CN1350507A - Production of hydrogen-containing gas streams - Google Patents

Production of hydrogen-containing gas streams Download PDF

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Publication number
CN1350507A
CN1350507A CN99815103A CN99815103A CN1350507A CN 1350507 A CN1350507 A CN 1350507A CN 99815103 A CN99815103 A CN 99815103A CN 99815103 A CN99815103 A CN 99815103A CN 1350507 A CN1350507 A CN 1350507A
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sieve
steam reforming
catalyzer
carrier
reforming catalysts
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C·－Y·黄
R·A·奥维比克
E·M·普拉特瓦特
R·E·特鲁巴
N·范德普尔
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CB&I Technology Inc
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ABB Lummus Global Inc
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/1094—Promotors or activators
    • 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
    • Y02P20/50—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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

Steam-reforming is accomplished by use of a steam-reforming catalyst (preferably supported on a particulate support), with such supported catalyst being supported on a mesh, e.g., as a coating or entrapped in the interstices of the mesh. Alternatively, the mesh may be formed from a steam-reforming catalyst.

Description

The production of hydrogen-containing gas streams
The application requires the right of priority in No. the 60/107th, 127, the U.S. Provisional Application patent of on November 5th, 1998 application.
The present invention relates to produce hydrogen-containing gas with the catalyzed conversion of hydrocarbon feed.
In the catalyzed conversion of the hydrocarbon feed of producing hydrogen-containing gas, in general such conversion is finished in the presence of suitable conversion catalyst by using reforming gas (as steam and/or carbonic acid gas, particularly steam).In general, such raw material comprises methane and hydrogen-containing gas contains hydrogen and carbon monoxide, and such gas often is called as " synthetic gas " in the art.
Steam reforming reaction absorbs heat, and at high temperature operation is so that balance helps the production of hydrogen.The conversion reaction institute heat requirement of heat absorption heats by preheating material with in conversion process to be supplied with, and especially, conversion reaction is finished in reactor (often being called as steam reformer in the art).Usually the steam reforming reaction device is a kind of tubular reactor, and wherein pipe heats in the incendiary stove.But other reactor structure also is possible, the adiabatic packed bed of for example on-fuel tubular reactor or preheating.
The present invention relates to the steam conversion process that improved hydrocarbon feed is converted into synthetic gas.
According to one aspect of the present invention, synthetic gas is (a kind of hydrogeneous, usually the gas that also contains carbon monoxide) react in the presence of steam reforming catalysts by steam and hydrocarbon (hydrocarbon optimization methane) and produce, wherein steam reforming catalysts is a carrier with sieve or class sieve material, perhaps catalyzer promptly sieves by the catalysis material and forms with the form of sieve.
Term " is carrier with the sieve " is included in sieve and goes up coated catalysts and hold back catalyzer on the gap of sieve.In a preferred embodiment, be that the catalyzer of carrier comprises the steam reforming catalysts that is stated from the particle carrier with the sieve, the steam reforming catalysts of carrying is stated from the sieve.
More particularly, class sieve material comprises fiber or wire, as wire or fiber sieve, metal felt or net, metal fiber filter or analogue.The class sieve structure can comprise individual layer (as the metal wire structure or the steel mesh structure of braiding), perhaps can comprise the wire more than one deck; Preferably include multiple layer metal silk or fiber to form the three-dimensional network material.In a preferred embodiment, carrier structure comprises the multi-layer fiber of random position on layer.Can use the metal of one or more to produce metallic screen.Perhaps, the sieve fiber can be by metal singly not being arranged or forming with the material of metal mixed or comprise above-mentioned materials, as carbon or metal oxide or pottery.In a preferred embodiment, sieve comprises metal.Under the situation with the sieve bearing catalyst, the material that forms sieve does not preferably have catalytic to steam reforming.As mentioned above, in one embodiment, the material that forms sieve is a steam reforming catalysts.
In a preferred embodiment, wherein the class sieve structure comprises the multi-layer fiber that forms the three-dimensional network material, and the thickness of this carrier is 5 microns at least, is no more than 10 millimeters usually.According to an embodiment preferred, network thickness is 50 microns at least, more preferably is 100 microns at least, is no more than 2 millimeters usually.
In general, the fiber thickness of formation multi-layer fiber or diameter preferably less than about 150 microns, are more preferably less than about 30 microns less than about 500 microns.In a preferred embodiment, the thickness of fiber or diameter are about 8 to about 25 microns.
Three-dimensional class sieve structure can be by United States Patent (USP) the 5th, 304, and No. 330, the 5th, 080, No. 962, the 5th, 102, No. 745 or the 5th, 096, No. 663 described productions.But, should be understood that such class sieve structure can generate with being different from the described method of above-mentioned patent.
In the embodiment preferred of class sieve structure as the carrier of the steam reforming catalysts on particle carrier, the particle-catalytic agent carrier is a porous support, and in a preferred embodiment, surface-area is greater than 1 meter 2/ gram, preferred surface is long-pending greater than 5 meters 2/ gram.In most cases, surface-area is no more than 100 meters 2/ gram.Surface-area is measured with (BET) (Brunauer Emmett andTeller) method.Carrier is heat-stable porous support, and the representative example of the carrier that the conduct that may mention is such has aluminum oxide, silicon carbide, silicon-dioxide, zirconium white, titanium dioxide, calcium aluminate, aluminium titanates calcium, silica/alumina carrier etc.
The support of the catalyst that is loaded with steam reforming catalysts is the carrier of particulate forms (such supported catalyst is stated from the class sieve structure).Here the term particle of usefulness comprises ball-type particle, slender particles, fiber etc.In general, the median size of particle carrier is at least 0.5 micron, is no more than 20 microns, although can use bigger particle.In some cases, particle diameter can be low to moderate 0.002 micron.Under the situation that carrier particle is trapped, particle is not more than 300 microns, preferably is not more than 200 microns, most preferably is not more than 100 microns.When coated catalysts on sieve, particle carrier in most of the cases is no more than 10 microns.
It can be one type known in the art that the steam catalyzer transforms.In general, such catalyzer comprises nickel, ruthenium or rhodium, is with or without promotor (as basic metal).
According to one aspect of the present invention, steam reforming catalysts (the being with or without carrier) quantity that is stated from the class sieve structure is 5% at least, preferably at least 10%, the amount of catalyzer is no more than 60% usually, more generally is no more than 50% (all being based on sieve, catalyzer and the particle carrier weight of (if existence)).
In one embodiment of the invention, being formed by steam reforming catalysts and/or have class sieve structure (the class sieve structure is preferably the carrier of the steam reforming catalysts on the particle carrier) as the steam reforming catalysts function vector is that form with the shaped structures weighting material exists so that gas phase turbulance on the catalyzer of flowing through is provided in the steam reforming pipe.Sieve structure can provide suitable ripple so that the turbulent flow of increase is provided.Perhaps, the class sieve structure can comprise that wavestrip or vortex generator are to provide turbulent flow.The existence of turbulent flow generator allows radially (with vertically) to mix, and allows simultaneously to improve heat passage on wall with respect to currently known methods in this area.This can be by realizing to increasing turbulent flow generator with the wall contacting structure.For example, the structure weighting material can be module form (as be placed in the reactor tube one or more pieces cylinder (roller)), so that make passage in the module along the longitudinal direction of pipe.Cylinder can contain flat, wrinkle or wavy sheet or its array configuration, and sheet can have the wing or hole to promote mixing.Also sheet can be moulded the strip of wrinkle, separate mutually, and be fixed together by welding, wire, round tube type flat board or its array configuration by the plain film that just in time is fit to the size of pipe.
To know that also the form that is formed or be loaded with the structure sheet that the sieve of steam reforming catalysts (steam reforming catalysts can or not be stated from the particle carrier) can be different by steam reforming catalysts is used.For example, sieve can form as ring-type, particulate state, band shape etc., and is used as packed bed in pipe.In one embodiment, the size of particle is less than the size of known packed bed particle in the prior art.Therefore, be that the catalyzer (no matter whether as structure weighting material) of carrier is preferably used as packed bed with the sieve.
With the class sieve structure is that the steam reforming catalysts of carrier can be present on the class sieve carrier as being coated to the wire that forms the class sieve structure or the applicator on the fiber, and/or may reside in and be retained in the gap of class sieve structure.
In one embodiment, the steam reforming catalysts that wherein is stated from particle carrier occurs with the applicator on the sieve, and sieve may apply with particle carrier at first, then doses steam reforming catalysts to the particle carrier as the applicator of sieving.Perhaps, the catalyzer that is loaded with of particle carrier can be coated on the sieve.The particle carrier that is with or without catalyzer can be coated on the sieve with multiple technologies (as dipping or spraying).
The supported catalyst particle can be used for the class sieve structure, method is: the class sieve structure is contacted with comprising the liquid application composition that is dispersed in particle in the liquid (the preferred form of bathing that applies), application composition is entered or suck the class sieve structure and at the inside and outside formation porous coating of class sieve structure.
Perhaps, the particle coating that the class sieve structure applies with the particle carrier that comprises active catalyst or the class sieve structure can catalyst precursor.
In a preferred embodiment, the kinematic viscosity of liquid application composition is not more than 175 centistokes, and surface tension is not more than 300 dynes per centimeter.
In one embodiment, supported catalyst or support of the catalyst are coated on the sieve in the dip-coating mode.In a preferred embodiment, the oxidation before coating of three-dimensional class sieve material is as heating under up to 700 ℃ temperature at 300 ℃ in air.Sometimes, as fruit sieve material contaminated with organic substances, class sieve material will purify before oxidation, for example used organic solvent (as acetone) to clean.
Apply the mixed solvent system of preferred organic solvent of body lotion and water (particle is scattered in wherein).The polarity of solvent system preferably is lower than water so that prevent the solvability that catalyzer is high and obtain the coating slurry of good quality.Solvent system can be the mixture of water, acid amides, ester and alcohol.The kinematic viscosity that applies body lotion preferably is lower than 175 centistokes, and its surface tension preferably is lower than 300 dynes per centimeter.
In an embodiment preferred of the present invention, the class sieve structure that applies comprises wire or fiber, wire that applies or fiber are with selecting someway or handling, so that its surface tension is higher than 50 dynes per centimeter (measuring by " chemical progress; 43, contact angle, wettability and sticking power; american chemical association, 1964 " described method).
In the coating of the class sieve structure that comprises steel fiber, the surface tension of liquid application composition is preferably about 50 to 300 dynes per centimeter, more preferably from about 50 to 150 dynes per centimeter are (by T.C.Patton at " coating flow and colo(u)rant dispersion ", second edition, Wiley-Interscience, capillary tube technique described in 1979, the 223 pages is measured).Simultaneously, the kinematic viscosity of liquid application composition is not more than 175 centistokes (by P.C Hiemenz in " colloid principle and surface chemistry ", second edition, Marcel Dekker Inc., 1986, the 182 pages of described capillary viscometers are measured).
In such embodiment, metal coated surface tension is adjusted into consistent with the viscosity and the surface tension of liquid application composition, thereby on the class sieve structure, produce particle coating so that the liquid application composition is inhaled into the inside of structure.Metal coated surface tension is greater than 50 dynes per centimeter, and is preferably greater than the surface tension of liquid application composition so that liquid is spontaneously wetting and be penetrated into the inside of sieve.
Metal in coated structure does not have under the capillary situation of ideal, can heat-treat to produce the ideal surface tension structure.
Liquid apply component can any tackiness agent or tackiness agent prepare because can cause particle coating to be attached on the structure.
The surface of coated structure also can be through chemistry or physically modified (as the thermal treatment or the chemical modifying on surface) to increase the surface and to form the interparticle magnetism of applicator.
The solids content that applies body lotion is usually from about 2% to about 50%, and preferably from about 5% to about 30%.
Body lotion also can contain additive, as tensio-active agent, dispersion agent etc.In general, the body lotion inner additive is to the weight ratio from 0.0001 to 0.4 of particle, and more preferably from 0.001 to 0.1.
Class sieve material is preferred to apply like this: class is sieved material be impregnated into coating body lotion one or many, dry or calcining between dipping simultaneously.The preferred room temperature of the temperature of body lotion, but must be more much lower than the boiling point of liquid in the bath.
After the coating, drying comprises the class sieve material of the porous applicator that contains a large amount of particles, and preferred substance adopts vertical direction.Drying preferably by with mobile gas (as air) from 20 ℃ to 150 ℃, more preferably contact under 100 ℃ to 150 ℃ the temperature and finish.After the drying, the class that applied sieve material preferred (for example, in temperature from 250 ℃ to 800 ℃, preferably from 300 ℃ to 500 ℃, most preferably under about 400 ℃) is calcined.In a preferred embodiment, adjust temperature and airflow so that produce the rate of drying that the catalyst-coated thing is not had disadvantageous effect (as cracking, consent etc.).As a rule, preferably lower rate of drying.
The thickness of formed applicator can change.In general, thickness is at least 1 micron, is not more than 100 microns usually.Typical applicator thickness is no more than 50 microns, more typically is no more than 30 microns.
The porosity of the inside of coated sieve material is enough big so that allow the particle penetration that applicator contains or move in the three-dimensional network.Therefore, in fact the particle diameter of the particle that the pore size of three-dimensional material and applicator contain has determined to be deposited on the amount and the homogeneity of the applicator of material network internal and/or the thickness of the applicator in the network.The aperture is big more, and is big more according to the thickness of the even applicator that applies of the present invention.
Be under the situation of form of catalyst precursor at particle, after the particle deposition, handle product so that catalyst precursor is converted into active catalyst.Particle in being deposited on three-dimensional material network is under the situation of support of the catalyst, active catalyst or catalyst precursor can be applied to this carrier (for example by spraying, flooding or soak into) subsequently.
When using the coating body lotion, apply body lotion and can comprise additive in some cases.These additives have changed the physical property (particularly viscosity and surface tension) that applies body lotion so that the infiltration of sieve takes place in steeping process, and the equally distributed coating of inside and outside acquisition of sieving.Colloidal sol not only changes the physical property that applies body lotion, but also is used as tackiness agent.After the deposition, with product drying and calcining.
Polymkeric substance such as polyacrylic acid, acrylamide, quaternary organic ammonium compounds or other special mixtures based on particle selection are arranged with regard to the representational stablizer of mentioning here.Perhaps, can use a kind of organic solvent for same purpose.The example of this solvent has alcohol or liquid paraffin.The pH value of control slurry (for example adds HNO 3) be another kind of viscosity and the capillary method that applies slurry that change.
In a preferred embodiment, wherein sieve comprises the multiple layer metal fiber, the particle carrier that is with or without catalyzer can be by being coated on the sieve with electrophoretic c. as U. S. application series number the 09/156th, No. 023 (applying on September 17th, 1998) is described.In this method, wire screen is as one of electrode, and particle carrier (alumina supporter as required particle diameter is with or without catalyzer, and the aluminum oxide that also preferably includes solation is attached on the wire screen than macroparticle with promotion) is suspended in and applies in the body lotion.Apply voltage between electrode, one of electrode is the sieve that is formed by multi-layer fiber, and sieve adopts alumina supporter (being with or without catalyzer) to carry out electrophoretic coating.If alumina supporter does not comprise catalyzer, steam reforming catalysts (preferably including the nickel particle that is with or without one or more promotor) subsequently by impregnated structures (wherein containing the alumina coated thing) or with suitable (containing nickel catalyzator and preferred one or more promotor) thus solution soaks into structure to be added in the catalyst structure.Embodiment is illustrated preparing catalyzer by electrophoretic coating.
As mentioned above, the steam reforming catalysts that (is with or without particle carrier) can be by being stated from the sieve material holding back on the gap of sieve or keep catalyzer.For example, when production comprises the randomly-oriented fiber of multilayer, can comprise particle carrier, make sieve thus and particle carrier is retained in the gap of sieve as the mixture of producing sieve.For example, such sieve can be produced by method described in the above-mentioned patent, and suitable alumina supporter is added in the sieve that contains fiber and tackiness agent (as Mierocrystalline cellulose).The sieve of Sheng Chaning contains the aluminium oxide particles that is retained in the sieve thus.The particle carrier that is retained in the sieve soaks into nickel with method as known in the art subsequently.
Here the term of usefulness " bed void volume " meaning is the open space in the reaction zone part (for example pipe of steam reforming catalysts) that is not occupied by sieve, thinks that the opening or the hole of any catalyzer on opening on the sieve wherein or hole and the sieve or particle carrier occupied by sieve.Therefore, when measuring " bed void volume ", the sheet that sieve is considered to seal, and any catalyzer and particle carrier on the sieve are imporous.
Term " void volume of the sieve catalyst " meaning is that sieve is gone up total open space and sieved the open space of going up any particle carrier and catalyzer.
To be the void volume of bed multiply by 100 to the ratio of the cumulative volume (wherein placing sieve) of reaction zone part to term " bed void volume percentage ".
" sieve catalyst void volume percentage " to be sieve, particle carrier and catalyzer void volume multiply by 100 divided by the ratio of the cumulative volume (comprising pore and opening) of sieve, particle carrier and catalyzer.
" sieve void volume percentage " to be the void volume that do not have catalyzer or particle carrier in the sieve multiply by 100 to the ratio of the cumulative volume of sieve structure (opening and sieve material).
The sieve void volume percentage of the class sieve structure (not having catalyzer and/or particle carrier on the sieve) that the present invention uses is 45% at least, preferably at least 55%, more preferably at least 65%, even more preferably at least about 85% or 90%.In general, sieve void volume percentage is no more than about 98%.In general, average empty opening is 10 microns at least, preferably at least 20 microns.
Steam reforming reaction carries out in tube furnace (often being called as steam reforming equipment or steam reforming stove) usually, and stove comprises a large amount of pipes that suitably heat in stove.According to a preferred aspect of the present invention, the sieve catalyst of some amount (with as the form of the wire screen of steam reforming catalysts or to be loaded with or not have the form of sieve of the steam reforming catalysts of particle carrier) is used for reaction zone (for example pipe of stove), thereby makes a void volume percentage reach 70% at least.In most of the cases, bed void volume percentage is not more than 97%.For example, steam reforming catalysts (being with or without particle carrier) was stated from situation on the sieve with the form of packed bed under, bed void volume percentage was usually between 70% to 97%.Be stated under the situation of sieve in the form of steam reforming catalysts (being with or without particle carrier) with structure weighting material (opposite with packed bed), bed void volume percentage is usually between 70% to 97%.Usually sieve catalyst void volume percentage is 50% at least, preferably at least 60%, be no more than 90% usually.Be stated from steam reforming catalysts under the situation of particle carrier, catalyzer is present in (based on catalyzer and particle carrier weight) on the particle carrier with from 3 to 20% amount usually.
Temperature out when steam reforming is finished usually is at least 700 ℃, and in most cases temperature out is no more than 900 ℃.About at least 500 ℃ usually of the temperature ins of steam reforming are no more than 600 ℃ usually.The top hole pressure of pipe that contains steam reforming catalysts is usually approximately from about 15 to 60 crust, and pressure descends along pipe, is no more than 0.42 crust/rice (pipe range) usually, preferably is no more than 0.31 crust/rice.The steam reforming raw material generally includes hydrocarbon (optimization methane) and steam, and the ratio of steam-hydrocarbon is at least 1.5 usually, is no more than 6: 1 usually.
Steam reforming reaction can be in multiple steam reforming stove any in finish, can combine with additive method.As the replacement that increases hydrocarbon content and minimizing carbon monoxide content is reacted.
Steam reforming was carried out in a plurality of stages independently in the embodiment at one, and the heat that wherein results from one of them stage is used to provide or replenishes other stage institute's heat requirements.Can be in tubular reactor be undertaken by hot gas heating or the raw material that uses the hot gas preheating to enter the adiabatic reactor.
With regard to following embodiment, the present invention will be described further.But, should be understood that therefore scope of the present invention is not restricted.
Embodiment 1
On wire screen, prepare nickeliferous steam reforming catalysts on a small scale.
5 * 5 centimetres carrier is a metallic screen, and thickness is 0.8 millimeter, and the diameter of Stainless Steel Fibre is 12 microns, and sieve void volume percentage is 90%.Metallic screen comprises the multiple layer metal fiber.Sieve vertically is positioned in the bath of slurry.Aqueous slurry comprises the alumina catalyst carrier of 10% (weight), and (surface-area is about 10 meters 2/ restrain, the Nyacol of 0.11% (weight) is arranged TMThe commodity chlorination quaternary ammonium reagent of 20% alumina sol and 0.055% (weight)).The rare HNO of pH value of slurry 3Be adjusted to 5.5.Sieve links to each other with the negative pole of power supply, is positioned between two vertical metal electrodes (positive pole of electrode and power supply links to each other) and parallel with them.Apply 5 volts voltage 2 minutes, alumina deposit is on sieve therebetween.Sample was calcined 60 minutes down at 500 ℃ in air.Be deposited on 25.1% (weight) of the amount of the support of the catalyst on the sieve for the gross weight of sieve carrier and catalyzer.Ni (the NO that the metallizing bolting silk is contained 20% (weight) with 1.10 grams 3) 26H 2The aqueous solution of O is impregnated into initial humidity point (Wetness point).The sample that soaks into heats under 525 ℃ in air made Ni (NO in 60 minutes 3) 2Be converted into NiO.Aluminum oxide on the carrier of calcining back contains the NiO of about 15% (weight).
Embodiment 2
The nickel oxide of 20% (weight) grinds in Eiger Mill further to obtain the slurry of median size＜3 micron on the calcium aluminate in the distilled water slurry.Add 1/10th centesimal Stockhausen (a kind of dispersion agent), the colloidal sol (Nyacol of 20% aluminum oxide of 0.1% (weight) in water TM) and use the magnetic stirring apparatus well blend.This slurry further is diluted to 10% (weight) with distilled water again and is used for immersion coating.
Three monolith structures weighting materials that employing is made from the Inconel of U.S. Filter company 600 fibers sieve material (diameter 1 " * length 1 ") clean with acetone, and 350 ℃ of following thermal treatments 1 hour.Each structure is impregnated in the slurry for preparing, then removes unnecessary slurry with air cannon, air-dry 15 minutes, drying was 1 hour in 125 ℃ of baking ovens.Such operation repeats more than four times.Each dipping back weight in average income is respectively 6.1,11.4,16.1,21.1 and 24.7% (weight).The material all in one piece of these coatings at last before the test of the reaction of synthetic gas 500 ℃ of calcinings 1 hour down.The average load of catalyzer is 21.6% (weight).
Embodiment 3
Use the method identical to prepare slurry and material all in one piece with embodiment 1 and 2.The immersion coating method is also identical, and difference is three monolith structures are carried out additional successive of two steps coated with obtaining higher catalyst load.Weight income behind each dipping is respectively 6.5,12.2,17.4,22.3,25.7,29.1 and 31.8% (weight).Calcining 1 hour rear catalyst load down at 500 ℃ is 28.2% (weight) after measured.
The present invention is particularly conducive to the mass transfer limit that reduces in the catalyzer (by the catalyzer at the surface-coated thin layer of multiporous fiber metallic screen).Therefore can be higher than or similar in appearance to the volume activity of the method for prior art with reduce the quantity of steam reforming catalysts.The result of high catalyst bed and sieve catalyst void volume is to implement steam reforming under the pressure drop that is lower than prior art approach.
In addition, the present invention allows to improve heat passage (for example will sieve as structurized weighting material) on wall, and the preferred turbulent flow generator that adopts the contact wall perhaps uses the packed bed of comparing reduced size known in the art to implement reaction.Heat passage and the improved mass transfer of improvement under the concrete heat flux in the unit pressure drop allows steam reforming process to operate under lower wall temperature, has prolonged the life-span of pipe like this.Lower temperature has reduced the coke that forms on catalyzer, thereby allows the ratio of use than the steam/carbon of the method lower (typically being lower than 3) of prior art.Higher volume activity and the improved heat passage higher heat flux that has also allowed by wall, high if desired methane conversion, this is useful especially.
According to top technology, a large amount of improvement of the present invention and variation are possible, and therefore, in the scope of appending claims, the present invention can put into practice with non-specific herein description.

Claims (22)

1. method of producing synthetic gas comprises: make hydrocarbon and steam in the steam reforming reaction district, be selected from the sieve that forms by steam reforming catalysts and be loaded with steam reforming catalysts sieve in the presence of react.
2. the process of claim 1 wherein that sieve is a steam reforming catalysts, the bed void volume percentage of reaction zone is 75% at least, is not more than 97%.
3. the process of claim 1 wherein that sieve is the sieve that is loaded with steam reforming catalysts, the bed void volume percentage of steam reforming zone is 70% at least, and the void volume percentage of sieve catalyst is 50% at least.
4. the method for claim 3, wherein steam reforming catalysts is stated from the particle carrier, and particle carrier is stated from the sieve.
5. the method for claim 4, wherein catalyzer and particle carrier are being that the amount of 5% (weight) is present on the sieve at least.
6. the method for claim 4, wherein catalyzer comprises a kind of in nickel, rhodium or the ruthenium at least.
7. the method for claim 6, wherein sieve comprises the multiple layer metal fiber.
8. the method for claim 7 wherein is coated to supported catalyst on the sieve.
9. the method for claim 7, wherein supported catalyst is trapped on the gap of sieve.
10. the method for claim 4, wherein based on the weight of catalyzer, particle carrier and sieve, the mixture of steam reforming catalysts and particle carrier is with at least 5%, and the amount that is not more than 60% (weight) exists.
11. the method for claim 10 wherein is not more than 0.42 crust/rice by the reaction zone pressure drop partly that contains catalyzer.
12. the method for claim 10, wherein based on the weight of catalyzer and particle carrier, catalyzer is present on the particle carrier with the amount of from 3% to 20% (weight).
13. the process of claim 1 wherein that steam reforming catalysts is stated from the particle carrier that is loaded with on the sieve.
14. the method for claim 13, wherein sieve is the form of structure weighting material.
15. the method for claim 13, wherein the median size of carrier is less than 200 microns.
16. the method for claim 15, wherein the median size of carrier is not more than 20 microns.
17. the method for claim 15, wherein Shai thickness is at least 5 microns, is not more than 2 millimeters, and comprises the multiple layer metal fiber.
18. the method for claim 17, wherein the bed void volume percentage of reaction zone is 60% at least, is not more than 97%.
19. the method for claim 18, wherein reaction zone is the pipe reaction district.
20. catalyzer comprises: with the sieve is the steam reforming catalysts of carrier, and described sieve comprises the multiple layer metal fiber, and described steel fiber thickness is less than 30 microns.
21. the catalyzer of claim 20, wherein steam reforming catalysts comprises the active catalyst on the particle carrier, and carrier is coated on the sieve.
22. the catalyzer of claim 20, wherein the median size of particle carrier is not more than 20 microns.
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