CN106964391A - The method for preparing and being formed the catalyst and precursor of supported active metals - Google Patents

The method for preparing and being formed the catalyst and precursor of supported active metals Download PDF

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Publication number
CN106964391A
CN106964391A CN201710229557.6A CN201710229557A CN106964391A CN 106964391 A CN106964391 A CN 106964391A CN 201710229557 A CN201710229557 A CN 201710229557A CN 106964391 A CN106964391 A CN 106964391A
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China
Prior art keywords
catalyst
zeolite
active metals
carrier
metal
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CN201710229557.6A
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Chinese (zh)
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理查德·海曼
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INGEN GTL Ltd
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INGEN GTL Ltd
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Priority claimed from GB201118228A external-priority patent/GB201118228D0/en
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Publication of CN106964391A publication Critical patent/CN106964391A/en
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
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Abstract

The application is related to the method for the catalyst and precursor that prepare and formed supported active metals.The present invention relates to the method for preparing loaded catalyst, it the described method comprises the following steps：(i) porous catalyst carrier is provided, it includes the framework with the internal pore structure for including one or more holes, the internal pore structure includes precipitating reagent；(ii) catalyst carrier is made to be contacted with solution or colloidal suspension liquid containing catalytically-active metals so that when being contacted with precipitating reagent, the particle containing catalytically-active metals is deposited in the internal pore structure of the framework of catalyst carrier.The invention further relates to the loaded catalyst prepared according to above method, and purposes of the catalyst in catalytic chemistry reaction, for example, the purposes in the F- T synthesis of hydro carbons.

Description

The method for preparing and being formed the catalyst and precursor of supported active metals
The application is Application No. 201280051673.9, and the applying date is on October 22nd, 2012, entitled " to prepare With formed supported active metals catalyst and precursor method " application divisional application.
Technical field
The present invention relates to the method for the catalyst and precursor for the supported active metals for preparing and being formed precipitation, and especially (but not solely) is related to the catalyst available for oxycarbide hydrogenation process.Especially, the present invention relates to prepare catalyst Method, the catalyst includes the porous carrier framework (as found in such as zeolite) of functionalization, and the framework contains Particle, nano particle or the cluster (cluster) for the catalytically-active metals encapsulated, it can partly or entirely be reduced.This Some aspects of invention are related to the application method of thus prepared catalyst, and are specifically for use in the synthesis of different types of hydrocarbon And/or conversion.
Background technology
Heterogeneous catalysis is used in many chemistry and petrochemical process.In many cases, the feasibility of technique Depending on the active of catalyst and its successful combination of selectivity and stability.With high activity but desired product is showed Going out the catalyst of weak selectivity may not be used to implement chemical reaction in commercial size.In addition, having to desired product Excellent activity and good selectivity but show that the catalyst of weak stability may be not suitable for commercial Application.In order to consider to urge The practical application of agent, it is necessary to reach the optimum balance between activity, selectivity and stability.
The practical application of catalyst is also limited by the economy and scalability of its preparation method.In scientific literature Describe many catalyst that acceptable performance is shown in terms of activity, selectivity and stability, but their preparation side Method outside chemical laboratory is generally impracticable, or in commercial Application is not economically feasible.
Small metallic particles or metal oxide particle with the diameter in the range of nanoscale are commonly known as cluster.By The performance that is shown by huger particle is largely different from them, therefore there is research metal cluster or metal oxygen The important motivation of the catalytic performance of compound cluster.Common situation is that unexpected catalytic effect may be attributed to the effect of cluster.
Cluster containing catalytically-active metals is supported on zeolitic material and there is advantage.The zeolite material for metal cluster Material is unique carrier, because the spatial obstacle assigned by its cage and hole limits the size for the cluster that can be formed among it. The obstacle that aperture (commonly known as " window ") between cage and hole is assigned, which is limited, can enter and leave the size in hole and cage. Therefore, cluster can be formed and be captured in cage by small precursor (for example, metal salt) in cage.
The cage of zeolitic material is the sufficiently small effect to apply similar solvent to cluster formed therein and therefore cage can Cause different catalytic performances to the cluster that it contains.The limitation of cluster in the cage of zeolitic material hinders the interaction of cluster and gathered Collection and the stability so as to enhance cluster.
The catalyst of carried metal and metal oxide cluster can be prepared by many different modes.US 4,552,855 is described Preparation method, it is described as the metal cluster for producing zero chemical valence being supported on zeolite.Pass through metal under a high vacuum Metal deposit occurs for gasification.
The alternative for producing the metal cluster catalyst of load is related to metal-carbonyl complex precursor impregnated carrier.This The example of the preparation method of sample is described in US 4,192,777.
US 5,194,244 describes the composition including zeolite and alkali metal compound, the wherein alkali metal in compound Summation plus the amount of any metal cation exchanged in zeolite exceedes the zeolite that the complete metal cation of offer is exchanged Required amount.When compound is loaded into zeolite, they are calcined at high temperature is used as alkalescence to produce formation and urges The basic matterial of agent or adsorbent.Haber et al., in Pure and Applied Chemistry, volume 67, the phase 8/9, the 1257-1306 pages, the deposition-precipitation method (chapters and sections 2.1.2.2) to form loaded catalyst is discussed, wherein active metal leads to Cross slowly addition precipitating reagent or be formed in situ precipitating reagent and be deposited on the carrier in precipitation solution.Note, carried for porous Body, deposition preferably occurs in exterior section.
US 4,113,658 is described to be included essentially homogeneously being deposited on nucleating surface (such as titanium dioxide for preparing Silicon) on metal material fine particle material deposition-precipitation technique.This by prepare nucleating surface suspension and Metallic compound is set to crystallize onto surface to realize from the solution including metallic compound at nucleation site.
EP 2 314 557 describes the catalyst for producing light alkene by synthesis gas, utilizes catalyst, wherein iron Be deposited over to iron is on chemically inert carrier (such as aluminum oxide).
Co-catalyst is added in solid catalyst or is added in the technique for be related to catalyst to improve it Performance in chemical reaction chemical substance.Individually, co-catalyst has minimum or no catalytic effect.It is some to help The active component interaction of catalyst and catalyst and thus change its chemical action to catalytic specie.Interaction can make The change of the electronic structure or crystal structure of Viability solid constituent.Conventional co-catalyst is to be impregnated in metallic catalyst and gold Belong to metal ion, reproducibility and the oxidizing gas or liquid in oxide catalyst, and during the course of the reaction or made With the bronsted lowry acids and bases bronsted lowry being added to before in catalyst.
Potassium is the co-catalyst of well known group VIII metallic catalyst, is usually used in the high temperature Fischer-Tropsch (High based on iron Temperature Fischer-Tropsch, HTFT) catalyst.However, potassium promotes group VIII metal and metal oxide Sintering.For example, US 6,653,357 describes the influence that potassium is migrated in fischer-tropsch process.If co-catalyst is for difunctional The second catalysis in catalyst is poisonous substance, then is especially relevant due to being inactivated caused by co-catalyst migration, for example, Hydrocarbon synthesis catalyst and acidic catalyst, such as such as US 7, described in 459,485 are utilized in hydro carbons synthesis technique. The high loading capacity of potassium can also cause loss of activity due to the obstruction in the hole of carrier, and in some applications, it has been shown that in potassium Facilitation effect is degenerated when loading capacity exceedes by weight 2%.
Another the related problem for preparing to metal supported catalyst is metal in use or for work Change the trend in required any high temperature preprocessing process with aggregation or sintering.Such aggregation or sintering reduction can be used for The effective surface area of the catalyst of catalytic reaction, it reduce catalyst activity.
Expect to provide metal or metal oxide catalyst with long-time stability, and provide such for manufacturing The method of catalyst, methods described avoids that such as sintering and activity of catalyst inactivation can be caused during synthesis or use The problem of catalytic component is migrated.
The content of the invention
According to the first aspect of the invention there is provided the method for preparing loaded catalyst, methods described includes following step Suddenly：
(i) porous catalyst carrier is provided, it includes the framework with internal pore structure, the internal pore structure includes heavy Shallow lake agent；
(ii) catalyst carrier is contacted with solution or colloidal suspension liquid containing catalytically-active metals so that with precipitation When agent is contacted, the particle containing catalytically-active metals is deposited in the internal pore structure of the framework of catalyst carrier.
On the one hand there is provided a kind of method for preparing loaded catalyst, it the described method comprises the following steps：
(i) porous catalyst carrier is provided, it includes the framework with internal pore structure, the internal pore structure includes one Individual or multiple holes and including precipitating reagent；
(ii) catalyst carrier is contacted with solution or colloidal suspension liquid containing catalytically-active metals so that with During the precipitating reagent contact, the particle containing the catalytically-active metals is deposited in the institute of the framework of the catalyst carrier State in internal pore structure.
In the method for the invention, the catalyst carrier can be oxide.
In the method for the invention, the internal pore structure can have one or more regions or " cage ", and it is by institute The smaller diameter portion or " window " for stating hole are enterable.
In the method for the invention, there can be the small diameter than the hole in the cluster containing catalytically-active metals Partly big effective diameter.
In the method for the invention, the diameter in the hole, or the diameter of " window " in the hole can be more than 0.2nm.
In the method for the invention, the catalyst carrier can have class zeolite structured.
In the method for the invention, the catalyst carrier can be aluminosilicate zeolite.
In the method for the invention, the aluminosilicate zeolite can have less than 10 silicon and aluminium mol ratio, for example, from In the range of 2 to 5.
In the method for the invention, according to zeolite structured International Zeolite Association's database, the frame of the catalyst carrier Frame can use FAU, BEA or MWW structure.
In the method for the invention, the catalyst carrier may include to balance by one or more charge balance cations Negatively charged framework.
In the method for the invention, the charge balance cation may be selected from alkali metal cation or alkaline-earth metal sun from Son, preferably potassium.
In the method for the invention, the charge balance cation of the framework can act as co-catalyst or co-catalyst.
In the method for the invention, the precipitating reagent may include and charge balance cation identical cation, and institute Total ion-exchange capacity of the catalyst carrier can be more than by stating the total content of the cation in loaded catalyst.
In the method for the invention, the particle containing catalytically-active metals can have crystal structure.
In the method for the invention, the catalytically-active metals may be selected from the one or more member of the group consisted of Element：Nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, manganese.
The method of the present invention can additionally include making the catalyst carrier with containing selected from by yttrium, lanthanum, cerium and any other The solution of one or more metals of the group of lanthanide series metal composition or colloidal suspension liquid contact, the metal also form described contain A part for the particle of catalytically-active metals.
The method of the present invention additionally can include making the catalyst carrier with being selected from the group being made up of copper, zinc, gallium, zirconium, palladium The contact of one or more elements, the element also forms a part for the particle containing catalytically-active metals.
The method of the present invention may include the other step of the material obtained by calcining in atmosphere, the resulting material Material includes the catalyst carrier with the particle containing catalytically-active metals, optionally, and the calcining is to dry the gained After the material arrived.
In the method for the invention, the particle containing catalytically-active metals can have crystal structure.
In the method for the invention, the particle containing catalytically-active metals can have spinel structure or perovskite Type structure.
In the method for the invention, the structure of the particle containing catalytically-active metals may include cation vacancy.
In the method for the invention, the electricity of the particle containing catalytically-active metals and the framework of the catalyst carrier Electrostatic interaction can occur for lotus balance cation.
In the method for the invention, the loaded catalyst may include Fe, Cu, K.
The method of the present invention may include the other step of the particle containing catalytically-active metals described in electronation, for example In the presence of hydrogen gas at high temperature.
In the method for the invention, the precipitating reagent can be first loaded into the described interior of the framework of the catalyst carrier In portion's pore structure.
In the method for the invention, the precipitating reagent can be alkaline.
In the method for the invention, the precipitating reagent can be carbonate or bicarbonate, such as potassium carbonate or bicarbonate Potassium.
In the method for the invention, the catalyst carrier is made and containing catalytically-active metals using incipient wetness Solution or colloidal suspension liquid contact.
In the method for the invention, the catalyst carrier can be made to be contacted with the solution with catalytically-active metals.
In the method for the invention, the loaded catalyst can be fischer-tropsch synthetic catalyst.
There is provided the loaded catalyst produced by above method according to the second aspect of the invention.
Purposes there is provided loaded catalyst in Catalytic processes according to the third aspect of the invention we, such as in Fischer-Tropsch Purposes in synthesis technique.
It is used for the one or more oxides and hydrogen gas production one from carbon there is provided a kind of according to the fourth aspect of the invention The technique of kind or hydrocarbons, including one or more oxides of carbon is connect with hydrogen in the presence of the catalyst of the invention Touch.
The internal pore structure of the framework of catalyst carrier can be loaded with precipitating reagent, example in the building-up process of catalyst carrier Such as, by the way that precipitating reagent is mixed in catalyst carrier synthetic mixture or gel.Alternatively, precipitating reagent can pass through catalyst carrier Post processing be loaded, for example, by using the infusion process of the solution including precipitating reagent, such as incipient wetness (incipient wetness impregnation).Result is that wherein precipitating reagent is positioned in the catalyst carrier in the internal pore structure of framework.
When catalyst carrier is contacted with solution or colloidal suspension liquid containing catalytically-active metals, solution or colloidal suspension Liquid enters the inner porosity of catalyst carrier framework, and when being contacted with precipitating reagent, occurs insoluble particle and sink Form sediment or form insoluble particle, the particle contains catalytically-active metals.Such particle containing catalytically-active metals Referred to herein as " cluster ".Generally, such cluster has the effective diameter less than 5.0nm, more preferably with less than 2.0nm Effective diameter, for example, the effective diameter less than 1.3nm.Generally, the full-size or effective diameter of cluster are by catalyst carrier frame The internal holes result of frame is limited.Catalytically-active metals can be dissolved in the solution, or can be colloid in suspension into Point, or both.
The cluster containing catalytically-active metals being thusly-formed can be catalytic activity with the factor of its own, or can quilt Processing is to form active catalyst, such as by electronation, heat treatment or by adding other component such as co-catalyst Or catalytic promoter.In one embodiment, precipitating reagent includes the source of another component, such as co-catalyst and/or co-catalysis Agent.
The hole of catalyst carrier advantageously comprise the diameter of its mesopore from small diameter be changed to larger-diameter one or Multiple regions or room.Such region or room are commonly known as " cage ".Preferably, these cages are only from the appearance of catalyst carrier Face can be entered by the smaller diameter portion in hole, and such smaller diameter portion is commonly known as " window ".In such embodiment party In formula, the formation of catalytically-active metals cluster occurs advantageously in cage so that cluster has the effective diameter more than window.This help hinders Only cluster migrates off cage in use or activation process, which improve its reservation in the hole of porous catalyst carrier, and Sintering is reduced or avoided in help.Sintering is desirably avoided by because cluster be gathered into larger cluster or particle reduce reactant can Therefore the total surface area of catalytically-active metals, cause it reduce catalytic activity and the inactivation of catalyst.
Catalyst carrier can be crystal or non-crystal, pore structure that carrier crystal is clearly defined due to it and generally Stronger stability but it is preferred that.Catalyst carrier is preferably inorganic carrier, and more preferably oxide carrier.Oxide The example of carrier includes silica, aluminum oxide, zirconium oxide, titanium dioxide, ceria, lanthana and its oxidation of mixing Thing, such as alumina silica.The catalyst that other examples of catalyst carrier include the phosphate structure with extension is carried Body, such as aluminate or phosphate, gallium phosphate, silicoaluminophosphate and silicon gallium phosphate.
Catalyst carrier is preferably the oxide material with class zeolite (zeotype) structure (with zeolite example).It is many Zeolite structured class is known, and is described in " the Atlas of Zeolite for being published and being possessed by International Zeolite Association In Structures ".It is preferred that result be intersect at the cage of the diameter of the diameter with more than hole there is two dimension or three-dimensional Those structures of porous network.With the zeolite structured example of class that such two and three dimensions hole is constructed include CHA, FAU, BEA, MFI, MEL and MWW.Three-D pore structure is most preferred, because this is intended to be used for catalytic chemistry reaction in catalyst When help to improve the diffusion of reactant and product.
For oxide material, hole " window " is generally by many so-called " T " atoms for the girth for forming hole or hole/cage opening Limit." T " atom is the atom of non-oxygen in the framework of oxide carrier.For example, in aluminosilicate material, " T " atom is aluminium And silicon, and in aluminum phosphate, " T " atom is aluminium and phosphorus.Preferably, at least internal pore structure of 1 size, hole window is by extremely The ring of few 10 " T " atoms is formed, and the ring of more preferably at least 12 " T " atoms is formed.It is preferred that structure be FAU, BEA, MFI and MWW。
For zeolite framework or the catalyst carrier including zeolite framework high surface area is provided so as to load containing catalysis live Property metal cluster and make the cluster with mean size realized among the pore structure of whole catalyst carrier it is scattered in order and point Cloth.
The framework of catalyst carrier can be made up of powered frame structure.For example, alumina silicate and SAPO are zeolite structured With negative electrical charge, it needs and extra framework cation balance.Utilize the catalyst with such negatively charged framework Carrier is probably favourable, because charge balance cation can be selected as the other component of final active catalyst, for example, Co-catalyst or catalytic promoter, the part interaction of itself and the cluster containing catalytically-active metals or can be formed containing urging Change a part for the cluster of active metal.
If catalyst carrier includes negatively charged framework, for example, aluminosilicate material, particularly aluminosilicate zeolite, then The framework of carrier advantageously comprises the mol ratio of medium or low silicon and aluminium.In this context, medium or low silicon with The mol ratio of aluminium means less than 10 ratio (that is, the SiO less than 202:Al2O3Than).Preferably, silicon：The mol ratio of aluminium is about (i.e. SiO in the range of 2 to 52:Al2O3Than in the range of 4 to 10).In the specific embodiment of the present invention, Si:Al ratios It is about 2.4 (that is, about 4.8 SiO2:Al2O3Than).In the optional embodiment of the present invention, the silicon in zeolite：Aluminium Than less than 2 (that is, the SiO less than 42:Al2O3Than), and in one embodiment, the silicon in zeolite：The ratio of aluminium is about 1.0 (that is, about 2 SiO2:Al2O3Than), such as X zeolite.
By providing the catalyst carrier with low or medium silicone content, zeolite framework has enhanced flat with electric charge Counter cation carries out the ability of ion exchange.If charge balance cation can be used as co-catalyst or catalytic promoter, then The increased loading capacity of such co-catalyst or catalytic promoter can be achieved.
Zeolite framework is many microporous frameworks, and it includes multiple cages connected by window.Preferably, the cage tool of zeolite framework has most Big size, it is more than the diameter for the window for providing the entrance for leading to cage.
The full-size of the cage of zeolite framework can be more than 5 angstroms (0.5 nanometer).Preferably, the maximum of the cage of zeolite framework Size is more than 10 angstroms (1 nanometer), and more preferably about 13 angstroms (1.3 nanometers).The present invention preferred embodiment in, Catalyst carrier is or including faujasite, it can be zeolite-Y or zeolite-X.In faujasite (FAU) structure, cage The maximum sized window that cage can be only less than by its full-size enters.Another example of desired structure is MWW structures, As for example found in zeolite MCM-22.
Preferably, catalyst carrier has hole, and it includes cage and window, for example, in class is zeolite structured or zeolite structured, its In the cluster containing catalytically-active metals be formed as kinetic diameters in cage, the kinetic diameters, which are more than, provides the entrance that leads to cage The diameter of window.By preparing the maximum sized cluster of the size with more than window, even if catalyst is subjected to high reaction temperature, gold The aggregation or sintering for belonging to the cluster of oxide are also mitigated or prevented.
The diameter for providing the window for the entrance for leading to cage is typically larger than 2 angstroms (0.2 nanometers).Preferably, the window of zeolite framework Full-size is more than 4 angstroms (0.4 nanometer), and more preferably about 7.4 angstroms (0.74 nanometer).Preferably, containing catalytic activity The cluster of metal has kinetic diameters, and the kinetic diameters are more than 2 angstroms (0.2 nanometer), preferably greater than 4 angstroms (0.4 nanometer), and more Preferably greater than 7.4 angstroms (0.74 nanometer).
For the catalytic applications using slurry or fluid-bed process, catalyst carrier should be preferably chosen from having well Those catalyst carriers of friction resistant performance.At this point, zeolite particularly aluminosilicate zeolite such as zeolite Y is favourable.
The supported catalyst produced according to the method currently protected can be used for catalytic chemistry reaction.By in catalyst There is the cluster of high dispersive in the whole internal pore structure of carrier frame, the surface area of the catalytically-active metals of reactant is exposed to It is high, this conversion number for being conducive to catalyst and the conversion of reactant.In addition, by the way that the cluster of catalytically-active metals is encapsulated in Kong Zhong, it is to avoid result in migration and the sintering of the cluster of larger cluster with relatively low total surface area.Which in turn reduces catalyst Inactivate and improve the life-span of catalyst.Loose structure include increase diameter cage in the case of, enhance encapsulation and The sintering of reduction, as described above, this pore structure is by the zeolite structured example of class.It is preferred that structure be included in and cage The two dimension or three-dimensional network of " window " compared to the hole intersected at the cage of increase diameter.The loose structure of interconnection be it is favourable, because Scattered realized for what catalytically-active metals improved in solution or colloidal suspension liquid by more efficiently diffusing through hole.Separately Outside, if being blocked in generation in the building-up process of loaded catalyst by some of cluster device to hole, or if process is being used Middle to occur any sintering, then the obstruction of porous network occurs less.
Catalytically-active metals are added to catalyst carrier, the solution or colloidal suspension as solution or colloidal suspension liquid Liquid is diffused into the internal pore structure of catalyst carrier framework.Hanged when using in the colloidal state containing catalytically-active metals of suspended phase During supernatant liquid, the effective diameter of suspended phase/colloidal solid sufficiently low should be entered and in allowing to lead to via openings or window In portion's loose structure.However, because compared with the catalytically-active metals being completely dissolved, the particle included in colloidal suspension liquid exists It will be slower when diffusing through the network in restricted hole, and with larger possibility pore structure will be caused to block, because There is the solution of catalytically-active metals to be preferred for this.
Other components of catalyst can also similar mode, i.e. be added to catalysis by solution or colloidal suspension liquid The internal pore structure of agent carrier framework.They can individually be impregnated in catalytically-active metals, or be used as same solution or colloidal state A part for suspension is impregnated in.
If catalyst carrier framework is substantially anion, for example, in alumina silicate and aluminosilicate zeolite, can carry out Ion exchange is to replace charge balance cation, for example, the cation of at least one I races or II races metal.Such process is led to " ion exchange " is commonly referred to as, and preferably, ion exchange includes including replacing cation by the way that zeolite framework is exposed to Salting liquid replacement cation is provided.Salting liquid can be aqueous.Optionally or additionally, solvent may include organic solvent, Such as alcohol.Cation is preferably the co-catalyst or co-catalyst of catalytically-active metals, and in a preferred embodiment, choosing The group that free lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium and barium are constituted.Preferably there is provided the cation of salting liquid form, such as carbon Hydrochlorate, and most preferably bicarbonate solution.Have found, the use of carbonate and particularly bicarbonate is carried to catalyst Body frame strip carrys out less destruction.In the case of alumina silicate and aluminosilicate zeolite, for example, the use of carbonate and bicarbonate It is intended to mitigate the dealuminated of the framework that would otherwise result in destruction frame structure and forms the extra of the aluminum oxide that can block hole Framework particle, and reduce the ability of the cluster containing catalytically-active metals.By destroying frame structure, the ability of sintering is reduced It is adversely affected.
According in an embodiment of the invention, catalyst carrier is or including anion zeolite framework, for example, silicic acid Aluminium zeolite.Method may include to carry out ion exchange using known technology to load cation to framework, for example, I races or II races The cation of metal.This ion exchange can be performed for more than once (if desired) to ensure that carrier frame is use up by cation Possibly complete exchange.If cation is co-catalyst or co-catalyst, this is used for increasing the loading capacity of co-catalyst, this Catalytic activity can be beneficial to.In addition, by reducing or eliminating any proton as the confrontation balance cation on framework, it is less The neutralization of alkaline precipitating agent occurs for ground.
In other embodiment, zeolite framework carrier is carried out the first ion exchange to implement to load to zeolite framework The cation of one or more I races or II races metal；And then carry out the second ion exchange.Second ion exchange can increase framework In cation co-catalyst loading capacity.The cation loaded in the second ion exchange preferably with the first ion exchange The cation identical of loading, but can be different cations.The present invention preferred embodiment in, method includes Zeolite framework is carried out first, second, and third ion exchange to increase the loading capacity of the preferred cationic in framework.
Ion exchange may include to heat ion exchanged soln.Ion exchange may additionally include catalytically-active metals be added or Drying and calcination ion exchanged zeolite before dipping.
If catalyst carrier includes anionic framework, for example, in alumina silicate and aluminosilicate zeolite, then passing through framework The degree that one or more charge balance cations carry out ion exchange is preferably more than 2% by weight.Preferably, electric charge is put down The ratio by mass of counter cation in the frame is more than 5%, and it is highly preferred that the ratio of charge balance cation in the frame Example is more than 10% by weight.In the specific embodiment of the present invention, the ratio of charge balance cation in the frame is pressed Weight meter is more than 12%.
Incipient wetness mixes catalytically-active metals and co-catalyst or co-catalyst in catalyst carrier framework A kind of mode in portion's pore structure.Incipient wetness includes the change of the dissolving containing one or more metals of addition certain volume The solution of compound (for example, salt), the volume is equal to the pore volume of the internal pore structure for the catalyst carrier being computed.It is just wet to contain Leaching method may include heated solution to improve the dissolving of metallic compound (for example, salt) in the solution.The suitable salt containing metal Example be nitrate, sulfate, carbonate, citrate, halide, alkoxide, phenates, acetate, benzoate, oxalates, Acetyl pyruvate and carboxylate.The preferred anion of salt is to be allowed into catalyst with sufficiently small effective diameter Those anion in the inner porosity of the framework of carrier.When salt is dissolved in aqueous, preferred anion has At least some acidic characters, then the aqueous solution can be with alkaline precipitating agent (such as alkali carbonate or bicarbonate) effectively React to form the cluster containing catalytically-active metals in ground.Nitrate is particularly preferred anion.
Method generally includes individually to handle catalyst carrier with the solution containing catalytically-active metals.If desired, Extra processing is carried out using identical or different metal, although this is preferred after the material of washing initial impregnation, and And if desired, add other precipitating reagent.
The technology can be considered as deposition-precipitation, and the material that it is related to catalytic activity is heavy from solution or colloidal suspension liquid Form sediment onto solid carrier, in the solid carrier precipitating reagent (in the internal pore structure of catalyst carrier) with dipping solution Or in solid phase during liquid contact.In a preferred embodiment, precipitation is reacted by acid/base and occurred.
The property of the solvent phase or liquid phase of solution or colloidal suspension liquid is not particularly limited.The purpose is to promote catalysis Active metal diffuses through the internal pore structure of catalyst carrier, and ensures change of the dissolving containing catalytically-active metals according to it The ability of compound makes the colloid-stabilised ability containing catalytically-active metals be selected so that the colloid for obtaining suitable size Particle.Solution or colloid can contain extra component, for example, one or more extra catalytically-active metals, any common catalysis The component of the component of agent or any co-catalyst.The mixture of the liquid as solvent phase or liquid phase can be used.Water is easily Solvent, particularly if it is desired to which the solution containing catalytically-active metals carries out pH controls to ensure Kong Zhongyou of the cluster in catalyst carrier Effect precipitation.However, the use of other solvent/liquid and mixture is not excluded.For example, organic liquid such as alcohol, ketone, aldehyde, carboxylic Acid esters and ether can individually or with other liquid be used in combination with.
Precipitating reagent in the internal pore structure of catalyst carrier framework makes colloid or solution of the catalytically-active metals from suspension It is middle to precipitate to form the cluster containing catalytically-active metals.Precipitating reagent is not a part for the frame structure of catalyst carrier, its The not exclusively such as charge balance cation of negative electrical charge frame structure.Generally, precipitating reagent is can to mix catalyst carrier framework Inner porosity in compound, for example, being included as the non-reactive component of synthesized gel rubber, or pass through rear synthesis skill Art such as incipient wetness is impregnated into inner porosity.Precipitating reagent can be, may include or can be converted to final activity Another component of catalyst, for example, optionally after further processing such as heating or electronation, it can be used as Co-catalyst or co-catalyst.
Precipitating reagent is based preferably on the dry weight of the catalyst carrier of optional ion exchange with 2wt% or more loading capacity bag Include in the internal pore structure of catalyst carrier.It is highly preferred that loading capacity is 5wt% or more, and even more preferably 10wt% or more.The precipitating reagent that can be included in the internal pore structure of catalyst carrier is more, accessible catalytic activity The potential loading capacity of metal is bigger.
Before being contacted with solution or colloidal suspension liquid containing catalytically-active metals, the catalyst carrier with precipitating reagent It is dried forms.Therefore, if precipitating reagent is added to catalyst carrier by the infusion process based on solution, solvent with Catalytically-active metals are removed before coming in contact.Which ensure that the internal pore structure of catalyst carrier is without can hinder containing urging Change any liquid phase that the solution or colloidal suspension liquid of active metal are penetrated into internal pore structure, and help improve containing catalysis The deposition efficiency and speed of the cluster of active metal.
Precipitating reagent can be worked by Acid-Base precipitation.In an example, precipitating reagent can be alkaline, such as, be Carbonate or bicarbonate alkali metal salt.When containing catalytically-active metals, (and such as other catalysis of optional extra component are lived Property metal, co-catalyst and co-catalyst) solution or colloidal suspension liquid contact alkaline precipitating agent when, contain catalytically-active metals Insoluble cluster for example formed by the precipitation of insoluble hydroxide or oxide material.Such precipitation Cluster can be before catalyst be used as by reducing process, for example, being turned by being heated in the reducing atmosphere containing hydrogen It is melted into metal cluster.
If precipitating reagent causes cluster to be formed by acid-base precipitation, the pH of the dipping solution containing catalytically-active metals can be pre- First controlled or adjusted to optimize the degree and efficiency of the precipitation in pore structure internally.PH can be adjusted by known means Section, such as by adding suitable hydroxide, carbonate or bicarbonate with increase the solution containing catalytically-active metals or The pH of colloidal suspension liquid, or by the suitable acid of addition to reduce pH.The example of merely exemplary property, for the aqueous solution or glue State suspension, hydroxide solution such as sodium hydroxide, potassium hydroxide, or preferably ammonium hydroxide can be used for increase pH, and nitre Acid or carbonic acid can be used for reducing pH.In embodiments, before addition catalyst carrier, solution or colloidal suspension liquid have From the pH of about 1 to 2 scope, for example, the pH of the scope from 1.1 to 1.7.Generally, with the catalyst carrier containing precipitating reagent After contact, the solution of colloidal suspension liquid or the pH of liquid phase will be preferably increased to 4 or bigger value, and more preferably 5 or bigger Value, such as 6 or bigger.The pH of dipping solution or colloidal suspension liquid obtained by control another method is that controlled loading is arrived The amount of alkaline precipitating agent in catalyst carrier so that higher loading capacity is by the pH of therefore dipping solution obtained by increase When with stronger effect.
PH with basic character and resulting solution is 4 or bigger precipitating reagent another advantage is that it can Reduction is neutralized related to solution or colloidal suspension liquid containing catalytically-active metals on a catalyst support any acid Any execution.For example, in the case of aluminosilicate zeolite, can be to crystallinity not exposed to acid solution by such zeolite Profit, causes the loss of frame structure.Destruction can be caused by some in peeling off component from framework, for example, aluminium can be peeled off from framework To form the additional frame particle of aluminum oxide in pore structure.This, which has not only broken up, can reduce the pore structure that sintering suppresses, and The obstruction in hole is also can result in, which also reduces the appearance available for the internal pore structure for forming the cluster containing catalytically-active metals Product.Therefore, such destruction is unfavorable result for preventing sintering, migration and/or the aggregation of active catalyst product, and this is again Adversely affect the surface area and performance (including its activity, selectivity and/or stability) of catalyst.
The use of alkaline precipitating agent itself is lived by allowing using the metal salt solution with bigger acidity come impregnation catalyst The possibility of property metal and other components also mitigates such effect.It additionally has an advantage that, if it is desired, it is possible to Using the solution or colloidal suspension liquid of the metal salt higher than previous expected concentration, this improves each metal in catalyst carrier Loading capacity.If catalyst carrier is substantially anion, it is ensured that anionic sites and charge balance cation such as alkali Metal cation complete exchange as far as possible, also helps to mitigate any effect of the acidity of any dipping solution or liquid, and also The possible loss of precipitating reagent activity is reduced by neutralizing.
Therefore, in the method according to the invention, although the framework destruction of a certain amount of catalyst carrier still can urged Occur in agent preparation process, but the invention provides the more preferable reservation of frame structure.This is to crystallization, porous The catalyst carrier of frame structure such as zeolite is particularly advantageous.
Optionally, any precipitating reagent on the outer surface for the particle that may be present in catalyst carrier is with containing catalytic activity It is washed off before solution or the colloidal suspension liquid contact of metal, while for example by avoiding repeated washing from avoiding internal pore structure In precipitating reagent removing.Remove outside precipitating reagent and can help to reduce metal cluster and catalyst carrier is formed in dipping process Trend on the outer surface of grain, is promoted containing the precipitation in catalytically-active metals internally pore structure.However, lacking on surface Amount alkaline precipitating agent can help to mitigate any possible of the acid dipping solution on the outer surface from catalyst carrier framework Damage.
(such as aluminosilicate zeolite and it is subjected to ion exchange in the case of the catalyst carrier with negative electrical charge framework Processing), catalyst carrier can be washed after ion exchange, and Zeolite support is partially dried, wet slurry or paste sample State.
In order to illustrate principle set forth above, the preparation of the iron catalyst of the potassium co-catalysis of load is now described.In order to prepare Such catalyst, the zeolite with anionic framework is used as catalyst carrier, such as aluminosilicate zeolite, and it is generally with sodium Supply or prepare as charge balance cation.Anionic catalytic agent carrier can be by one or many leachings of the sylvite aqueous solution Stain is exchanged by potassium completely so that the framework complete charge balance of potassium, and excessive sylvite is internally kept in pore structure.At this In the case of kind, the easily source of sylvite is potassium carbonate and/or saleratus, and so, the property of salt is alkaline, and is not become Significant damage or destruction is produced to the frame structure to catalyst carrier.So, excessive potassium carbonate or saleratus are available Make precipitating reagent.The material of potassium loading leniently can be washed or be rinsed to remove potassium carbonate/carbon from the outer surface of catalyst carrier The marks on surface of potassium hydrogen phthalate precipitating reagent, but the precipitating reagent in internal pore structure is not removed to any significant journey too much Degree.So, the zeolite that the potassium obtained by the salting liquid of iron content such as ferric nitrate (III) aqueous solution can be added to is modified, this leads The cluster of iron content is caused to be deposited in the internal pore structure of zeolite.
In certain aspects of the invention and embodiment, method may include the metal oxide to form cation vacancy Cluster.The cluster of the metal oxide of cation vacancy is the oxide material with cation vacancy, wherein by room cause can The excessive negative electrical charge of energy is compensated by the increase of the oxidation state from other cations in cluster, and the cluster has using many The ability of individual oxidation state, such as transition metal or lanthanide series metal.Alternatively, as described in more detail below, excessive negative electricity Lotus can be balanced by different cations, for example, the charge balance cation of framework, or the cation related to precipitating reagent.
The structure of cluster can be crystal.In one embodiment, the cluster containing catalytically-active metals is formula ABO3 Perovskite structure or formula AB2O4Spinel structure.Perovskite structure is by compound CaTiO3The crystallization of use Phase, although Ca and Ti can be replaced with other elements while keeping identical structure type.Spinel structure is to be based on MgAl2O4 Structure, wherein Mg and Al can be replaced similarly with other elements while keeping identical structure.With perovskite structure The example of catalyst includes those being described in WO2007/076257, and it can be used for fischer-tropsch reaction, and including containing element K, Fe, Cu and La catalyst.Include with spinel structure and its example to the active catalyst of fischer-tropsch reaction US 4,537, those described in 867, including formula FexCoyO4(x+y=3) iron and cobalt is respectively as metal A's and metal B Those, and it can also promote by alkali metal.According to the present invention, this material of perovskite structure or spinel structure can Prepared by following steps, add the solution containing catalytically-active metals and any co-catalyst and co-catalyst (for example, bag The aqueous solution of Fe, Mn and/or Co salt of dissolving is included, or includes the aqueous solution of Fe, Cu and La salt), and dipping contains K salt conducts The carrier of precipitating reagent, for example, for example in the form of alkaline potassium salt, potassium carbonate or carbon in the aluminosilicate zeolite that complete potassium is exchanged Potassium hydrogen phthalate, is optionally washed with water or rinses, and then dries the material of dipping to remove any water, and high temperature (for example, from Temperature in the range of 500 DEG C to 630 DEG C) under dry material is calcined in oxygenous atmosphere, this can cause in catalyst The perovskite-type material or spinel type materials of crystallization are formed in the internal pore structure of carrier frame.Perovskite-type material or point are brilliant Stone-type material can be made with cation vacancy, or cation defect.Due to the small size of cluster, and because cluster is by solvable Precursor formed, then the temperature required for producing any such crystalline phase is usually less than the side of manufacture large volume crystalline texture Method, the crystalline texture of the large volume is generally used as parent material by the use of individually insoluble oxide material.
The cluster of the metal oxide of different type and structure can be produced using the method for the present invention.The structure totally obtained will The property of metal itself is depended not only on, their compare and its positive charge is additionally depended on.Therefore, metal and its relative quantity Appropriate selection can be used for the structure of the cluster of the metal oxide obtained by instructing.
It is assumed that the cluster containing metal of cation vacancy (sometimes referred to as " cation defect " or " metal defect ") will be with phase Cation on the framework of negative electrical charge has electrostatic interaction, and it is assumed that electrostatic interaction can help to relax or hinder The only migration of charge balance cation and cluster, this sintering for being further utilized to relax or preventing cluster or aggregation, in " window "/" cage " knot Structure is particularly so such as in zeolite structured those structures such as showed in zeolite of class.Migrate and/or sinter and be poly- Collection is generally not favored catalyst performance.By prevent charge balance cation (and wherein charge balance cation be used as co-catalysis Agent or co-catalyst) migrated from catalyst, the cluster containing catalytically-active metals can by higher loading capacity co-catalyst/help and urge Agent is formed, and which enhance any co-catalysis effect or co-catalyst effect.This in contrast to the prior art, teaching in prior art Excessive co-catalyst loading capacity is unfavorable for the performance of active metal particles, if excessive co-catalyst is moved from catalyst carrier Moving causes the loss of activity, then it can also influence that the other components existed can be combined with loaded catalyst, for example, dual catalyst Or the second catalyst in bifunctional catalyst system.
After being contacted with solution or colloidal suspension liquid containing catalytically-active metals, catalyst carrier can be dried, example Such as, in the air of conventional drying baking oven.Alternatively, drying can be carried out by microwave.In other embodiments, drying can lead to Cross and be freeze-dried to carry out in oxidizing atmosphere or neutral atmosphere.Any one in these dry methods can be under vacuo Carry out.
After the cluster of catalytically-active metals is formed, resulting material can be forged in neutral atmosphere or oxidizing atmosphere Burn, and may also include discharge gaseous oxygen compound.Before calcining or other post processings are such as dried or reduced, catalyst carrier It can be washed to remove excessive liquid from the outer surface of catalyst carrier.It is favourable thoroughly to be washed at this stage, Because precipitated catalyst or catalytically-active metals are trapped within the inner porosity of catalyst carrier framework, and therefore will Any obvious degree will not be removed to by washing, it is allowed to which any impurity or unreacted material are removed, without bright The cluster containing catalytically-active metals of the aobvious precipitation for being unfavorable for loading.
The previous method of the cluster containing catalytically-active metals for preparing encapsulation does not tend to be easy to carry out on a large scale. Process provides the metal and metal oxide catalyst particle of the encapsulation for being commercialized a large amount of manufacture thermostable loads Economic method.
The loaded catalyst of process according to the invention manufacture can be applied in catalytic chemistry reaction.
For example, catalyst can be used for catalytic steam reforming reaction or water-gas transformationreation.In steam reformation, water with Hydro carbons or other organic material contacts are to produce synthesis gas.Water-gas transformationreation makes carbon monoxide be transformed into presence of water Carbon dioxide and hydrogen.Metal oxide cluster such as spinel structure or perovskite structure are used as such anti- The catalyst answered, reduces to form metal cluster in advance without catalyst.
Fischer-Tropsch (FT) technique be can by the reaction of catalyst made according to the method for the present invention another example. FT techniques can be used for by synthesis gas (carbon monoxide, hydrogen and generally also have carbon dioxide) change into liquid hydrocarbon.Synthesis gas It can be produced by following technique, such as partial oxidation or steam reformation raw material, such as, biomass, natural gas, coal or SOLID ORGANIC Discarded object or rubbish or carbonaceous refuse or rubbish.The product of FT techniques can be adjusted by changing reaction condition and catalytic component It is whole, for example, paraffin/alkene ratio to change hydro carbons, and to increased or decrease the oxidation product that can be generated (such as alcohol, ketone And aldehyde) degree.In FT reactions, the cluster containing catalytically-active metals generally will be before the use for example by using at high temperature Hydrogen treat is chemically reduced.
It typically, there are two kinds of Fischer-tropsch process, i.e. high-temperature technology (HTFT) and low temperature process (LTFT).In FT catalysis Usually used catalytically-active metals include those selected from the group consisted of in agent：Nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, Rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, manganese and combinations thereof.This group of metal is referred to herein as A races (Group).Catalytically-active metals or catalysis At least one of active metal is preferably selected from iron and cobalt.
FT catalyst may also include one or more alkali metal or alkaline-earth metal, be preferred from the group consisted of：Lithium, Sodium, potassium, rubidium, caesium, magnesium, calcium, strontium and barium.Alkali and alkaline earth metal ions co-catalyst is used as the co-catalyst of unique type, Or be applied in combination with other co-catalysts.Preferred co-catalyst is potassium in the species.
Can be used for the example of other co-catalysts in fischer-tropsch synthetic catalyst is included selected from the group consisted of Metal：Yttrium, lanthanum, cerium, any other lanthanide series metal, and combinations thereof.This group of metal is referred to herein as B races.Such co-catalyst The co-catalyst of unique type is used as, or is applied in combination with other co-catalysts.Preferred helping in the group is urged One or more of the agent in lanthanum and cerium.
The other example for the co-catalyst that can be used includes the metal selected from the group consisted of：Copper, zinc, gallium, Zirconium, palladium and combinations thereof.This group of metal is referred to herein as C races.Such co-catalyst is used as the co-catalyst of unique type, Or be applied in combination with other co-catalysts.Preferred co-catalyst is copper in this set.
Fischer-Tropsch gas phase process is typically categorized into high temperature (HTFT) and low temperature (LTFT) technique.HTFT techniques, which are generally utilized, to be contained The catalyst of iron is catalyzed, and in the temperature of the scope from 300 DEG C to 400 DEG C and (1.0MPa is extremely from 10 bars to 25 bars Operated under the pressure of scope 2.5MPa).LTFT techniques are generally catalyzed using the catalyst of iron content or cobalt, and from 150 DEG C operated to the temperature of 240 DEG C of scope and under 10 bars to -25 bars (1.0MPa to 2.5MPa) pressure.LTFT gas phase works Skill typically facilitates the formation of longer chain hydro carbons.However, catalyst prepared according to the methods of the invention is at relatively high temperatures It is stable, and therefore this method provide can be by the flexibility in the range of the treatment conditions that resulting catalyst is allowed, it is permitted Perhaps the temperature of the reaction zone of catalytic reaction is adjusted.
One or more catalytically-active metals can be unique metal in the cluster by the method formation of the present invention.Can Selection of land, cluster may include one or more extra catalyst metals, co-catalyst and co-catalysts.For for the negative of FT techniques Supported catalyst, catalytically-active metals are preferably selected from A races or its combination.Preferably for HTFT techniques, catalyst metals At least one be iron, and for LTFT techniques, at least one of catalyst metals is cobalt.Preferably, what is be additionally present is Metal, B race metal and C race metal of the one or more selected from alkali metal or alkaline-earth metal.It preferably, there are at least one alkali gold Category, it is preferably potassium.
In one embodiment, method of the invention includes：
Offer includes the catalyst carrier of zeolite framework, and zeolite framework contains at least one group i metal or group ii gold The charge balance cation of category or its combination；
Metal salt solution is provided, it includes：
First salt of the metal selected from above A races and combinations thereof；
Second salt of the metal selected from above B races and combinations thereof；And
Metal C selected from above C races and combinations thereof the 3rd salt；
Zeolite framework is impregnated using metal salt solution by incipient wetness；And
Calcine the zeolite framework carrier of dipping to form the cluster of the metal oxide of mixing in zeolite framework carrier, mix The cluster of metal oxide there is formula AxByCzOn, wherein x, y and z are metal A, B and C relative scale respectively in the oxide, Wherein x+y+z is integer, and wherein n is the relative scale for the oxygen for making oxide charge neutral.
In this embodiment, in addition to I races metal or II races metal, the cluster formed includes coming from for oxide form The catalytically-active metals of A races and other metals of B races and C races.Zeolite in the embodiment is preferably aluminosilicate zeolite.
The cluster being thusly-formed can be or may include dipping and the metal of charge balance hydroxide or oxide.Cause This, method may include to reduce and/or the cluster that is carbonized is with before starting the reaction by forming metal or carbide material activating catalytic Agent.
At reaction conditions, the cluster containing catalytically-active metals can come from reactant and production according in reaction condition and reaction The amount of the oxygen of thing shows a variety of oxidation state.For example, in FT reactions, the presence of carbon monoxide and carbon dioxide provides reaction In oxygen source, this can be terminated with the product of oxidized compound form, such as alcohol, ketone, aldehyde and carboxylic acid.They may also provide can The source of the oxygen of oxidation or partial oxidation catalyst component.Therefore, in reaction such as FT courses of reaction, cluster can be oxidized or part Oxidation, is partially or even wholly restored to metallic state, and/or Carbide Phases or partially carbonized thing phase.
Loaded catalyst prepared by process according to the invention for example can form difunctional with other catalyst combinations Or multifunction catalyst.
For example, the loaded catalyst optionally produced by the method for the present invention can be with acidic catalyst in single reaction Combined in area.By using the loaded catalyst combined with acidic catalyst, the product quilt formed on loaded catalyst Further upgrade to the product of higher commercial value.For example, by the way that acid catalyst is added into FT catalyst, olefin oligomerisation Degree can increase, and this can increase the yield of the liquid hydrocarbon of the available hydrocarbon chain length for having and being suitable as in the range of diesel oil.
The advantage of the method for the present invention be by the component that reduces catalyst for example catalytically-active metals, co-catalyst, The migration of co-catalyst and charge balance cation, then this cation leaves the migration of the internal pore structure of catalyst carrier It is suppressed, such as it prevents them from contacting other components, extra acid catalyst, and it is reduced by neutralizing technique or other techniques Or eliminate inactivation.Therefore, or even if using loaded catalyst, it may for example comprise the alkaline kation or alkaline earth of a large amount sun from Those of the zeolite of son, the acidity for reducing or even eliminating the bifunctional catalyst caused by the migration of these cations is urged The inactivation of agent component.
In one embodiment, such bifunctional catalyst oxygen supply carbon hydrogenation process is used, and including basis The FT catalyst and acidic catalyst of load prepared by the above method.Acidic catalyst can be selected from by acid zeolite, dioxy The solid of the group of SiClx-aluminum oxide, the oxide of vulcanization, acidic resins, solid phosphoric acid, acid clay or combinations thereof.This The example of the acidic catalyst of sample is H-ZSM-5 zeolites.
Acidic components can contribute to the reaction of such as hydrocarbon pyrolysis, oligomerization, cyclisation and isomerization and oxidation dehydration Activity.
Loaded catalyst can be or may include that zeolite framework is as catalyst carrier and all containing catalytically-active metals Such as the cluster of iron, the catalyst carrier may include the charge balance cation of at least one I races metal or II races metal, example again Such as, potassium as described above.
In such embodiment, the One function component (FT synthesizes component) of bifunctional catalyst can pass through alkaline sun Ion is by co-catalysis, while avoiding single function ingredients (acidic components) of this alkaline kation to bifunctional catalyst Adverse effect.
Therefore, catalyst prepared according to the methods of the invention can be used in bifunctional catalyst, for example, in hydrocarbon generation Effective bifunctional catalyst in (for example, F-T techniques) is reacted, the hydrocarbon reaction of formation, which is utilized, to be included containing catalytically-active metals Cluster loaded catalyst and acidic catalyst combination, for example, its can be hydrocarbon isomerization with gasoline boiling range produce Raw high-octane hydrocarbon.
Bifunctional catalyst may include the different catalyst components combined in single main body, main body for example, particle, bead, Extrudate or granule.Alternatively, bifunctional catalyst may include the independent of the different catalyst components that can physically mix , uncombined main body, for example, being substantially random distribution or separation in layer in catalyst bed.
Carbon monoxide/carbon dioxide hydrogenation can be used for by the loaded catalyst of the technique formation of the present invention In.
E.g., including the gas raw material of hydrogen and at least one of carbon monoxide and carbon dioxide can be fed into containing negative The reative cell of supported catalyst so that in the presence of loaded catalyst (optionally before reactions, electronation it Carbon monoxide and/or carbon dioxide are hydrogenated to produce hydrocarbon product afterwards), and hydrocarbon product can be removed from reactor.
Hydrocarbon product may include it is saturation, undersaturated, oxidation, it is non-oxide, aromatics, straight chain, side chain or The hydro carbons of ring-type.In one embodiment, it is preferred to hydrocarbon product be oxidation hydrocarbon, wherein alcohol is highly desirable.Another It is excellent in side chain and/or straight chain the non-oxide hydro carbons in the range of C4-C9 in the range of such as C6-C9 in individual embodiment The hydrocarbon product of choosing.In further embodiment, in straight chain, the non-oxygen in the range of C10-C23 in the range of such as C16-C20 The hydro carbons of change is preferred hydrocarbon product.Selectivity to desired product can be controlled by many means, for example, passing through control The relative concentration or partial pressure of reaction temperature and pressure, reactant and catalytic component, and by adding or following again to reactor The different component of ring.Hydrogenation of carbon monoxide technique and carbon dioxide hydrogenation process are well known in the art.In an embodiment In, second group of hydrocarbon product can be by all or part of and different catalyst or double-function catalyzing of the product for making reactor The component reaction of agent and produce, for example, by improving reaction to produce the gasoline component of high or higher octane.Second group of hydro carbons Product can be saturation and undersaturated C in gasoline, kerosene, diesel oil or lube oil boiling range or its combination4+ hydro carbons.
Improve first group of hydrocarbon product or one part may include to change into the hydrocarbon product with low octane rating and have Any technique of the product of higher octane rate, including but not limited to oligomerization, isomerization aromatization, hydrogen cracking, hydrocarbyl reaction Or its combination.
Brief description of the drawings
Now by the different embodiments only by way of embodiment with reference to the accompanying drawings to describe the present invention, in the accompanying drawing In：
Figure 1A is the schematic illustration of the structure of zeolite Y；
Figure 1B is the schematic illustration of zeolite MCM-22 structure；
Fig. 2 shows the schematic illustration of catalyst according to the embodiment of the present invention；
Fig. 3 is the block diagram for schematically showing the conventional method for preparing catalyst according to the embodiment of the present invention；
Fig. 4 is the schematic illustration of bifunctional catalyst bead according to the embodiment of the present invention；
Fig. 5 is the schematic illustration of the wherein reaction scheme that catalyst according to the invention can be used；
Fig. 6 is the schematic illustration for testing the experimental provision of the catalyst of the present invention；
Fig. 7 is conversion ratio and the selection for showing the catalyst according to the embodiment of the present invention tested in CO hydrogenation applications The figure of property；And
Fig. 8 is the conversion ratio for the catalyst for showing the optional embodiment according to the present invention tested in CO hydrogenation applications With the figure of selectivity.
Embodiment
The present invention can be by for hydrocarbon production or preparing the production of catalyst used and illustrate, and it will be with reference to one Carbonoxide is described to the hydrogenation of carbon dioxide with the non-limiting example in the related application of the hydro carbons being formed with. Principle of the present invention with wider application and the present invention illustrates the theoretical application with reference to correlation theory and inventor.
Zeolite support framework is used as the catalyst carrier of the catalyst of active metal cluster.Figure 1A shows zeolite Y The schematic illustration of alkaline frame unit, is typically depicted as 10.Zeolite Y uses the life according to the structure committee of International Zeolite Association Name method faujasite (FAU) it is zeolite structured.X zeolite is another zeolite structured example of faujasite, in its chemistry It is different from the mol ratio of zeolite Y, particularly its relatively low silicon and aluminium on composition.
Zeolite with faujasite structure is suitable carrier for carbon monoxide-olefin polymeric described herein, because There is void space or cage in the crystalline texture of the zeolitic material with about several angstroms to one or two nanometer of size for them 12.These void spaces or cage are entered by hole or window 14, and it is typically below the maximum for the void space that they are surrounded The full-size of size.Void space can be referred to as according to its position in lattice and its size nanocages (nanocage) or Super cage (supercage).In corresponding to Figure 1A the faujasite of represented zeolite Y it is zeolite structured in the case of, surpass The void space of level cage has 1.3 nanometers of full-size.Giving into the hole of the void space of super cage has 0.74 nanometer Full-size and formed by twelve-ring.Faujasite it is zeolite structured in super cage void space also by smaller chi Ten very little sodalite cages are surrounded, and it is connected by hexagonal prism.
The zeolite of structure with faujasite is suitable for the method according to the invention production carbon monoxide-olefin polymeric, because tool There is the maximum sized cluster bigger than the size of zeolite pore to be formed in void space.By this way, relaxed containing catalysis The aggregation of the cluster of active metal or sintering, because cluster is encapsulated in connecing in the super cage of carrier therefore between prevention adjacent clusters Touch.
Figure 1B shows the construction unit (Mobil Composition No. 22 material) of MCM-22 zeolites, typically with 20 describe, and it uses the MWW frame structures according to the structure committee of International Zeolite Association.Zeolite MCM-22 has super cage 22, It is as defined in its crystalline texture and is 1.82 nanometers with full-size and minimum widith is 0.71 nanometer of space Space.The void space of the super cages of zeolite MCM-22 is entered by hole 24, and the full-size in the hole 24 is less than the sky of super cage The size in gap space.As the zeolite of faujasite, metal oxide is likely to form in the void space of MCM-22 zeolites Cluster to relax or prevent aggregation or the sintering of the cluster of metal oxide.
Fig. 2 schematically shows the construction unit of catalyst according to the embodiment of the present invention, typically describes with 30. The catalyst elements represented in Fig. 2 are loaded on zeolite Y framework 32, and it is passed through with I races cation or II races cation 34 By ion exchange, it is potassium cationic in this case.Potassium cationic is additional frame cation and is attached to zeolite Y crystalline substance Exchange (negatively charged) position of lattice.Potassium cationic is loaded and is attached on the framework around the void space of zeolite Y cage. Known potassium ion and other I races and II races ion have promotes catalysis in hydrocarbon production technique (such as Fischer-tropsch process) Effect, especially, in Fischer-tropsch process, potassium reduces the selectivity of methane, and the possibility and the olefinic of product that increase chain increases are special Property.Inventor thinks to wish to promote cation to be loaded on framework to provide excessive ion-exchange capacity, and therefore from Son exchanges complete exchange on site.It is not used as in the excessive potassium of charge balance cation is present in single salt or compound In portion's pore structure.In this embodiment, total loading capacity of the potassium in zeolite Y is more than 14% by weight, and preferably big In 15wt%, and even more preferably greater than 20wt%.If the precipitating reagent used is potassium carbonate or saleratus, based on from The loading capacity of potassium carbonate or saleratus on the zeolite that potassium is exchanged is preferred as the dry weight of sub- exchanging zeolite catalyst carrier It is 5wt% or more, more preferably 10wt% or more.
In the void space of zeolite Y cage, (that is, the catalysis being intended in catalyst is anti-for the clusters 36 of reactive metal oxides It is active in answering) formed by the way that metal salt is immersed in void space.Gold in void space and after calcining Belong to salt sediment formation metal oxide.Metal oxide is formed with the full-size in the hole with more than the cage for entering zeolite Y Kinetic diameters.It reduce cluster movement possibility and therefore reduce aggregation or the sintering of adjacent clusters.
The particular combination of metal can form the cluster of the metal oxide of mixing, and it is cation defect.In an implementation In mode, the cluster of such mixed-metal oxides has perovskite structure or spinel structure.The cluster for being not bound by opinion is tied up, Think that by forming the cluster of such cation vacancy or defect metal oxide the steady of resistance migration and sintering can be improved It is qualitative.The cluster of the metal oxide of cation vacancy is the metal oxide in structure or lattice with cation vacancy Cluster.The cluster of cation defect can be combined or be received charge balance cation, such as potassium promoter with charge balance cation Ion, this is related to zeolite framework.
It is not intended to be tied up by theoretical cluster, inventor thinks that this combination causes additional frame cation (to be in this case Potassium promoter charge balance cation) and cation vacancy metal oxide cluster between electrostatic interaction.It is this Interaction can further help to reduce the migration of co-catalyst cation.In the catalyst prepared by aforementioned known method In, the migration of I races and II races co-catalyst atom is the common cause of the catalyst inactivation of alkali co-catalysis.By limiting or preventing Migration, reduces the stability for inactivating and enhancing catalyst.In addition, can be included in the catalyst co-catalyst sun from The ratio of son can increase.In the past, during due to the effect observed by catalyst stability and co-catalyst cation transport Inactivation, accreditation presence can mix the upper limit of the amount of co-catalyst cation in active metal catalyst.Conversely, it is assumed that In the preparation method of the present invention, the combination of the cation co-catalyst of high loading capacity and the cluster of cation vacancy can produce stabilization Frame structure and limit cation transport.
It is preferred that carrier structure be those zeolites with medium or relatively low dioxide-containing silica because these boil The negatively charged site that stone can mix its cationic co-catalyst that tend to the framework with greater number, and therefore may be used Allow the cation co-catalyst of largely loading capacity.
The cluster of the metal oxide of mixing can have formula AxByCzOn, wherein x, y and z be respectively in oxide metal A, B and C relative scale.The summation of x, y, z is integer, and n is the relative scale for the oxygen for making oxide charge neutral.
Metal A is catalytically-active metals, selected from the group consisted of：Nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, rhenium, molybdenum, chromium, Tungsten, vanadium, rhodium, manganese and combinations thereof.Iron is used in many applications, including Fischer-tropsch process, and in a preferred embodiment, gold It is iron or cobalt to belong to A.
Metal B is selected from by yttrium, lanthanum, cerium or any lanthanide series metal, and combinations thereof composition group.Metal B presence is considered as It is (again without being limited by theory) characteristic for assigning cluster cation vacancy, it can not only improve the stability of cluster, and can change The stability of kind framework.In addition, metal B can also assign improved hydrogen absorption characteristic to loaded catalyst.
Metal C is selected from the group being made up of copper, zinc, gallium, zirconium, palladium and combinations thereof.The cluster for being not bound by opinion is tied up, except reduction mixing gold Belong to the reduction temperature of cluster of oxide to be formed beyond metal cluster, the presence of metal C particularly copper is considered as to have to metal A Positive promoting catalysis.In a preferred embodiment, metal C is copper.
Fig. 3 is the schematic block diagram for the conventional method for showing the catalyst that display is prepared according to the embodiment of the present invention, one As with 40 describe.Follow the steps below to prepare catalyst according to the invention.
For aluminosilicate zeolite catalyst carrier, carrier material is generally provided or prepared by sodium charge balance cation；That is, The cation of the negative electrical charge of BALANCE CARRIERS framework is sodium (Na+).Position of the charge balance cation in zeolite framework is clear and definite Definition, and the number of tradable cation depends on the silica of carrier material and the ratio of aluminum oxide.Advantageously but Not necessarily using the carrier material of the ratio with low silica and aluminum oxide because they provide bigger exchanges sun from The ability of son.In a preferred embodiment, zeolite Y or X zeolite are the carrier materials used.
If it is desired to replace the sodium ion of charge balance with different cations, then class Zeolite support material 51 can be carried out Ion exchange 41.This is such technique, wherein the cation being present in class zeolitic material and other cation exchanges.The work Skill can be carried out by certain methods as known in the art.Most commonly ion exchange in the solution, including waiting to hand over The weak solution 52 of one or more salt of the one or more cations changed is stirred and carrier material is added to the solution In.In ion exchange process, the cation in solution progressively replaces ionic bonding to the cation of carrier frame, and from The solution 53 that ion-exchange process is obtained is dropped.
Solution can be heated to the speed that increase is exchanged.In order to reach the water of desired ion exchange in the present invention It is flat, it may be necessary to be performed for more than ion-exchange process once, may not be real in one step because completely exchanging It is existing.
If the ratio of silica and aluminum oxide is known, the ion-exchange capacity of certain kinds zeolitic material can be counted Calculate, and content of the metal in class zeolitic material can be determined and compare content of the metal in class zeolite and the friendship calculated Transducing power.This indicates whether to reach complete exchange, or more than maximum exchange ability or whether few metal is retained in class boiling In stone material.
In an exemplary embodiment of the present invention embodiment, ion exchange by the use of zeolite Na-Y as carrier material and potassium carbonate or Saleratus is carried out as charge balance cation source and precipitating reagent.After each ion-exchange step, it is washed with water Resulting material.Final ion-exchange step can obtain in the pore structure of zeolite containing excessive potassium carbonate or bicarbonate The material of potassium, it is used as precipitating reagent.In this case, final washing step can stay in the appearance of material partly to remove Carried out for the purpose of the excessive salting liquid of the inside in the hole of potassium carbonate or saleratus salting liquid rather than carrier on face.Can Selection of land, after final ion-exchange step, the zeolitic material of ion exchange can thoroughly be washed after ion exchange completion Wash, and be then dried before resulting material is subsequently with excessive potassium carbonate or potassium bicarbonate solution processing, located Reason for example utilizes potassium carbonate or potassium bicarbonate solution by incipient wetness, to be boiled with potassium carbonate or the loading of saleratus precipitating reagent The hole of stone.At this point, gentle wash/rinse can be carried out to remove the potassium carbonate or saleratus of excess from outer surface to keep away Exempt from the precipitation of the cluster of catalytically-active metals on the outer surface.Alternatively, such washing can be avoided by, and this can help to protect catalysis Damage of the outer surface of agent carrier from the solution containing acidic catalytic activity metal.Utilize the final first wet impregnation of precipitating reagent Method is favourable, such as by using the precipitant solution of concentration known, and the knowledge of the pore volume using catalyst carrier, The precipitating reagent of known quantity can be loaded into the internal holes of carrier, and this can help to control the final of the cluster containing catalytically-active metals Loading capacity.
After such a washing step, resulting material by drying to remove excessive moisture.Drying can be by this area Any conventional drying methods known are carried out, for example, material can be dried overnight in 100 DEG C to 120 DEG C of stove.
After material is dried, solution or colloidal suspension liquid containing catalytically-active metals are using such as just wet impregnation Method is carried out.Incipient wetness technology be related to the salt forms that produce for example one or more dissolvings containing catalytically-active metals Solution or colloidal suspension liquid, the salt are impregnated in catalyst carrier material.Liquid (solution or the colloidal suspension mixed with carrier Liquid) volume close to or slightly above used in carrier hole volume, so as to substantially all liquid enter carrier hole In.The amount for being used to the salt of solution or colloidal suspension liquid will determine the final Metal loading amount of catalyst.Generally, it is catalyzed Active metal (and any other metal such as co-catalyst or co-catalyst) is impregnated into carrier using the aqueous solution.The present invention The incipient wetness of illustrative embodiments utilize double deionized waters as the solvent for salt, such as molysite, cerium salt and copper Salt.However, the present invention expands to the use of other metal salts and solvent.
During incipient wetness 42a, the solution containing catalytically-active metals 54 can be acid solution, for example, It may include for acid nitrate.Solution is penetrated into the hole of carrier, wherein there is precipitating reagent such as I races metal or II races gold Belong to carbonate or bicarbonate.Now, due to the presence of alkaline precipitating agent, the pH of solution increases to catalytically-active metals to aoxidize The point 42b of the form precipitation of thing or hydroxide.This pH increase cause the salt of the precursor containing catalytically-active metals effectively and The hole of carrier and the inside of cage is equably deposited in form the cluster containing catalytically-active metals.Therefore, this method is by first The deposition-precipitation method of wet impregnated with method.Resulting material can remove excess in the stage wash from framework and outer surface Nitrate and potassium ion.
Before impregnation, the pH of the solution containing catalytically-active metals can be conditioned become it is more alkaline, to firm Fortunately the point under the pH of the point precipitated, to maximize the precipitation degree in internal holes, and also weakens acidity Adverse effect, the frame structure of the acidity erodable zeolite.Control pH, which is also assisted in, improves the journey precipitated by precipitating reagent Degree.
After impregnation steps, material is dried 43.Slurry can be kept drying in stove or it can be by other normal The method of rule carrys out drying.Water 55 is removed from material.
When material is dried, by calcined material 44.The calcining step is to be heat-treated 56 in atmosphere, and it is removed for soaking The anion of the salt used in stain processing, produces the metal oxide of the material as catalytic activity.For example, nitrate decompose with Form metal oxide and volatile nitrogen compound 57.The metal oxide formed in calcination process is predominantly located at zeolite material In the cage of material, and nitrogen-containing compound leaves carrier if not washed off in washing process from material as gas.Formerly In preceding method, if fruit catalytically-active metals are added to catalyst carrier (for example, zeolite) as charge balance cation, Calcination process can partly influence the class zeolite framework of crystallization by the way that it to be partly transformed into amorphous material.Oxide cluster Excessive aggregation can also produce structural failure to the class zeolite framework of material.However, in this embodiment, it is believed that due to precipitation Agent, producing stabilization, in calcination process (or during use continuous behind) is not assembled so as to metal oxide.With this The mode of kind, the damage to class zeolite framework can be limited, and the cluster of reactive metal oxides is protected, and produce stabilization , load mixed oxide cluster catalyst precarsor 58.
Catalyst can be used in fixed bed reactors, fluidized-bed reactor or slurry reactor.In order to be used for fixing In bed reactor, it is advantageous that combined catalyst and adhesive and formed the particle or bead of suitable size so as to avoid across The excess pressure drop of reactor, to improve the structural intergrity and wear resistance of catalyst.Suitable adhesive is viscous including kaolinite Soil, titanium dioxide, calcium oxide, barium monoxide, silica, aluminum oxide, its mixture and other bondings as known in the art Agent.Even in no adhesive, (it is favourable in fixed bed, liquid bed and slurry technique to catalyst prepared in accordance with the present invention ) in the case of also tend to have high wear resistance.
Catalyst can be used in hydrocarbon production technique such as Fischer-tropsch process, in carbon dioxide capture technique, to subtract Lack CO2 emissions and produce valuable hydro carbons and other hydrocarbon conversion techniques, the hydrogen of such as ethylbenzene dehydrogenation or hydro carbons Change isomerization.Catalyst made according to the present invention may be additionally used for the conversion for not being related to hydro carbons synthesis or conversion, such as by nitrogen Gas and hydrogen manufacture ammonia, or by synthesis gas synthesizing methanol.
One or more embodiments of the principle itself of the present invention based on the present invention, which are provided, produces difunctionalization catalyst. Fig. 4 shows bifunctional catalyst, typically describes with 60, by by major metal oxide according to the embodiment of the present invention Catalyst 30 combines to prepare with solid acid catalyst 62 (it is H-ZSM-5 zeolites in this embodiment).Double-function catalyzing Agent 60 with can the alumina adhesive of peptization combined to form bead 64.It is difunctional that other solid acid catalysts can be used for production Catalyst.
The bifunctional catalyst of present embodiment can be used for such as hydrocarbon production technique, and the technique, which is used, is rich in dioxy Change the raw material of carbon.The function of solid acid catalyst is by aoxidizing major metal to the reaction that solid acid catalyst is generally produced The primary product improvement that the catalyst of thing cluster is produced is the product with higher octane rate.This reaction includes isomerization, fragrance Change, oligomerization and hydrogen cracking reaction.Bifunctional catalyst is produced the vapour of upgrading by hydrocarbon production technique with enhanced commercial value Oily range products.
Due to compared with other catalyst as known in the art, the migration of I races or II races cation from dominant catalyst Substantially reduce, the specific characteristics of Fig. 4 bifunctional catalyst are to inactivate by the poisoning of solid acid catalyst.Although rising The I races of high content or II races cation, it is also connected to the framework of dominant catalyst.The poisoning of this reduction is attributed to the present invention Dominant catalyst characteristic.Therefore, Fig. 4 catalyst is double work(of I races with high content or II races co-catalysis cation Can catalyst, it shows the low-level poisoning of drop into H-ZSM-5 acid catalysts due to I races or II races cation transport, Therefore can reforming function to be kept longer run time.
Fig. 5 represents basic hydrocarbon production technique 70, and it is carried out in fluidized-bed reactor 72, the fluidized-bed reactor 72 be typical case's application for the present invention.Reactor includes cooling element and heating element heater 74.Cooling is passed through anti-by water circulation Answer the inside of device to complete, and heat by the heating coil being arranged in the inside of reactor to enter by water steam OK.
Reactor feed stream is synthesis air-flow and introduced by the entrance 76 in the bottom of reaction vessel 78.In reactor The pressure of bottom be enough to overcome the pressure drop of reaction medium carrier and be enough to make catalyst bed liquefy.
Synthesis gas is converted into hydrocarbon product when it flows through fluid bed 80.Hydrocarbon product passes through in reaction vessel The outlet 82 at top is extracted.Fluid bed is comprising catalyst according to the embodiment of the present invention and helps to protect catalyst bed It is held in liquefaction and the other materials of uniform temperature is kept between whole catalyst beds.
Embodiment
Now, here is the detailed description of the illustrative embodiments of the present invention.What embodiment was schematically shown in figure 6 Tested in experimental provision.Experimental provision 90 includes the reactor 92 of the volume with 840ml, and the volume is by filling water gravity point Analysis is determined.
In experimentation, raw material flow rate is normally maintained at 1000 sccms (sccm), in test During its be changed to 200sccm or 100sccm sometimes.The raw material flow rate of catalyst and 1000sccm to 5g, improvement Holdup time is changed into 0.3 gram-second per standard cubic centimeter (gs/sccm).Gas hourly space velocity is 7800 (h per hour-1)。
Catalyst basket 94 (7cm diameters) includes two circular 3mm grid of holes, and each of which is by 15 microns of sintering Stainless steel felt (hole with 15 microns) is held in position in.Sieve/felt closure below and above after screening Between catalyst (5g) there is 35 microns of average particulate diameter to be less than 25 microns of part to remove.Catalyst filling sieve Hole, equably cover basket floor area to 2mm depth.
Before starting the reaction, catalyst can under 723K in hydrogen by in-situ reducing 18h.The one of reactor effluent Fraction by needle-valve 96 to sampling valve GC-FID 98 (being equipped with the nonpolar capillary columns of CP-Sil 5B), its be thereby returned to Derogatory section of (knock-out stage) 99 is struck to sample with condensed water before being analyzed as follows permanent gas and C5+ in micro--GC-TCD Hydro carbons：With H2The CO of carrier gasxAr, CO, CH on post4、CO2, and for H2、CH4, the molecular sieves that are separated with Ar carrier gas of CO Post.
Embodiment 1- catalyst A
Follow the steps below to prepare catalyst A (Fe/Ce/Cu/KY).
Prepare Na+The Y- zeolites of cation exchange form.However, implementing and K+The ion exchange of progress, reason is for base In Fe HTFT catalyst, K+It is to compare Na+Good co-catalyst.
NaY ion exchange is by the way that 12g NaY to be added to 600ml 0.5M K in double deionized waters2CO3In solution Come carry out.K2CO3Amount in the solution represents K+Relative to 6 times of excess of the amount in the cation exchange site of zeolite.Resulting Suspension is stirred and heated at 80 DEG C with minimum 4 hours of the cooling that flows back.The ion exchanged zeolite then obtained is filtered simultaneously And washed with double deionized waters.
The process is repeated for three times to obtain complete ion exchange, and provides the ion-exchange capacity more than framework Excessive cation, and dry before the use.
Resulting KY zeolites are with proper amount of Fe (NO3)2、Ce(NO3)3With Cu (NO3)2Solution impregnates.
The volume of used solution is equal to the pore volume of the zeolite of addition.These nitrate are high solubles and permitted Perhaps the dipping of metal is completed simultaneously.
The slurry of gained is dried at 120 DEG C and 18h is calcined in 550 DEG C of air.
The overall composition of the transition metal ions of dipping so in catalyst reflects following atomic ratio：Fe:Ce:Cu= 86:9.5:4.5.Zeolite-Y with 2.9 Si/Al ratio contains the K of 14.4wt.% in theory when by complete exchange.
Catalyst obtained by 5g is loaded into reactor.Before reactions, catalyst is former in hydrogen under 723K Position reduction 18h.
Reactor feed stream by 159ml/min CO, 100ml/min Ar, 635ml/min H2With 106ml/min's CO2Composition, they are mixed before entering the reactor.Compare H2/(2CO+3CO2) it is equal to 1.When reaction temperature is 603K and gas Air speed (GHSV) is 7800h-1.Pressure in reactor is 20 bars.
CO2Hydrogenation is two-step process, and catalyst shows high activity to anti-water gas shift reaction first, by CO2Change into CO, then changes into hydro carbons by CO.
Test result is diagrammatically shown in Fig. 7 and is summarized in Table A.
It can be seen that, stable state CO conversion ratios are 74% and catalyst inactivation are not present, such as observable in the figure 7.May be used also It was observed that, within the transformation period, there is downtrend, such as carbon dioxide by declining in the activity of water-gas transformationreation What selectivity was proved, and there is increased trend in the selectivity to C5+ hydro carbons and in carbon monoxide conversion aspect.Methane is selected Selecting property shows highly stable curve.
It will be readily apparent that the chain obtained in this embodiment increases the high level of possibility, this is in conventional HTFT catalyst In be not observed.Under the reaction condition of the test, the chain of commercialization high temperature fischer-tropsch Fe base catalyst increases possibility Representative value (its maximum theoretical is 1) is about 0.70.However, the embodiment in the test implemented and described in this embodiment The catalyst chain with 0.81 increase possibility, and show high CO conversion (74%) in the steady state, it is low Methane selectively (84%) and high concentrating part (condensate fraction) (59.2%).
Observed good performance is stable over time and the not to be noted Inactivation Effect in test process. This stability makes the present invention be very suitable for the hydro carbons shape using the catalyst manufactured according to the method for the invention described Business into technique is realized.
Table A
Catalyst A is also used for test carbon dioxide hydrogenation.Catalyst A test result is summarized in carbon dioxide hydrogenation In table B.
Reactor feed stream by 100ml/min Ar, 675ml/min H2With 225ml/min CO2Composition, they are entering It is mixed before entering reactor.Compare H2/(2CO+3CO2) it is equal to 1.Reaction temperature is 603K and gas hourly space velocity (GHSV) is 7800h-1.Pressure in reactor is 20 bars.
The concentrating part of acquisition is the 45.6% of product.It is about 0.7 that chain, which increases possibility,.Methane selectively be 9.3 and Selectivity to C5+ hydro carbons is 21.8.
For comparison purposes, in addition to mantoquita is not added to incipient wetness step, another catalyst is urged Agent B is produced according to the identical program of catalyst A preparation.Catalyst B test result is summarized in carbon dioxide hydrogenation In table B.
CO2Conversion ratio is similar with B for two kinds of catalyst A with CO selectivity.Catalyst A produces slightly more oxygen Agent and methane selectively are less than catalyst B.Catalyst A chain growing ability and C5+ is selectively higher.Using urging The concentrating part that agent A is obtained is 45.6, and is 33.7 using the catalyst B concentrating parts obtained.
It is this compare illustrate the addition (being copper in this case) of the metal selected from C races with formed load, mixing The catalyst of oxide cluster has additionally relative to the catalyst for load, mixing the oxide cluster for not containing C races metal Benefit.
Table B
Embodiment 2- catalyst E
As described above, catalyst of the invention is still used for the suitable component for preparing bifunctional catalyst. In this embodiment, catalyst E by merge 5g catalyst A and 5g ZSM-5 zeolite extrudate (80%H-ZSM-5 zeolites, 20% alumina adhesive) prepare, the ZSM-5 zeolite extrudate is placed in the catalyst basket of STIRR reactors On catalyst A.This arrangement is equal to the bifunctional catalyst containing catalyst A and H-ZSM-5 zeolite.
With different weight (hourly) space velocity (WHSV) test catalyst E in hydrogenation of carbon monoxide.Test result is shown in Fig. 8 and table C summarises the test result under used highest weight (hourly) space velocity (WHSV).
In fig. 8, catalyst E is in the steady state in 7800h-1Gas hourly space velocity under show 74.3% carbon monoxide conversion Rate, and 43.4% concentrating part and 35.9% C5+ selectivity in the product.Methane selectively is 19.3%.
Table C
Table D is the comparison of the test result of catalyst A and catalyst E carbon dioxide under the conditions of same test.C5+ is selected The main distinction of selecting property is that catalyst A is 21.8% and catalyst E is 30.0%, and the master of the selectivity to oxidant Distinguish and be that catalyst A is 7.6% and catalyst E is 0.9%.Catalyst E concentrating part is 49.3%, and catalyst A concentrating part is 45.6%.
By the comparison of test result it is inferred that catalyst E produces liquid hydrocarbon product more than catalyst A and than catalyst A Few oxidant.
Visible Fig. 8 of stability of catalyst E performance, it shows the sign that conversion ratio declines.Generally, double-function catalyzing The acid function of agent moves to the acidic site of solid acid catalyst from dominant catalyst by alkaline kation and is poisoned.Entering After row 340 hours, due to without I races or II races cation from the migration of dominant catalyst, the constant choosing to aromatic compounds Selecting property is that acid function keeps unaffected evidence.The change when carrying out 268 hours is due to GHSV in the point in fig. 8 Place becomes from 7800 turns to 1560.
Table D
Table E illustrates effect of the potassium precipitating reagent in the internal pore structure of catalyst carrier framework.Catalyst A is analyzed as being 19%K and catalyst A2880 analyzed as being 13%K.
Table E
Different changes can be made as contemplated herein within the scope of the invention, and embodiments of the present invention can Include the combination of the feature of those different from clearly stating herein.

Claims (10)

1. a kind of method for preparing loaded catalyst, the described method comprises the following steps：
(i) porous catalyst carrier is provided, it includes anion zeolite framework, the anion zeolite framework, which has, limits ion The ion exchange site of exchange capacity and with including the internal pore structure in one or more hole, wherein the internal holes knot Structure includes alkaline precipitating agent, wherein the alkaline precipitating agent includes the cation of I races or II races metal；And the cation phase It is present in excess for the ion-exchange capacity in the anion zeolite framework；And
(ii) porous catalyst carrier of dried forms is made to be connect with the solution or colloidal suspension liquid containing catalytically-active metals Touch so that when being contacted with the alkaline precipitating agent, the particle containing the catalytically-active metals is deposited in the porous catalytic In the internal pore structure of the framework of agent carrier.
2. according to the method described in claim 1, wherein the internal pore structure has one or more regions (cage), it is logical The smaller diameter portion (window) for crossing the hole is enterable.
3. according to the method described in claim 1, wherein the porous catalyst carrier is aluminosilicate zeolite.
4. the step of according to the method described in claim 1, methods described is included additionally below：
Optionally drying includes the porous catalyst carrier of the particle containing the catalytically-active metals；And/or
Calcining includes the porous catalyst carrier of the particle containing the catalytically-active metals in atmosphere；And/or
Electronation contains the particle of the catalytically-active metals, for example in the presence of hydrogen gas at high temperature.
5. according to the method described in claim 1, wherein the alkaline precipitating agent is first loaded into the porous catalyst load In the internal pore structure of body framework.
6. according to the method described in claim 1, wherein the alkaline precipitating agent is carbonate or bicarbonate.
7. according to the method described in claim 1, wherein making the porous catalyst carrier be urged with containing using incipient wetness Change solution or the colloidal suspension liquid contact of active metal.
8. according to the method described in claim 1, wherein the loaded catalyst is fischer-tropsch synthetic catalyst.
9. a kind of loaded catalyst, it by producing according to the method described in claim 1.
10. the method that loaded catalyst according to claim 9 is used in catalytic chemistry technique as catalyst.
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