CN109590019A - Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas - Google Patents

Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas Download PDF

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Publication number
CN109590019A
CN109590019A CN201710917428.6A CN201710917428A CN109590019A CN 109590019 A CN109590019 A CN 109590019A CN 201710917428 A CN201710917428 A CN 201710917428A CN 109590019 A CN109590019 A CN 109590019A
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China
Prior art keywords
catalyst
molecular sieve
zsm
core
preparation
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CN201710917428.6A
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椿范立
杨国辉
高潮
柴剑宇
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MOHAN Co.,Ltd.
Highchem Co Ltd
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High Chemical Technology Co Ltd
Kk Model
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Priority to CN201710917428.6A priority Critical patent/CN109590019A/en
Priority to PCT/CN2018/107966 priority patent/WO2019062815A1/en
Priority to EA202090904A priority patent/EA202090904A1/en
Priority to JP2020539126A priority patent/JP7232836B2/en
Publication of CN109590019A publication Critical patent/CN109590019A/en
Priority to JP2022187184A priority patent/JP7443474B2/en
Pending legal-status Critical Current

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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The present invention relates to a kind of core-shell catalysts, its core is HZSM-5 molecular sieve, the modified zsm-5 zeolite or its mixture of all or part of replacement of (non-) metallic element defined by specification of the H in HZSM-5 molecular sieve, and shell is selected from carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotube, metal organic frame MOF, graphite, active carbon, metal oxide film.The composite catalyst that the catalyst and the catalyst for methanol of synthesis gas conversion are constituted not only makes the high conversion rate of Selectivity for paraxylene height and synthesis gas, but also selectivity of the paraxylene in dimethylbenzene is also high when being used for one-step conversion synthesis gas.Therefore the invention further relates to comprising core-shell catalyst and for catalyze and synthesize gas be converted into methanol catalyst composite catalyst and aforementioned catalytic agent preparation and use.

Description

Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas
Technical field
The present invention relates to a kind of core-shell catalyst and its preparations.The invention further relates to answering comprising the core-shell catalyst Catalyst and its preparation, and the application of core-shell catalyst of the present invention and composite catalyst are closed, for directly being made by synthesis gas Standby paraxylene.
Background technique
Paraxylene is widely used in weaving and packaging material field as important organic synthesis raw material.Paraxylene Be mainly used for producing terephthaldehyde's ester and terephthalic acid (TPA) etc., the latter be used as plastics and polyester fiber intermediate and coating, The raw material of dyestuff and pesticide.Currently, industrial most common paraxylene production method is toluene disproportionation and C9 aromatic alkyl Transfer.In the method, due in product paraxylene content limited by thermodynamical equilibrium, be usually only capable of obtaining concentration being about 24 The paraxylene of weight %.However, on dimethylbenzene market, it is desirable that para-xylene concentration is 60 weight % or more, therefore should Concentration is far from meeting industrial demand, such as the production of polyester material.And in order to obtain high concentration paraxylene and Paraxylene yield is improved, is needed by a series of subsequent processings.In particular, the boiling point between three isomers of dimethylbenzene differs Very little cannot obtain the paraxylene of high-purity using common distillation technique, and must use expensive adsorptive separation technology, This just brings the loss of raw material and the promotion of cost.With the worsening shortages of petroleum-based energy, either still from the market demand From the angle of oil replacement, developing new aromatic hydrocarbons synthesis route all has high value.
Bridge of the synthesis gas as energy conversion can convert clear gusoline for coal, natural gas, biomass, be recognized To be one of most potential oil replacement approach.Wherein, with the composite catalyzing of metallic catalyst and suitable molecular sieve combination Agent can effectively regulate and control the distribution of Fischer-Tropsch reaction product, and such research makes great progress in recent years.Successfully utilizing After F- T synthesis prepares the oil product in different carbon number sections, more and more scientific workers are directly high by sight steering synthesis gas Selectivity prepares high valuable chemicals, including low-carbon alkene, low-carbon alcohols etc..Although one-step method from syngas aromatic hydrocarbons such as benzene, first Benzene, dimethylbenzene method have relevant research report, but in product paraxylene selectivity is not usually high and the technology still Industrialization is not implemented.The problem of being primarily present is that the regulation of selectivity of product is difficult to make a breakthrough.In addition, catalyst is easy to inactivate, The stability of catalytic performance is difficult to keep.
It improves one-step method from syngas and prepares the selectivity of paraxylene it is critical that the development of high performance catalyst and opening Hair.Wherein, there is preferable catalytic performance using the dual-function composite catalyst being made of methanol synthesis catalyst and molecular sieve. The reaction route includes the tandem reaction of some column: synthesis gas preparing methanol by hydrogenation, and methanol adds hydrogen dehydration, aromatization reaction, Xylene isomerization reaction etc..The route has very big benefit to synthesis gas conversion process is developed, and can not only promote country Energy strategy safety, and one of the solution of reply globalization petroleum-based energy exhaustion potential threat.Therefore, it improves to diformazan The selectivity of benzene reduces process complexity and cost, is that synthesis gas directly prepares paraxylene technological difficulties urgently to be solved.
Studies have shown that synthesis gas aromatic hydrocarbons directly processed need to generally undergo two step process, that is, first convert synthesis gas to methanol or Dimethyl ether, then by methanol or dimethyl ether aromatic hydrocarbons (MTA).For example, two reactor used by the coalification of Shanxi is respectively provided with two Synthesis gas can be aromatic hydrocarbons (CN101422743A) through dimethyl ether conversion by seed type catalyst.The synthesis gas aromatisation of use is urged Agent are as follows: HNKF-5: aluminium phosphate molecular sieve: Ga2O3:ZnO:BaO.Methanol-fueled CLC and first of the patent by synthesis gas by one section After the mixed catalyst of dehydration of alcohols, be packed into second stage reactor the mixed catalyst of aromatized catalyst and one section of catalyst into Row aromatisation, finally obtains aromatic product.
Above-mentioned two-stage method is prepared paraxylene there is only steps more by synthesis gas, and second-stage reaction process is longer, and energy consumption is high And method for preparing catalyst it is complicated the problems such as, and the selectivity of paraxylene in hydrocarbon less than 30 weights Measure %.
Lasa et al. reporting is on Cr-Zn/ZSM-5 catalyst by the performance of synthesis gas aromatic hydrocarbons (Ind.Eng.Chem.Res., 1991,30,1448-1455), wherein aromatic hydrocarbons selectively can reach in hydrocarbon 70.8%, but the specific product distribution of aromatic hydrocarbons is not referred to.It is subsequent but report on Cr-Zn/ZSM-5 composite catalyst by closing At the performance (Appl.Catal.A, 1995,125,81-98) of gas aromatic hydrocarbons, wherein 3.6-4.5MPa's is anti-at 356-410 DEG C Under the conditions of answering, arenes selectivity reaches 75% in hydrocarbon, but the selectivity of dimethylbenzene is no more than 20%.Wang Desheng et al. The Fe/ that (catalytic chemistry journal, 2002,23 (4), 333-335) are mixed using F-T synthesis Fe base catalyst with aromatisation molecular sieve MnO-ZnZSM-5 composite catalyst makes synthesis gas generate lower carbon number hydrocarbons intermediate in Fischer-Tropsch reaction and is converted into over a molecular sieve Aromatic hydrocarbons, CO conversion ratio therein reaches 98.1% at 270 DEG C, however the arenes selectivities such as benzene, toluene are lower.Recently, Martin With Fan Weibin team (Chem, 2017,3,323-333) by ferrum-based catalyst Na-Zn-Fe5C2(FeZnNa) and after modification Mesoporous HZSM-5 molecular sieve mixing, has effectively achieved and directly prepares aromatic hydrocarbons by the synthesis gas of intermediate of alkene.340 DEG C, Under conditions of 2MPa in hydrocarbon product most available 51 weight % aromatic hydrocarbons, wherein based on light aromatics.However simultaneously The selectivity of the paraxylene in aromatic hydrocarbons is not referred to.Wang Ye team, Xiamen University (Chem, 2017,3,334-347) is based on development The academic thought of coupling reaction, ingehious design go out Zn doping ZrO2/ H-ZSM-5 bifunctional catalyst realizes one step of synthesis gas Highly selective, high stability prepares aromatic hydrocarbons.In order to improve the content of light aromatics BTX (benzene, toluene, dimethylbenzene), author passes through Silanization treatment is carried out to H-ZSM-5 molecular sieve outer surface to poison to reachThe purpose of acidic site, successfully mentions BTX selectivity in high final aromatic product.Ratio of the BTX in aromatic hydrocarbons can be improved to 60 weight %, however wherein diformazan The content of benzene and paraxylene also never refers to.
Although above-mentioned catalyst can be obtained aromatic hydrocarbons by one step of synthesis gas, the selectivity of paraxylene is not often high, and And the isomerization reaction of dimethylbenzene cannot be effectively inhibited.
Summary of the invention
The present invention is intended to provide a kind of with the highly selective catalyst for directly preparing paraxylene by synthesis gas and its preparation Methods and applications.Designed method for preparing catalyst is simple, synthesis gas high conversion rate, Selectivity for paraxylene are high, is expected to Industrial application.
It is an object of the present invention to provide a kind of core-shell catalysts.When the catalyst is converted with for catalyzing and synthesizing gas When being used in combination for the catalyst of methanol, not only make the high conversion rate of Selectivity for paraxylene height and synthesis gas, but also to two Selectivity of the toluene in dimethylbenzene is also high.
Another object of the present invention is to provide a kind of method for preparing core-shell catalyst of the present invention.
Another object of the present invention be to provide it is a kind of for directly preparing the composite catalyst of paraxylene by synthesis gas, should Catalyst include for catalyze and synthesize gas be converted into methanol catalyst and core-shell catalyst of the present invention.The composite catalyst exists When catalyzing and synthesizing gas and being converted into hydrocarbon, not only make the high conversion rate of Selectivity for paraxylene height and synthesis gas, but also paraxylene Selectivity in dimethylbenzene is also high.
It is yet another object of the invention to provide a kind of methods for preparing composite catalyst of the present invention.
Final object of the present invention is to provide core-shell catalyst of the present invention or composite catalyst of the present invention by closing The purposes in paraxylene is directly prepared at gas.It is used as using core-shell catalyst or composite catalyst of the invention by synthesis gas The catalyst for directly preparing paraxylene, not only makes the high conversion rate of Selectivity for paraxylene height and synthesis gas, but also to two Selectivity of the toluene in dimethylbenzene is also high.
Solving the technical solution that above-mentioned technical problem of the present invention uses can be summarized as follows:
1. a kind of core-shell catalyst, center are H-type ZSM-5 molecular sieve, H whole or portion in H-type ZSM-5 molecular sieve Divide and is selected from Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn and B by one or more Element M replacement modified zsm-5 zeolite or their any mixture, shell be selected from carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotube, metal organic frame MOF, graphite, work Property charcoal, metal oxide film (such as MgO, P2O5, CaO) one of or it is a variety of.
2. center is H-type ZSM-5 molecular sieve, the H in H-type ZSM-5 molecular sieve according to the 1st core-shell catalyst Partly or entirely by the Zn modified zsm-5 zeolite replaced or their any mixture；And/or shell is selected from silica Film, Silicalite-1, metal oxide film (such as MgO, P2O5, CaO), one of MCM-41, SBA-15, KIT-6 or more Kind, preferably Silicalite-1；It is particularly preferred that element M accounts for M-ZSM- in the modified M-ZSM-5 molecular sieve of element M The 0.5-15 weight % of 5 molecular sieve total weights, preferably 1-10 weight %, particularly preferred 1-5 weight %.
3. the weight ratio of center and shell is 100:1-1:100, preferably according to the 1st or 2 core-shell catalyst 10:1-1:10, more preferably 5:1-1:5, particularly preferred 5:1-1:1.
4. a kind of method prepared according to any one of 1-3 core-shell catalysts, comprising:
1) core of a granular form is provided, is H-type ZSM-5 molecular sieve, the H in H-type ZSM-5 molecular sieve is all or part of Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B are selected from by one or more Element M replacement modified zsm-5 zeolite or their any mixture；And
2) carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphite will be selected from Alkene, carbon nanotube, metal organic frame MOF, graphite, active carbon, metal oxide film (such as MgO, P2O5, CaO) one of or Multiple material is coated on core surface of a granular form.
5. it is a kind of for directly preparing the composite catalyst of paraxylene by synthesis gas, it includes:
A) for catalyzing and synthesizing the catalyst A that gas is converted into methanol；With
B) for be catalyzed the catalyst B for forming dimethylbenzene, catalyst B is that such as any one of 1-3 hud typed is urged Agent,
Preferably, composite catalyst is in the form of mixtures of catalyst A and catalyst B, and catalyst A is physical or chemical The form or catalyst B of property encapsulated catalysts B be physical or form of chemically encapsulated catalysts A.
6. according to the 5th composite catalyst, wherein catalyst A include the first metal component and the second metal component or It is made of the first metal component and the second metal component, the first metal component is the member selected from Cr, Fe, Zr, In, Ga, Co, Cu Element, its oxide, its composite oxides or their any mixture, the second metal component be selected from Zn, Na, Al, Ag, Ce, K, the element of Mn, Pd, Ni, La, V, its oxide, its composite oxides or their any mixture；Preferably, the first gold medal Category group is divided into element, its oxide, its composite oxides or their any mixture selected from Cr, Co, Cu, Zr；And/or Second metal component is element, its oxide, its composite oxides or their any mixture selected from Zn, Al；It is especially excellent Selecting catalyst A is ZnO-Cr2O3。
7. according to the 5th or 6 composite catalyst, wherein the first metal component and the second metal component in catalyst A Molar ratio with elemental metal is 1000:1-1:100, preferably 100:1-1:50, more preferably 10:1-1:10, particularly preferably For 3:1-1:3.
8. wherein the weight ratio of catalyst A and catalyst B is 1:99- according to any one of 5-7 composite catalysts 99:1, preferably 20:80-80:20, more preferably 30:70-70:30, particularly preferred 50:50-75:25.
9. a kind of method prepared according to any one of 5-8 composite catalysts, comprising:
1) catalyst A powder and catalyst B powder are prepared respectively；With
2a) catalyst A powder and catalyst B powder and optional adhesive are mixed, are then shaped to compound Catalyst；
2b) catalyst A powder and catalyst B powder are separately formed, obtain catalyst A formed body and catalyst B molding Then body mixes these formed bodys；
It is 2c) hull shape into physical or chemically encapsulated forms by core, catalyst B of catalyst A；Or
It is 2d) hull shape into physical or chemically encapsulated forms by core, catalyst A of catalyst B.
10. wherein catalyst A is by being selected from sequence infusion process, co-impregnation, urea method and being total to according to the 9th method The preparation of any one or more of precipitation method；Preferably, in sequence infusion process, co-impregnation, urea method and/or co-precipitation In the roasting technique of legal system catalyst A, process conditions are as follows:
Calcination atmosphere is air；And/or
Maturing temperature is 200-700 DEG C, preferably 400-600 DEG C；And/or
Calcining time is 3-8h, preferably 4-6h.
11. according to any one of 1-3 nucleocapsid catalysts, the nucleocapsid catalyst, the root that are prepared according to the 4th method According to any one of 5-8 composite catalysts or the composite catalyzing prepared by the method according to any one of 9-10 Agent is directly being prepared the purposes in paraxylene as catalyst by synthesis gas.
12. wherein the molar ratio of the hydrogen in synthesis gas and carbon monoxide is 0.1-5, preferably according to the 11st purposes For 1-4；Reaction pressure is 1-10MPa, preferably 2-8MPa；Reaction temperature is 150-600 DEG C, preferably 250-500 DEG C；With/ Or, air speed is 200-8000h-1, preferably 500-5000h-1。
13. according to the 12nd purposes, wherein composite catalyst first to be restored to pre- place before being passed through synthesis gas reaction Reason is preferably as follows under the process conditions of reduction pretreatment:
Also Primordial Qi is pure hydrogen；
Pretreatment temperature is 300-700 DEG C, preferably 400-600 DEG C；
Pretreatment pressures are 0.1-1MPa, preferably 0.1-0.5MPa；
Pretreatment hydrogen volume air speed is 500-8000h-1, preferably 1000-4000h-1；And/or
The pretreatment recovery time is 2-10h, preferably 4-6h.
Detailed description of the invention
Fig. 1 is the SEM photograph of Zn/ZSM-5 and Zn/ZSM-5@S1 molecular sieve involved in embodiment 2, wherein figure a is Zn/ The SEM photograph of ZSM-5 molecular sieve, figure b are the SEM photographs of Zn/ZSM-5@S1 molecular sieve.
Fig. 2 is that figure is swept in the STEM figure of the Zn/ZSM-5@S1 molecular sieve prepared in embodiment 2 and the face corresponding element EDS.
Specific embodiment
According to the first aspect of the invention, a kind of core-shell catalyst is provided, center is H-type ZSM-5 molecular sieve, H in H-type ZSM-5 molecular sieve it is all or part of by it is one or more selected from Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, The modified zsm-5 zeolite or their any mixture of the element M replacement of Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn and B, Shell is selected from carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanometer Pipe, metal organic frame MOF, graphite, active carbon, metal oxide film (such as MgO, P2O5, CaO) one of or it is a variety of.
Core-shell catalyst of the invention has core/shell structure.Core is that H-type ZSM-5 molecular sieve (is expressed as sometimes below HZSM-5), H in H-type ZSM-5 molecular sieve it is all or part of by it is one or more selected from Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, The modified zsm-5 zeolite of the element M replacement of La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B is (sometimes below It is expressed as M/ZSM-5 molecular sieve) or their any mixture.These molecular sieves are referred to as ZSM-5 molecule in the present invention Sieve.ZSM-5 molecular sieve catalysed promoted can be converted to hydro carbons in the reaction that one-step method from syngas prepares hydrocarbon compound.This hair Bright people's discovery is being used for synthesis gas hydrocarbon before these catalytic active components compare after according to present invention covering without surface covering When, the selectivity of paraxylene in the selectivity of paraxylene, especially dimethylbenzene can be significantly improved, while keeping high CO Conversion ratio.Moreover, compared to the mixed catalyst for obtaining nuclear material and shell material physical mixed under equal conditions, it is of the invention Core-shell catalyst can also significantly improve the selectivity of paraxylene, the selectivity of paraxylene especially in dimethylbenzene, together When keep high CO conversion ratio.
As core component, H-type ZSM-5 molecular sieve and all both commercially available acquisitions of M/ZSM-5 molecular sieve can also pass through this field Conventional method be made, such as pass through hydrothermal synthesis method, infusion process, ion-exchange, vapour deposition process, liquid phase deposition etc. make It is standby.In general, HZSM-5 molecular sieve and Na/ZSM-5 can be prepared by hydrothermal synthesis method, then again by ion-exchange by HZSM-5 molecular sieve and Na/ZSM-5 prepare M/ZSM-5 molecular sieve.
By taking the hydrothermal synthesis method of HZSM-5 zeolite molecular sieve as an example.By silicon source (TEOS, ethyl orthosilicate), silicon source (Al (NO3)3·9H2O), organic formwork agent (TPAOH, tetrapropylammonium hydroxide), ethyl alcohol and deionized water in molar ratio (2TEOS: xAl2O3:0.68TPAOH:8EtOH:120H2O, x=0.002-0.2) resulting mixture is prepared, 4-6h is stirred at room temperature and obtains colloidal sol, Then the colloidal sol being stirred is transferred in polytetrafluoroethylene (PTFE) crystallizing kettle, is sealed thereafter, 160-200 DEG C at a temperature of with 2- The rotation speed crystallization 24-72h of 5rpm.It is cooled to room temperature after crystallization, resulting product is washed to filtrate pH=7-8, It is dried overnight, is subsequently placed in Muffle furnace and rises to 550-650 DEG C with 1 DEG C -3 DEG C/min heating rate, after roasting 4-8h, obtain ZSM-5 molecular sieve is HZSM-5.SiO in the ZSM-5 molecular sieve2/Al2O3For 10-1000.
In order to prepare M/ZSM-5 molecular sieve, when element M is metallic element, ion can be used by raw material of HZSM-5 Exchange process, infusion process, vapour deposition process and liquid phase deposition etc. prepare M/ZSM-5 molecular sieve；It, can when M is nonmetalloid B To prepare M/ZSM-5 molecular sieve using infusion process, vapour deposition process and liquid phase deposition etc. using HZSM-5 as raw material.
By taking ion-exchange process prepares Zn/ZSM-5 molecular sieve as an example.For example, the HZSM-5 molecular sieve of 1.5g is added to In the zinc nitrate aqueous solution of 1mol/L, it is stirred continuously 10-15h at 80-100 DEG C, carries out ion exchange.After ion exchange It is cooled to room temperature, products therefrom is washed to filtrate pH=7-8, is dried overnight, be subsequently placed in 500 DEG C of Muffle kiln roasting, roasting After burning 4-6h, Zn/ZSM-5 molecular sieve is obtained.
In a preferred embodiment of the invention, in the modified M/ZSM-5 molecular sieve of element M, element M accounts for M/ The 0.5-15 weight % of ZSM-5 molecular sieve total weight, preferably 1-10 weight %, particularly preferred 1-5 weight %.
In HZSM-5 molecular sieve of the invention or the M/ZSM-5 molecular sieve being modified by M, Si/Al molar ratio is usually 10-1000, preferably 20-800.The particle size of these molecular sieves is usually 0.01-20 μm, and preferably 0.1-15 μm.
The shell of core-shell catalyst of the present invention is selected from carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU Serial (pure silicon molecular sieve), silica, graphene, carbon nanotube, metal organic frame MOF (such as ZIF-8, ZIF-11), One of graphite, active carbon, metal oxide film (such as MgO, P2O5, CaO) are a variety of.These materials are coated on the appearance of core Face forms shell.These shell materials itself do not have activity at dimethyl benzene to hydrocarbon aromatizing, but by them to ZSM-5 points The cladding of son sieve core, affects the exposed acidic site of the outer surface ZSM-5, these exposed acidic sites can be covered or be disposed, So as to reduce side reaction, the final selectivity for improving target product paraxylene.As shell material, it is preferably selected from dioxy SiClx film, Silicalite-1, metal oxide film (such as MgO, P2O5, CaO), one of MCM-41, SBA-15, KIT-6 or It is a variety of, in particular Silicalite-1.
The dosage of shell does not select particularly, as long as can coat by core.In core-shell catalyst of the present invention An embodiment in, the weight ratio of core and shell is 100:1-1:100, preferably 10:1-1:10, more preferably 5:1-1:5, Particularly preferred 5:1-1:1.
According to the second aspect of the invention, a kind of method for preparing core-shell catalyst of the present invention is provided, comprising:
1) core of a granular form is provided, is H-type ZSM-5 molecular sieve, the H in H-type ZSM-5 molecular sieve is all or part of Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B are selected from by one or more Element M replacement modified zsm-5 zeolite or their any mixture；And
2) carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphite will be selected from Alkene, carbon nanotube, metal organic frame MOF, graphite, active carbon, metal oxide film (such as MgO, P2O5, CaO) one of or Multiple material is coated on core surface of a granular form.
The nuclear material and shell material of core-shell catalyst of the present invention are all conventional.In order to provide the core in step 1), when When nuclear material itself has been size suitable particle, then be used directly the nuclear material；When the size of nuclear material is larger, crush It is used for step 2) afterwards.The cladding to nuclear particle is realized in step 2).Different shell materials are to the cladding of nuclear particle, this is in this field In belong to common sense.As method for coating, it can be mentioned that hydrothermal synthesis method, vapour deposition process, infusion process, sputtering method,Method Deng, this can according to the property of covering material carry out conventional selection.For example, the cladding of molecular sieve shell material, can be used hydro-thermal Vapour deposition process can be used in synthetic method, the cladding of carbon film, graphene and carbon nanotube, and dipping can be used in the cladding of metal oxide The cladding of method and sputtering method, silica can be usedMethod.
Zn/ZSM-5 is coated by hydrothermal synthesis method with Silicalite-1 and obtains Zn/ZSM-5@Silicalite-1 nucleocapsid For type catalyst.By silicon source (TEOS), organic formwork agent (TPAOH), ethyl alcohol and deionized water (1.00SiO in molar ratio2: 0.06TPAOH:16.0EtOH:240H2O resulting mixture) is prepared, 4-6h is stirred at room temperature, before obtaining Silicalite-1 molecular sieve Liquid solution.With gained Silicalite-1 molecular sieve precursor solution one after the Zn/ZSM-5 zeolite molecular sieve of above-mentioned preparation is crushed Rise be transferred in polytetrafluoroethylene (PTFE) crystallizing kettle, then seal, 180 DEG C at a temperature of with the rotation speed crystallization 24- of 2-5rmp 72h.It is cooled to room temperature after crystallization, products therefrom is washed with deionized to filtrate pH=7-8, is dried overnight, then It is placed in Muffle furnace and rises to 550-650 DEG C with 1 ° -3 °/min heating rate, after roasting 4-8h, obtain Zn/ZSM-5@ Silicalite-1 core-shell catalyst, wherein Zn/ZSM-5 is core, and Silicalite-1 is shell.
One-step method from syngas preparation aromatic hydrocarbon can be greatly classified into two stages, and a stage is that synthesis gas is converted to methanol Stage, another stage is that methanol further reacts the stage for finally obtaining aromatic hydrocarbons such as paraxylene.Nucleocapsid of the invention The selectivity that type catalyst improves paraxylene for second stage is highly effective, can not only significantly improve paraxylene Selectivity, the selectivity of paraxylene especially in dimethylbenzene, while also keeping high CO conversion ratio.
Therefore, according to the third aspect of the invention we, provide a kind of for directly preparing answering for paraxylene by synthesis gas Catalyst is closed, it includes:
A) for catalyzing and synthesizing the catalyst A that gas is converted into methanol；With
B) for being catalyzed the catalyst B for forming dimethylbenzene, catalyst B is core-shell catalyst of the invention.
As catalyst A, it can be any catalyst that synthesis gas can be promoted to be converted into methanol.Of the invention one In a preferred embodiment, catalyst A includes the first metal component and the second metal component or catalyst A by the first metal Component and the second metal component composition, wherein the first metal component is element, its oxygen selected from Cr, Fe, Zr, In, Ga, Co, Cu Compound, its composite oxides or their any mixture, the second metal component be selected from Zn, Na, Al, Ag, Ce, K, Mn, The element of Pd, Ni, La, V, its oxide, its composite oxides or their any mixture.Preferably, the first metal group It is divided into element, its oxide, its composite oxides or their any mixture selected from Cr, Fe, Co, Zr, Cu；And/or the Two metal components are element, its oxide, its composite oxides or their any mixture selected from Zn, Al.Particularly preferably , catalyst A is ZnO-Cr2O3。
The commercially available acquisition of catalyst A, or prepared by any conventional method, such as sequence infusion process, co-impregnation, urine Plain method and coprecipitation, preferably coprecipitation.For the catalyst A comprising the first metal component and the second metal component, when this When catalyst is prepared by preceding method, it finally can all be related to mixing the precursor comprising the first metal component and the second metal component Object is closed to be roasted.Advantageously, calcination atmosphere is air；And/or maturing temperature is 200-700 DEG C, preferably 400-600 DEG C； And/or calcining time 3-8h, preferably 4-6h.
Using coprecipitation preparation as the ZnO-Cr of catalyst A2O3For.In order to prepare the catalyst, usually by chromium, zinc Respective nitrate precursors are made into the mixed nitrate that concentration is 1mol/L in chromium needed for catalyst A/zinc ratio with deionized water Saline solution；(other precipitating reagents, such as sodium carbonate, hydroxide is can also be used into the ammonium carbonate solution of this solution and 1mol/L Sodium, ammonium hydroxide) it is added drop-wise in beaker and is co-precipitated simultaneously, it is stirred continuously in coprecipitation process, precipitation temperature 50-90 DEG C, pH value controls between 6-8, this is controlled by two kinds of solution with respect to adding speed；After charging, continue stirring gained Sediment and kept at 50-90 DEG C 60-240 minutes to carry out aging；Filtering aging after sediment and be washed with deionized water It washs；Product after washing is put into baking oven at 80-120 DEG C dry 8-12h；It places into Muffle furnace at 350-550 DEG C 3-6h is calcined to get ZnO-Cr2O3Catalyst.
The first metal component and second in a preferred embodiment of composite catalyst of the present invention, in catalyst A Metal component is 1000:1-1:100 with the molar ratio of elemental metal, preferably 100:1-1:50, more preferably 10:1-1:10, Particularly preferably 3:1-1:3.
In another embodiment, the weight ratio of catalyst A and catalyst B is 1:99-99:1, preferably 20:80-80: 20, more preferably 30:70-70:30, particularly preferred 50:50-75:25.
For the purpose of the present invention, composite catalyst can be in the form of mixtures of catalyst A and catalyst B, catalyst A physics Property or the chemically form of encapsulated catalysts B or catalyst B is physical or form of chemically encapsulated catalysts A.
According to the fourth aspect of the present invention, a kind of method for preparing composite catalyst of the present invention is provided, comprising:
1) catalyst A powder and catalyst B powder are prepared respectively；With
2a) catalyst A powder and catalyst B powder and optional adhesive are mixed, are then shaped to compound Catalyst；
2b) catalyst A powder and catalyst B powder are separately formed, obtain catalyst A formed body and catalyst B molding Then body mixes these formed bodys；
It is 2c) hull shape into physical or chemically encapsulated forms by core, catalyst B of catalyst A；Or
It is 2d) hull shape into physical or chemically encapsulated forms by core, catalyst A of catalyst B.
It in the present invention, is conventional by catalyst A and catalyst the B technology being combined with each other.Catalyst A and catalyst B is usually made with powder.Then, in scheme 2a), catalyst A powder is mixed with catalyst B powder and optional adhesive Together, then it is shaped to composite catalyst.As adhesive, it can be mentioned that water, aluminium oxide, silica etc..By catalyst A powder End mixed with catalyst B powder and optional adhesive, gained mixture of powders can be shaped to tablet, pellet, The forms such as graininess.It is hull shape into physical or chemically encapsulated forms by core, catalyst B of catalyst A in scheme 2c), It is hull shape into physical or chemically encapsulated forms by core, catalyst A of catalyst B in scheme 2d).Variance in form form Method be conventional.
For example, 1. prepare the A B catalyst of catalyst B encapsulated catalysts A using physics coating method: first by adhesive liquid Body is immersed in the surface pellet type catalyst A with certain size, then removes extra binder, then by surface wettability The catalyst A of state is put into the round-bottomed flask for filling powder catalyst B, and the rotation round-bottomed flask of fast powerful guarantees to urge The surface agent A is all coated by catalyst B.This process is 2-3 times repeatable.Finally catalyst is dried overnight, in Muffle furnace 3-6h being calcined at 350-550 DEG C, A@B catalyst being made, wherein catalyst A is core, and catalyst B is shell.When catalyst to be prepared When the B@A catalyst of A physics encapsulated catalysts B, by the above method catalyst A and catalyst B exchange.
For example, 2. prepare the A@B catalyst of catalyst B encapsulated catalysts A using chemical method: will have certain size first Pellet type catalyst A hydrothermal synthesis is carried out together with ZSM-5 Synthesis liquid, concrete operation step can refer to ZSM-5 molecule above The preparation method of sieve.The A@ZSM-5 catalyst collected after hydro-thermal.Then by A@ZSM-5 catalyst with Silicalite-1 molecular sieve carries out hydrothermal synthesis together.Catalyst is rinsed with deionized water to pH=after last hydro-thermal 7, it is dried overnight, in 500-600 DEG C in Muffle furnace, after roasting 4-6h, obtains A@B catalyst, wherein catalyst A is core, is urged Agent B is shell.When the B@A catalyst of catalyst A chemistry encapsulated catalysts B to be prepared, the method for hydrothermal synthesis is used first Catalyst B is prepared, concrete operation step can refer to the preparation method of Zn/HZSM5@S1 molecular sieve above, then will be granular Catalyst B carries out hydrothermal synthesis together with the precursor solution of catalyst A, 220 DEG C at a temperature of with the rotation speed of 2-5rmp Crystallization 24-72h.It is cooled to room temperature after crystallization, products therefrom is washed with deionized to filtrate pH=7-8, it is dried Night is subsequently placed in Muffle furnace and rises to 550-650 DEG C with 1 ° -3 °/min heating rate, after roasting 4-8h, obtains B@A catalyst, Wherein catalyst B is core, and catalyst A is shell.
The last one aspect according to the present invention provides nucleocapsid catalyst of the present invention, prepared according to the methods of the invention Nucleocapsid catalyst, composite catalyst of the present invention or the composite catalyst prepared by the method for the invention are directly being made by synthesis gas Purposes in standby paraxylene as catalyst.Due to having used these catalyst of the invention, not only paraxylene is selected The high conversion rate of selecting property height and synthesis gas, and selectivity of the paraxylene in dimethylbenzene is also high, while keeping synthesis gas High conversion.
In composite catalyst of the invention for before catalyzing and synthesizing gas paraxylene, it is advantageous to by composite catalyzing Agent elder generation reduction pretreatment.Advantageously, the process conditions of reduction pretreatment are as follows: also Primordial Qi is pure hydrogen；Pretreatment temperature is 300-700 DEG C, preferably 400-600 DEG C；Pretreatment pressures are 0.1-1MPa, preferably 0.1-0.5MPa；Pre-process hydrogen Product air speed is 500-8000h-1, preferably 1000-4000h-1；And/or the pretreatment recovery time is 2-10h, preferably 4-6h. After reduction pretreatment, it is passed through synthesis gas and is reacted to convert obtained paraxylene.The hydrogen in synthesis gas used thus Molar ratio with carbon monoxide is 0.1-5, preferably 1-4.Reaction pressure is 1-10MPa, preferably 2-8MPa.Reaction temperature is 150-600 DEG C, preferably 250-500 DEG C.Air speed is 200-8000h-1, preferably 500-5000h-1。
The conversion of synthesis gas is carried out using composite catalyst of the invention, synthesis gas conversion ratio can achieve 55% or more, Selectivity of the paraxylene in xylene isomer can reach 70% or more, and the selectivity of paraxylene is brighter than under equal conditions It is aobvious to improve.Paraxylene can be converted by one step of synthesis gas using composite catalyst of the invention, need not move through comprising it is a variety of not The multistage reactor that same type catalyst is used in mixed way, reaction process is more simple, easily operated.In catalyst of the present invention The synthesis gas conversion process of upper progress, can obtain higher Selectivity for paraxylene, while keep higher CO conversion ratio.
Embodiment
Comparative example 1
The preparation of a.Cr/Zn catalyst
By the Cr (NO of 23.6g3)3·9H2Zn (the NO of O and 9.0g3)2·6H2O is dissolved in 100ml deionized water.By gained Mixed nitrate saline solution and 1mol/L (NH4)2CO3Aqueous solution is (by (NH of 9.6g4)2CO3It is dissolved in 100ml deionized water In be made) be added drop-wise in the beaker for filling a small amount of deionized water and be co-precipitated simultaneously.It is stirred continuously in coprecipitation process, 70 Constant temperature at DEG C, pH value are maintained at 7 or so, this is controlled by the relative velocity of two kinds of solution.It is quiet at 70 DEG C after co-precipitation Set aging 3h.Sediment is filtered, is then washed with deionized.By clean sediment in an oven in 120 DEG C of baking 12h, 5h is calcined at 400 DEG C in Muffle furnace again.Methanol synthesis catalyst is obtained, Cr/Zn catalyst is denoted as, wherein based on the element Chromium/zinc molar ratio is 2:1.
The preparation of b.HZSM-5 molecular sieve
By silicon source (TEOS), silicon source (Al (NO3)3·9H2O), organic formwork agent (TPAOH), ethyl alcohol and deionized water massage You are than (2TEOS:0.02Al2O3:0.68TPAOH:8EtOH:120H2O resulting mixture) is prepared, 6h is stirred at room temperature, obtains colloidal sol. Then the colloidal sol being stirred is transferred in polytetrafluoroethylene (PTFE) crystallizing kettle, is sealed thereafter, 180 DEG C at a temperature of with 2rmp speed Rotate crystallization for 24 hours.It is cooled to room temperature after crystallization, products therefrom is washed with deionized to filtrate pH=7, it is dried Night is subsequently placed in Muffle furnace and rises to 550 DEG C with 1 DEG C/min heating rate, obtains ZSM-5 molecular sieve after roasting 6h, is HZSM- 5.Si/Al molar ratio is 46 in the HZSM-5 molecular sieve.
C. the preparation of bifunctional catalyst
By the Cr/Zn catalyst of preparation and HZSM-5 molecular sieve powder physical mixed, 10min, then compression molding are ground, i.e., The bifunctional catalyst of mechanical mixing preparation is obtained, Cr/Zn-HZSM-5 is denoted as, wherein Cr/Zn catalyst and HZSM-5 molecule The mass ratio of sieve is 2:1.
D. Catalysis experiments
0.5g Cr/Zn-HZSM-5 catalyst is filled in fixed bed high-pressure reactor with fixed bed form, it is continuous logical Enter H2The synthesis gas that volume ratio with CO is 2.1, control reaction pressure are 5MPa, and synthesis gas air speed is 1200h-1, reaction temperature It is 400 DEG C.To reaction product and unstripped gas gas-chromatography on-line analysis after reaction 4h, reactivity worth is shown in Table 1.
Comparative example 2
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " in comparative example 1 is repeated, Cr/Zn catalyst is obtained.
The preparation of b.Zn/ZSM-5 molecular sieve
" preparation of HZSM-5 molecular sieve " in comparative example 1 is repeated, HZSM-5 molecular sieve is obtained.Then, by 1.5g's HZSM-5 molecular sieve is added in the zinc nitrate aqueous solution of 1mol/L, and 15h is stirred continuously at 80 DEG C, carries out ion exchange.From It is cooled to room temperature after son exchange, resulting product is washed to filtrate pH=7-8, is dried overnight, 500 DEG C of horses are subsequently placed in Not kiln roasting obtains Zn/ZSM-5 molecular sieve after roasting 4h.Based on the total weight of Zn/ZSM-5 molecular sieve, the content of Zn is 1 Weight %.
C. the preparation of bifunctional catalyst
" preparation of bifunctional catalyst " in comparative example 1 is repeated, but HZSM-5 molecular sieve is replaced with into Zn/ZSM-5 Molecular sieve is denoted as Cr/Zn-Zn/ZSM-5 catalyst, wherein Cr/Zn to get to the bifunctional catalyst of mechanical mixing preparation The mass ratio of catalyst and Zn/ZSM-5 molecular sieve is 2:1.
D. Catalysis experiments
" Catalysis experiments " in comparative example 1 are repeated, but Cr/Zn-Zn/ZSM-5 catalyst is used to replace Cr/Zn-HZSM- 5 catalyst.Reaction result is shown in Table 1.
Embodiment 1
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " in comparative example 1 is repeated, Cr/Zn catalyst is obtained.
The preparation of b.HZSM-5@S1 catalyst
" preparation of HZSM-5 molecular sieve " in comparative example 1 is repeated, HZSM-5 molecular sieve is obtained.
By silicon source (TEOS), organic formwork agent (TPAOH), ethyl alcohol and deionized water (1.0SiO in molar ratio2: 0.06TPAOH:16.0EtOH:240H2O resulting mixture) is prepared, 4h is stirred at room temperature, obtains Silicalite-1 molecular sieve precursor Solution.It is transferred to together after the HZSM-5 molecular sieve of above-mentioned preparation is crushed with gained Silicalite-1 molecular sieve precursor solution In polytetrafluoroethylene (PTFE) crystallizing kettle, seal thereafter, 180 DEG C at a temperature of with 2rmp rotation speed crystallization for 24 hours.It is cold after crystallization But to room temperature, products therefrom is washed with deionized to filtrate pH=7, is dried overnight, be subsequently placed in Muffle furnace with 1 DEG C/ Min heating rate rises to 550 DEG C, after roasting 4h, obtains HZSM-5@Silicalite-1 molecular sieve, is denoted as HZSM-5@S1 catalysis Agent, wherein HZSM-5 molecular sieve is core, and Silicalite-1 molecular sieve is shell, HZSM-5 molecular sieve and Silicalite-1 molecule The weight ratio of sieve is 3:1.
C. the preparation of bifunctional catalyst
" preparation of bifunctional catalyst " in comparative example 1 is repeated, but HZSM-5@S1 catalyst is used to replace HZSM-5 Molecular sieve is denoted as Cr/Zn-HZSM-5@S1 catalyst, wherein Cr/Zn to get to the bifunctional catalyst of mechanical mixing preparation The mass ratio of catalyst and HZSM-5@S1 catalyst is 2:1.
D. Catalysis experiments
" Catalysis experiments " in comparative example 1 are repeated, but Cr/Zn-HZSM-5@S1 catalyst is used to replace Cr/Zn- HZSM-5 catalyst.Reaction result is shown in Table 1.
Embodiment 2
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " in comparative example 1 is repeated, Cr/Zn catalyst is obtained.
The preparation of b.Zn/ZSM-5@S1 molecular sieve
" preparation of Zn/ZSM-5 molecular sieve " in comparative example 2 is repeated, Zn/ZSM-5 molecular sieve is obtained.Then by silicon source (TEOS), organic formwork agent (TPAOH), ethyl alcohol and deionized water (1.0SiO in molar ratio2:0.06TPAOH:16.0EtOH: 240H2O resulting mixture) is prepared, 4h is stirred at room temperature, obtains Silicalite-1 molecular sieve precursor solution.By the Zn/ of above-mentioned preparation It is transferred to polytetrafluoroethylene (PTFE) crystallizing kettle together with gained Silicalite-1 molecular sieve precursor solution after ZSM-5 molecular sieve crushing In, seal thereafter, 180 DEG C at a temperature of with 2rmp speed rotation crystallization for 24 hours.It is cooled to room temperature after crystallization, by gained Product is washed with deionized to filtrate pH=7, is dried overnight, and is subsequently placed in Muffle furnace and is risen to 1 DEG C/min heating rate 550 DEG C, after roasting 4h, Zn/ZSM-5@Silicalite-1 molecular sieve is obtained, is denoted as Zn/ZSM-5@S1 catalyst, wherein Zn/ ZSM-5 molecular sieve is core, and Silicalite-1 molecular sieve is shell, the weight of Zn/ZSM-5 molecular sieve and Silicalite-1 molecular sieve Amount is than being 3:1.
Fig. 1 is the SEM photograph of Zn/ZSM-5 and Zn/ZSM-5@S1 involved in the embodiment, wherein figure a is Zn/ZSM-5 SEM photograph, figure b be Zn/ZSM-5@S1 SEM photograph.As seen from Figure 1, before Silicalite-1 molecular sieve cladding, The size of Zn/ZSM-5 molecular sieve is 0.5-1 μm, after Silicalite-1 molecular sieve coats Zn/ZSM-5, gained The size of Zn/ZSM-5@S1 molecular sieve becomes 1.5-2 μm.It therefore deduces that, Silicalite-1 molecular sieve is raw in situ It grows on Zn/ZSM-5 molecular sieve core, forms shell.
In order to further intuitively show that Zn/ZSM-5@S1 molecular sieve is coreshell type structure, STEM and EDS is used thus It sweeps figure and is proved in face.
Fig. 2 is that figure is swept in the STEM figure of the Zn/ZSM-5@S1 molecular sieve prepared in embodiment 2 and the face corresponding element EDS, In the middle: the STEM figure that a figure is Zn/ZSM-5@S1, b figure is the figure of Si element；C figure is the figure of Al element；D is the figure of O element；e For the figure of Zn element；F is the combination chart of each element.From Figure 2 it can be seen that Zn is largely supported on above ZSM-5 molecular sieve, therefore It is the core-shell type molecular sieve of shell that Zn/ZSM-5@S1 molecular sieve, which is by core, Silicalite-1 of Zn/ZSM-5,.
To sum up, in Zn/ZSM-5@S1 molecular sieve, Zn/ZSM-5 is core, and Silicalite-1 molecular sieve is cladding core Shell.
C. the preparation of bifunctional catalyst
" preparation of bifunctional catalyst " in comparative example 1 is repeated, but Zn/ZSM-5@S1 catalyst is used to replace HZSM-5 molecular sieve is denoted as Cr/Zn-Zn/ZSM-5@S1, wherein Cr/ to get to the bifunctional catalyst of mechanical mixing preparation The mass ratio of Zn catalyst and Zn/ZSM-5@S1 catalyst is 2:1.
D. Catalysis experiments
" Catalysis experiments " in comparative example 1 are repeated, but are urged using Cr/Zn-Zn/ZSM-5@S1 instead of Cr/Zn-HZSM-5 Agent.Reaction result is shown in Table 1.
Comparative example 3
" Catalysis experiments " of comparative example 1 are repeated, but catalyst is only with Cr/Zn catalyst therein, not used point Son sieve.Reaction result is shown in Table 1.
Comparative example 4
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " in comparative example 1 is repeated, Cr/Zn catalyst is obtained.
B. the preparation of beta-molecular sieve
By silicon source (SiO2), silicon source (aluminium isopropoxide), organic formwork agent (TEAOH), NaOH and deionized water in molar ratio (1SiO2:0.023Al2O3:0.0425TEAOH:0.049NaOH:6.8H2O resulting mixture) is prepared, 6h is stirred at room temperature, obtains molten Glue.Then the colloidal sol being stirred is transferred in polytetrafluoroethylene (PTFE) crystallizing kettle, is sealed thereafter, 150 DEG C at a temperature of with 2rmp Speed rotates crystallization time 72h.It is cooled to room temperature after crystallization, products therefrom is washed with deionized to filtrate pH=7, It is dried overnight, is subsequently placed in Muffle furnace and rises to 550 DEG C with 1 DEG C/min heating rate, obtain beta-molecular sieve after roasting 6h.The β Si/Al molar ratio is 20 in molecular sieve.
C. the preparation of bifunctional catalyst
" preparation of bifunctional catalyst " in comparative example 1 is repeated, but HZSM-5 molecular sieve is replaced with into beta-molecular sieve, The bifunctional catalyst for obtaining mechanical mixing preparation, is denoted as Cr/Zn- beta catalyst, wherein Cr/Zn catalyst and beta-molecular sieve Mass ratio be 2:1.
D. Catalysis experiments
" Catalysis experiments " in comparative example 1 are repeated, but Cr/Zn- beta catalyst is used to be catalyzed instead of Cr/Zn-HZSM-5 Agent.Reaction result is shown in Table 1.
Comparative example 5
The preparation of b.HZSM-5&S1 physical mixed catalyst
Repeat " preparation of HZSM-5@S1 catalyst " in embodiment 1, but by HZSM-5 molecular sieve and Silicalite-1 molecular sieve physical mixed is denoted as HZSM-5&S1 catalyst, wherein HZSM-5 to get bifunctional catalyst is arrived The weight ratio of molecular sieve and Silicalite-1 molecular sieve is 3:1.
C. the preparation of bifunctional catalyst
" preparation of bifunctional catalyst " in comparative example 1 is repeated, but HZSM-5&S1 catalyst is used to replace HZSM-5 Molecular sieve is denoted as Cr/Zn-HZSM-5&S1 physical mixed catalyst to get to the bifunctional catalyst of mechanical mixing preparation, Wherein the mass ratio of Cr/Zn catalyst and HZSM-5&S1 catalyst is 2:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 1 are repeated, but use Cr/Zn-HZSM-5&S1 catalyst for Cr/Zn-HZSM-5 Catalyst.Reaction result is shown in Table 1.
Comparative example 6
The preparation of " preparation of Cr/Zn catalyst " and " Zn/ZSM-5@S1 molecular sieve " in embodiment 2 is repeated, respectively To Cr/Zn catalyst and Zn/ZSM-5@S1 catalyst.
" Catalysis experiments " in embodiment 2 are repeated, but Cr/Zn catalyst and Zn/ZSM-5@S1 catalyst are not mixed Together, but by both catalyst it is respectively separately fixed on fixed bed form in two sections of fixed bed high-pressure reactor, Centre is separated with silica wool, wherein along gas streams direction, preceding, Zn/ZSM-5@S1 catalyst section exists Cr/Zn catalyst section Afterwards.Reaction result is shown in Table 1.
Embodiment 3
The preparation of a.Fe/Zn/Cu catalyst
By the Fe (NO of 9.0g3)3·9H2O, the Zn (NO of 3.8g3)2·6H2Cu (the NO of O and 1.3g3)2·3H2O is dissolved in The mixed aqueous solution of iron content zinc-copper is obtained in 200mL deionized water.Take the Na of 10.0g2CO3It is dissolved in 100mL deionized water and obtaining Aqueous sodium carbonate.Both solution are added dropwise simultaneously and are co-precipitated in the beaker for filling a small amount of deionized water.Co-precipitation It is stirred continuously in the process, and maintains the temperature at 85 DEG C, pH=8-8.5, this is controlled by the relative velocity of two kinds of solution.Precipitating knot Aging 2h is stood after beam at 85 DEG C.Sediment is filtered, is then washed with deionized.In an oven by clean sediment It is roasted 5 hours at 320 DEG C in 120 DEG C of baking 12h, then in Muffle furnace, obtains methanol synthesis catalyst, be denoted as Fe/Zn/Cu and urge Agent.The molar ratio of metal based on the element in the catalyst are as follows: Fe/Zn/Cu=55: 32: 13.
The preparation of b.Zn/ZSM-5@S1 molecular sieve
" preparation of Zn/ZSM-5@S1 molecular sieve " in embodiment 2 is repeated, Zn/ZSM-5@S1 molecular sieve is obtained.
C. the preparation of bifunctional catalyst
By the Fe/Zn/Cu catalyst of preparation and Zn/ZSM-5@S1 molecular sieve powder physical mixed, 10min is ground, then is pressed Sheetmolding is denoted as Fe/Zn/Cu-Zn/ZSM-5@S1, wherein Fe/Zn/ to get to the bifunctional catalyst of mechanical mixing preparation The mass ratio of Cu catalyst and Zn/ZSM-5@S1 molecular sieve is 2:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 2 are repeated, but use Fe/Zn/Cu-Zn/ZSM-5@S1 catalyst for Cr/Zn- Zn/ZSM-5@S1 catalyst.Reaction result is shown in Table 1.
Embodiment 4
The preparation of a.Zr/Zn catalyst
With the ZrO of the zinc nitrate aqueous solution dipping 2.0g of 1mol/L2, then it is dried overnight at a temperature of 120 DEG C, then sets In 400 DEG C of Muffle kiln roastings, ZrO is obtained after roasting 3h2ZnO catalyst is denoted as Zr/Zn catalyst, wherein based on the element Zirconium/zinc molar ratio is 13.5:1.
The preparation of b.Zn/ZSM-5@S1 molecular sieve
" preparation of Zn/ZSM-5@S1 molecular sieve " in embodiment 2 is repeated, Zn/ZSM-5@S1 molecular sieve is obtained.
C. the preparation of bifunctional catalyst
By the Zr/Zn catalyst of preparation and Zn/ZSM-5@S1 molecular sieve powder physical mixed, grind 10min, then tabletting at Type to get to mechanical mixing preparation bifunctional catalyst, be denoted as Zr/Zn-Zn/ZSM-5@S1, wherein Zr/Zn catalyst with The mass ratio of Zn/ZSM-5@S1 molecular sieve is 2:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 2 are repeated, but use Zr/Zn-Zn/ZSM-5@S1 catalyst for Cr/Zn-Zn/ ZSM-5@S1 catalyst.Reaction result is shown in Table 1.
Embodiment 5
The preparation of a.Cr/Zn/Al catalyst
By the Cr (NO of 23.6g3)3·9H2Zn (the NO of O, 9.0g3)2·6H2Al (the NO of O and 5.4g3)3·9H2O is dissolved in 100ml deionized water.Subsequent coprecipitation method is identical as " preparation of Cr/Zn catalyst " in comparative example 1, obtains Cr/Zn/Al Catalyst, wherein the Cr/Zn/Al molar ratio remembered with element are as follows: 4:2:1.
The preparation of b.Zn/ZSM-5@S1 molecular sieve
" preparation of Zn/ZSM-5@S1 molecular sieve " in embodiment 2 is repeated, Zn/ZSM-5@S1 molecular sieve is obtained.
C. the preparation of bifunctional catalyst
By the Cr/Zn/Al catalyst of preparation and Zn/ZSM-5@S1 molecular sieve powder physical mixed, 10min is ground, then is pressed Sheetmolding is denoted as Cr/Zn/Al-Zn/ZSM-5@S1, wherein Cr/Zn/ to get to the bifunctional catalyst of mechanical mixing preparation The mass ratio of Al catalyst and Zn/ZSM-5@S1 molecular sieve is 3:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 2 are repeated, but use Cr/Zn/Al-Zn/ZSM-5@S1 catalyst for Cr/Zn- Zn/ZSM-5@S1 catalyst.Reaction result is shown in Table 1.
Embodiment 6
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " in comparative example 1 is repeated, Cr/Zn catalyst is obtained.
The preparation of b.Ag/ZSM-5@S1 molecular sieve
" preparation of HZSM-5 molecular sieve " in comparative example 1 is repeated, HZSM-5 molecular sieve is obtained.Then, by 1.5g's HZSM-5 molecular sieve is added in the silver nitrate aqueous solution of 1mol/L, and 15h is stirred continuously at 80 DEG C, carries out ion exchange.From It is cooled to room temperature after son exchange, resulting product is washed to filtrate pH=7-8, is dried overnight, 500 DEG C of horses are subsequently placed in Not kiln roasting obtains Ag/ZSM-5 molecular sieve after roasting 4h.Based on the total weight of Ag/ZSM-5 molecular sieve, the content of Ag is Weight 1%.
" preparation of HZSM-5@S1 catalyst " in embodiment 1 is repeated, but Ag/ZSM-5 is used to replace HZSM-5 molecule Sieve.Ag/ZSM-5@Silicalite-1 molecular sieve is obtained, Ag/ZSM-5@S1 catalyst is denoted as, wherein Ag/ZSM-5 molecular sieve is Core, Silicalite-1 molecular sieve are shell, and the weight ratio of Ag/ZSM-5 molecular sieve and Silicalite-1 molecular sieve is 3:1.
C. the preparation of bifunctional catalyst
By the Cr/Zn catalyst of preparation and Ag/ZSM-5@S1 molecular sieve powder physical mixed, grind 10min, then tabletting at Type to get to mechanical mixing preparation bifunctional catalyst, be denoted as Cr/Zn-Ag/ZSM-5@S1, wherein Cr/Zn catalyst with The mass ratio of Ag/ZSM-5@S1 molecular sieve is 1:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 2 are repeated, but use Cr/Zn-Ag/ZSM-5@S1 catalyst for Cr/Zn-Zn/ ZSM-5@S1 catalyst.Reaction result is shown in Table 1.
Embodiment 7
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " repeated in comparative example 1 is identical, obtains Cr/Zn catalyst.
The preparation of b.HZSM-5@MgO catalyst
" preparation of HZSM-5 molecular sieve " in comparative example 1 is repeated, HZSM-5 molecular sieve is obtained.With the magnesium nitrate of 1mol/L Aqueous solution impregnates the HZSM-5 molecular sieve of 2.0g, is then dried overnight, is subsequently placed in 500 DEG C of Muffle furnaces at a temperature of 120 DEG C Roasting obtains HZSM-5@MgO molecular sieve after roasting 4h, is denoted as HZSM-5@MgO, and wherein HZSM-5 molecular sieve is core, and MgO is Shell.Based on the total weight of HZSM-5 MgO molecular sieve, the content of MgO is weight 1%.
C. the preparation of bifunctional catalyst
By the Cr/Zn catalyst of preparation and HZSM-5@MgO catalyst powder physical mixed, grind 10min, then tabletting at Type to get to mechanical mixing preparation bifunctional catalyst, be denoted as Cr/Zn-HZSM-5@MgO, wherein Cr/Zn catalyst with The mass ratio of HZSM-5@MgO catalyst is 2:1.
D. Catalysis experiments
0.5g Cr/Zn-HZSM-5@MgO catalyst is filled in fixed bed high-pressure reactor with fixed bed form, even It is continuous to be passed through H2The synthesis gas that volume ratio with CO is 2.1, control reaction pressure are 3MPa, and synthesis gas air speed is 1200h-1, reaction Temperature is 400 DEG C.To reaction product and unstripped gas gas-chromatography on-line analysis after reaction 4h, reactivity worth is shown in Table 1.
Embodiment 8
The preparation of a.Cr/Zn catalyst
" preparation of Cr/Zn catalyst " repeated in comparative example 1 is identical, obtains Cr/Zn catalyst.
b.HZSM-5@SiO2The preparation of molecular sieve
" preparation of HZSM-5 molecular sieve " in comparative example 1 is repeated, HZSM-5 molecular sieve is obtained.UsingMethod system Standby SiO2The ethyl alcohol of the HZSM-5 molecular sieve of 1.0g, the TEOS and 15ml of 5-10 μ L is put in the beaker of 20ml by film, is then dripped The 25 weight % ammonia spirits for adding 2.3ml, then stir 2h.After reaction, by resulting product ethanol washing until filter Liquid pH=7, is dried overnight, and is subsequently placed in 500 DEG C of Muffle kiln roastings, obtains HZSM-5 SiO after roasting 4h2Catalyst is denoted as HZSM-5@SiO2.In order to make SiO2Film is evenly coated, this system can carry out 2-3 times.Finally, it is based on HZSM-5@SiO2Molecule The total weight of sieve, SiO2Content be 1 weight %.
C. the preparation of bifunctional catalyst
By the Cr/Zn catalyst of preparation and HZSM-5@SiO2Catalyst fines physical mixed, grind 10min, then tabletting at Type is denoted as Cr/Zn-HZSM-5@SiO to get to the bifunctional catalyst of mechanical mixing preparation2, wherein Cr/Zn catalyst with HZSM-5@SiO2The mass ratio of catalyst is 2:1.
D. Catalysis experiments
" Catalysis experiments " in embodiment 2 are repeated, but use Cr/Zn-HZSM-5@SiO2Catalyst is for Cr/Zn-Zn/ ZSM-5@S1 catalyst.Reaction result is shown in Table 1.
Comparative example 7
" Catalysis experiments " of embodiment 3 are repeated, but catalyst is not used only with Fe/Zn/Cu catalyst therein Molecular sieve.Reaction result is shown in Table 1.
Comparative example 8
" Catalysis experiments " of embodiment 4 are repeated, but catalyst is only with Zr/Zn catalyst therein, not used point Son sieve.Reaction result is shown in Table 1.
Table 1
Note:
MeOH: methanol
DME: dimethyl ether
C2-C5: C2-C5Hydrocarbon
Remaining: remaining all product
MX: meta-xylene
OX: ortho-xylene
PX: paraxylene
PX/X: selectivity of the paraxylene in dimethylbenzene.

Claims (13)

1. a kind of core-shell catalyst, center are H-type ZSM-5 molecular sieve, the H all or part quilt in H-type ZSM-5 molecular sieve One or more members selected from Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn and B The modified zsm-5 zeolite or their any mixture of plain M replacement, shell are selected from carbon film, Silicalite-1, MCM- 41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotube, metal organic frame MOF, graphite, active carbon, Metal oxide film (such as MgO, P2O5, CaO) one of or it is a variety of.
2. core-shell catalyst according to claim 1, center are H-type ZSM-5 molecular sieve, the H in H-type ZSM-5 molecular sieve Partly or entirely by the Zn modified zsm-5 zeolite replaced or their any mixture；And/or shell is selected from silica Film, Silicalite-1, metal oxide film (such as MgO, P2O5, CaO), one of MCM-41, SBA-15, KIT-6 or more Kind, preferably Silicalite-1；It is particularly preferred that element M accounts for M-ZSM- in the modified M-ZSM-5 molecular sieve of element M The 0.5-15 weight % of 5 molecular sieve total weights, preferably 1-10 weight %, particularly preferred 1-5 weight %.
3. the weight ratio of core-shell catalyst according to claim 1 or 2, center and shell is 100:1-1:100, preferably 10:1-1:10, more preferably 5:1-1:5, particularly preferred 5:1-1:1.
4. a kind of method for preparing core-shell catalyst as claimed in one of claims 1-3, comprising:
1) core of a granular form is provided, is H-type ZSM-5 molecular sieve, the H in H-type ZSM-5 molecular sieve is all or part of by one Kind or a variety of members selected from Sn, Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B The modified zsm-5 zeolite or their any mixture of plain M replacement；And
2) carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon will be selected from Nanotube, metal organic frame MOF, graphite, active carbon, metal oxide film (such as MgO, P2O5, CaO) one of or it is a variety of Material is coated on core surface of a granular form.
5. it is a kind of for directly preparing the composite catalyst of paraxylene by synthesis gas, it includes:
A) for catalyzing and synthesizing the catalyst A that gas is converted into methanol；With
B) for being catalyzed the catalyst B for forming dimethylbenzene, catalyst B is that the hud typed of any one of claim 1-3 such as is urged Agent,
Preferably, composite catalyst is in the form of mixtures of catalyst A and catalyst B, and catalyst A is physical or chemically wraps The form or catalyst B of capsule catalyst B be physical or form of chemically encapsulated catalysts A.
6. composite catalyst according to claim 5, wherein catalyst A include the first metal component and the second metal component or It is made of the first metal component and the second metal component, the first metal component is the member selected from Cr, Fe, Zr, In, Ga, Co, Cu Element, its oxide, its composite oxides or their any mixture, the second metal component be selected from Zn, Na, Al, Ag, Ce, K, the element of Mn, Pd, Ni, La, V, its oxide, its composite oxides or their any mixture；Preferably, the first gold medal Category group is divided into element, its oxide, its composite oxides or their any mixture selected from Cr, Co, Cu, Zr；And/or Second metal component is element, its oxide, its composite oxides or their any mixture selected from Zn, Al；It is especially excellent Selecting catalyst A is ZnO-Cr2O3。
7. according to the composite catalyst of claim 5 or 6, wherein the first metal component and the second metal component in catalyst A Molar ratio with elemental metal is 1000:1-1:100, preferably 100:1-1:50, more preferably 10:1-1:10, particularly preferably For 3:1-1:3.
8. wherein the weight ratio of catalyst A and catalyst B is 1:99- according to the composite catalyst of any one of claim 5-7 99:1, preferably 20:80-80:20, more preferably 30:70-70:30, particularly preferred 50:50-75:25.
9. a kind of method for preparing the composite catalyst according to any one of claim 5-8, comprising:
1) catalyst A powder and catalyst B powder are prepared respectively；With
2a) catalyst A powder and catalyst B powder and optional adhesive are mixed, are then shaped to composite catalyzing Agent；
2b) catalyst A powder and catalyst B powder are separately formed, obtain catalyst A formed body and catalyst B formed body, so These formed bodys are mixed afterwards；
It is 2c) hull shape into physical or chemically encapsulated forms by core, catalyst B of catalyst A；Or
It is 2d) hull shape into physical or chemically encapsulated forms by core, catalyst A of catalyst B.
10. method according to claim 9, wherein catalyst A is by being selected from sequence infusion process, co-impregnation, urea method and being total to The preparation of any one or more of precipitation method；Preferably, in sequence infusion process, co-impregnation, urea method and/or co-precipitation In the roasting technique of legal system catalyst A, process conditions are as follows:
Calcination atmosphere is air；And/or
Maturing temperature is 200-700 DEG C, preferably 400-600 DEG C；And/or
Calcining time is 3-8h, preferably 4-6h.
11. the nucleocapsid catalysis of nucleocapsid catalyst as claimed in one of claims 1-3, method according to claim 4 preparation Agent according to the composite catalyst of any one of claim 5-8 or passes through the method according to any one of claim 9-10 The composite catalyst of preparation is directly being prepared the purposes in paraxylene as catalyst by synthesis gas.
12. purposes according to claim 11, wherein the molar ratio of the hydrogen in synthesis gas and carbon monoxide is 0.1-5, preferably For 1-4；Reaction pressure is 1-10MPa, preferably 2-8MPa；Reaction temperature is 150-600 DEG C, preferably 250-500 DEG C；With/ Or, air speed is 200-8000h-1, preferably 500-5000h-1。
13. purposes according to claim 12, wherein composite catalyst first to be restored to pre- place before being passed through synthesis gas reaction Reason is preferably as follows under the process conditions of reduction pretreatment:
Also Primordial Qi is pure hydrogen；
Pretreatment temperature is 300-700 DEG C, preferably 400-600 DEG C；
Pretreatment pressures are 0.1-1MPa, preferably 0.1-0.5MPa；
Pretreatment hydrogen volume air speed is 500-8000h-1, preferably 1000-4000h-1；And/or
The pretreatment recovery time is 2-10h, preferably 4-6h.
CN201710917428.6A 2017-09-30 2017-09-30 Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas Pending CN109590019A (en)

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