubes.
  • These tubes are usually 100 to 150mm in diameter and around 10m in length; heat transfer from hot flue gases on the outside of the tubes to the reacting mixture within is a major rate-limiting step in the overall process.
  • Thermal driving forces for heat transfer are large and tube layout is dictated, to a large degree, by the need for sufficient radiation view-factors to avoid the formation of hot and cold-spots on the tubes. This results in a need for large furnace volumes and plan areas - a constraint more difficult to accept in some applications than in others.
  • US Patent No. 3524819 describes a process in which a mixture of hydrocarbons and steam is reformed in an internal-free fluidized bed of fine-grained catalyst. Heat for the reforming reaction is provided by continuously withdrawing a portion of the catalyst and heating this catalyst by contact with hot flue gases before returning it to the reforming bed. However, this process exposes the catalyst (in bulk) to high temperatures which may cause the catalyst to sinter, thereby losing catalytic activity and requiring rapid (and costly) replacement.
  • an object of the present invention is to provide an alternative process utilising fluidized bed technology, which may permit a reduction in the size of the steam reforming plant.
  • the present invention provides a process for producing a gaseous product comprising passing reactants into a fluidized bed operated under conditions such that a reaction takes place in the fluidized bed to produce the gaseous product, the fluidized bed comprising particles having a density and size distribution such that at least a portion of the particles are entrained by the gaseous product leaving the fluidized bed, removing the gaseous product and entrained particles from the fluidized bed, substantially separating the particles entrained in the gaseous product from the gaseous product and returning the separated particles to the fluidized bed wherein at least a portion of the energy required for the reaction is supplied by heating the separated particles during their return to the fluidized bed.
  • the separated particles are preferably heated by passing the particles through a chamber where fuel gas or the like is combusted._ he separated particles may be catalytic or inert.
  • the fluidized bed is a multi-solid fluidized bed.
  • the present invention provides a process for producing a gaseous product comprising passing reactants into a fluidized bed operated under conditions such that a reaction takes place to produce the gaseous product, the fluidized bed comprising first particles having a density and size distribution such that at least a portion of the first particles are entrained by the gaseous product leaving the fluidized bed and second particles having a density and size distribution such that said second particles substantially remain in the fluidized bed, substantially removing the gaseous product and entrained first particles from the fluidized bed, separating the first particles entrained in the gaseous product from the gaseous product and returning the separated first particles to the fluidized bed wherein at least a portion of the energy required for the reaction is supplied by heating the separated first particles during their return to the fluidized bed.
  • any second particles are substantially separated from the first particles and returned to the fluidized bed.
  • This arrangement also permits the fluidized bed to be operated such that an amount of a mixture of first and second particles is normally entrained in the gaseous product.
  • the present invention provides a process for producing a gaseous product comprising passing reactants into a fluidized bed operated under conditions such that a reaction takes place to produce a gaseous product, the fluidized bed comprising first and second particles having density and size distributions such that at least a portion of both first and second particles are entrained by the gaseous product leaving the fluidized bed, removing the gaseous product and entrained first and second particles from the fluidized bed, separating the first and second particles entrained in the gaseous product from the gaseous product, substantially separating the first and second particles, and thereafter separately returning the separated first particles and separated second particles to the fluidized bed wherein at least a portion of the energy required for the reaction is supplied by heating the separated first particles during their return to the fluidized bed.
  • the surface area of the first particles is not critical.
  • the first particles are preferably catalytically inert.
  • suitable materials include but are not limited to dense alumina, zirconia, rutile, metals such as nickel or mixtures thereof.
  • the second particles are preferably catalytically active.
  • the first and second particles may be separated by a fluidized bed segregator.
  • the fluidized bed reactor and associated equipment to facilitate the separation and return of particles entrained in the gaseous product comprise a circulating fluidized bed system.
  • the process according to the invention may be suitable for a number of heat driven reactions including pyrolysis reactions, naptha cracking, ethane conversion to ethane and maleic anhydride synthesis.
  • the processes are particularly suitable for steam reforming of hydrocarbons to produce a gaseous product containing hydrogen and carbon oxides. Accordingly, the invention is hereinafter described in relation to this application.
  • the reactants are hydrocarbons and steam and the fluidized bed is operated under conditions such that a steam reforming reaction takes place.
  • the fluidized bed reformer may be operated at a temperature from 750 to 950°C preferably in the range of 800 to 900°C and at a pressure in the range of 5 to 80 bar, preferably 10 to 30 bar.
  • the first particles are preferably catalytically inert and have a maximum particle size of less than about 0.5mm with an average particle size preferably lying in the range of about 0.03 to 0.3mm.
  • the second particles are preferably catalytically active and may have a function and chemical composition typical of known steam reforming catalysts (e.g. Ni or Ru supported on alumina, calcium alumnate or zirconia) . These particles may be porous and display high catalytic activity for the steam reforming reaction. Average particle size preferably lies in the range of 0.7 to 7mm with little or no material smaller in size than 0.5mm.
  • the suspension density of the reformer vessel may be about 200 to 2000 kg/m , preferably about 1000 to 1800kg/m .
  • the separated particles are preferably heated to a temperature of about 950 to 1200°C, preferably about 1000 to 1100 C during their return to the fluidized bed reformer.
  • Figures 1 and 2 provide diagrammatic representations of apparatus suitable for performing the process of the present invention.
  • a mixture of hydrocarbons (natural gas or higher hydrocarbons such as ethane or naphtha) and steam 101 is pre-heated in heat exchanger 102 before being fed into the bottom of the fluidized bed reformer 103.
  • Unit 103 contains a dense-phase fluidized bed with two types of particle present:
  • a component which is catalytically active similar in structure and purpose to conventional alumina-supported Ni catalysts (e.g. ICI 57-series catalysts). These particles may be porous and display high catalytic activity for the steam reforming reaction. Average particle size lies in the range 0.7 to 7mm, with little or no material smaller in size than 0.5mm.
  • a component e.g. fused alumina which has low specific surface area and is catalytically inert. This component of the population is smaller in size than the catalytically active component, all particles being smaller than 0.5mm and average size for the inert component lying in the range 0.03 to 0.3mm.
  • Fluidized bed reformer 103 is operated such that the fine, inert component of the particle population is preferentially entrained from the top of the vessel while the coarse, catalytic component remains in the vessel. Steam reforming takes place within vessel 103 at a temperature of about 850°C and a pressure in the range 10 to 30 bar. Effluent gas 104, along with entrained fine solids, enters cyclone 105. Bulk disengagement occurs and the cyclone overhead stream enters hot gas cleaner 106. In this unit the bulk of the remaining solid is removed by, for example, a hot multicyclone system. Cleaned gas 107 leaves the cleaning unit 106 and passes to heat exchanger 102 before being scrubbed and passed on for use downstream.
  • Solids from the underflow of cyclone 105 are fed, via pressure recovery system such as loopseal 108, to chamber 109 where fuel gas and air are combusted at a pressure similar to that in vessel 103. Solids are heated from 800-850°C to around 1000-1100°C and are subsequently removed from the hot flue gases in cyclone 110. From here the hot solids are returned to the base of the reforming vessel 103 via pressure recovery system 111 to provided the heat necessary for the reforming reaction.
  • the bottom inlet system for hot solids is designed to ensure a large mass flux of bed material is available to rapidly dilute the hot solids stream, thereby avoiding the exposure of catalytically active particles to (destructive) high temperatures.
  • Hot, pressurised flue gas from the overflow of cyclone 110 is used for energy recovery purposes.
  • Hot gas cleaning is carried out in unit 112, the precise form of which is not critical. Partial cooling (to 800°C for example) followed by a micro-cyclone system may be used, or a ceramic barrier-filter system similar to those currently under development for pressurised fluidized bed combustion and gasification.
  • the cleaned gas is subsequently expanded through turbine 113. From here it is subjected to further heat recovery and finally vented.
  • a mixture of hydrocarbons (natural gas or higher hydrocarbons such as ethane or naptha) and steam 201 is pre-heated in heat exchanger 202 before being fed into the bottom of a fluidized bed reformer 203.
  • Unit 203 contains a dense-phase fluidized bed with two types of particles as described in Example 1.
  • Unit 208 contains a low velocity bubbling fluidized bed within which the coarse (catalytically active) particles preferentially sink to the bottom and are returned, along with some fine heat-carrier solids, to unit 203.
  • the fluidizing gas for unit 208 may be any convenient gas, but is preferentially steam or fuel gas.
  • Fine heat-carrier solids substantially free of coarse (catalytically active) solids, leave the top of unit 208 and enter unit 209 where fuel gas and air are combusted at a pressure similar to that in vessel 203.
  • Solids are heated from 800"-850 ⁇ C to around 1000°-1100°C and are subsequently removed from the hot flue gases in cyclone 210. From here the hot solids are returned to the base of reforming vessel 203 via pressure recovery system 211 to provide the heat necessary for the reforming reaction.
  • Hot, pressurised flue gas from the overflow of cyclone 210 is used for energy recovery purposes.
  • Hot gas cleaning is carried out in unit 212. Partial cooling (to 800°C for example) followed by a micro-cyclone system or a ceramic barrier-filter system may be used.
  • the cleaned gas is subsequently expanded through turbine 213, after which it may be subjected to further heat recovery and finally vented.
  • the present invention offers a compact system, that may be operated free of the need for oxygen, for application to processing in situations such as shipboard reforming.
  • the reforming vessel itself is free of expensive, high-maintenance tubes of high-alloy metal and associated maintenance and safety issues arising from wave motion. It may be configured to avoid substantial exposure of catalyst particles to high temperatures which would otherwise promote sintering, thereby achieving good catalyst utilisation.

Landscapes

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

Abstract

Un procédé pour fabriquer un produit gazeux est décrit, dans lequel les réactifs (par exemple Hydrocarbures et vapeur) sont introduits dans un lit fluidisé fonctionnant dans des conditions telles qu'une rßction ait lieu dans un lit fluidisé pour produire le prosuit gazeux (par exemple un gaz de synthèse), le lit fluidisé comprend des particules ayant une densité et une granulométrie telles qu'au moins une partie des particules soit entraînée par le produit gazeux quittant le lit fluidisé, le produit gazeux et les particules entraînées sont séparés du lit fluidisé, les particules entraînées dans l'effluent gazeux sont séparées pour l'essentiel des produits gazeux et les particules séparées sont retournées dans le lit fluidisé. Au moins une partie de l'énergie nécessaire à la réaction est fournie en chauffant les particules séparées durant leur retour vers le lit fluidisé. Des procédés à lits fluidisés pour des solides multiples sont également décrits.
EP93905114A 1992-03-06 1993-03-05 Procede pour fabriquer un produit gazeux. Withdrawn EP0629176A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
AU1240/92 1992-03-06
AUPL124092 1992-03-06
AUPL349392 1992-07-14
AU34/93 1992-07-14
PCT/AU1993/000099 WO1993017958A1 (fr) 1992-03-06 1993-03-05 Procede pour fabriquer un produit gazeux

Publications (2)

Publication Number Publication Date
EP0629176A1 true EP0629176A1 (fr) 1994-12-21
EP0629176A4 EP0629176A4 (fr) 1995-11-22

Family

ID=25644204

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93905114A Withdrawn EP0629176A4 (fr) 1992-03-06 1993-03-05 Procede pour fabriquer un produit gazeux.

Country Status (6)

Country Link
EP (1) EP0629176A4 (fr)
JP (1) JPH07505570A (fr)
CA (1) CA2130994A1 (fr)
NO (1) NO943113L (fr)
NZ (1) NZ249452A (fr)
WO (1) WO1993017958A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318796C (zh) * 2004-07-26 2007-05-30 中国科学院工程热物理研究所 煤气一蒸汽联产方法及带热解气化室的循环流化床锅炉
WO2008082312A1 (fr) * 2007-01-05 2008-07-10 Sinvent As Production d'hydrogène
JP4835581B2 (ja) 2007-11-14 2011-12-14 株式会社Ｉｈｉ 循環流動層改質装置
JP2009298618A (ja) * 2008-06-11 2009-12-24 Ihi Corp 有機化合物改質装置及び改質方法
JP7118341B2 (ja) * 2020-08-07 2022-08-16 株式会社堤水素研究所 水素製造装置

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US2523284A (en) * 1945-08-17 1950-09-26 Texas Co Method of manufacturing hydrogen and carbon monoxide
US2448922A (en) * 1946-01-23 1948-09-07 Socony Vacuum Oil Co Inc Continuous cracking process
US2783133A (en) * 1952-12-05 1957-02-26 Socony Mobil Oil Co Inc Hydrogen production
US2875150A (en) * 1953-11-12 1959-02-24 Hydrocarbon Research Inc Heavy oil conversion with low coke formation
US3342561A (en) * 1963-01-22 1967-09-19 Universal Oil Prod Co System for hydrogen production by catalytic decomposition of a hydrocarbon stream
US3573224A (en) * 1967-11-14 1971-03-30 Chemical Construction Corp Production of hydrogen-rich synthesis gas
JPS5575901A (en) * 1978-11-30 1980-06-07 Nippon Kokan Kk <Nkk> Production of reducing gas
DE3680122D1 (de) * 1985-02-13 1991-08-14 Shell Int Research Verfahren zur erzeugung eines wasserstoff enthaltenden gases aus kohlenwasserstoffen, wasserdampf und/ggf. kohlendioxid.
HU9201539D0 (en) * 1990-09-11 1992-08-28 Kortec Ag Method and device for gasifying gasifiable materials and/or transforming gas as well as heat exchanger of high temperature for executing said method
US5160456A (en) * 1991-06-07 1992-11-03 Exxon Research And Engineering Company Catalyst/heat-transfer medium for syngas generation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9317958A1 *

Also Published As

Publication number Publication date
WO1993017958A1 (fr) 1993-09-16
NO943113D0 (no) 1994-08-23
NZ249452A (en) 1996-01-26
CA2130994A1 (fr) 1993-09-16
JPH07505570A (ja) 1995-06-22
NO943113L (no) 1994-08-23
EP0629176A4 (fr) 1995-11-22

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