CN111686789A - Na atom modified MOR-based catalyst and method for preparing liquid fuel by directly converting synthesis gas - Google Patents

Na atom modified MOR-based catalyst and method for preparing liquid fuel by directly converting synthesis gas Download PDF

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CN111686789A
CN111686789A CN201910189823.6A CN201910189823A CN111686789A CN 111686789 A CN111686789 A CN 111686789A CN 201910189823 A CN201910189823 A CN 201910189823A CN 111686789 A CN111686789 A CN 111686789A
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潘秀莲
封景耀
焦峰
包信和
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention belongs to direct preparation of liquid fuel from synthesis gas, and particularly relates to a Na atom modified MOR-based catalyst and a method for preparing liquid fuel by direct conversion of synthesis gas, wherein the synthesis gas is used as a reaction raw material, and a conversion reaction is carried out on a fixed bed or a moving bed, the catalyst is a composite catalyst, a component A and a component B are compounded together in a mechanical mixing manner, the active component of the component A is a metal oxide, and the component B is a molecular sieve with an MOR structure; the weight ratio of the active component in the component A to the component B is 0.1-20. The reaction process has high product yield and selectivity, the selectivity of gasoline in the liquid fuel can reach 50-80%, and meanwhile, the selectivity of the byproduct methane is low (< 12%), so that the method has a good application prospect.

Description

Na atom modified MOR-based catalyst and method for preparing liquid fuel by directly converting synthesis gas
Technical Field
The invention belongs to the field of liquid fuel preparation by synthesis gas, and particularly relates to a Na atom modified MOR-based catalyst and a method for preparing liquid fuel by directly converting synthesis gas.
Background
With the development of economy and the improvement of living standard, the demand of liquid fuels and chemicals is also sharply increased year by year. Gasoline production is currently predominantly obtained by catalytic reforming of heavy naphtha. With the gradual consumption of global petroleum resources and the rising price of crude oil, especially for China with shortage of petroleum resources, over 60% of petroleum consumption depends on import every year, a replaceable process route is sought, and a method for preparing liquid fuel by using non-oil-based carbon resources such as coal, biomass and the like is developed and utilized, so that the method has important social significance and strategic significance.
China is rich in coal resources, and the coal is used as a raw material to obtain synthesis gas (namely CO and H) through gasification2Mixed gas of (a) conventional fischer-tropsch routes can achieve direct conversion of syngas to liquid fuels, however limited by their reaction mechanisms, CO and H2Dissociative adsorption of molecules on the surface of the catalyst to generate surface C atoms and O atoms, and reaction between the C atoms and the O atoms and hydrogen adsorbed on the surface of the catalyst to form CHxIntermediate, with the production of water molecules. CH (CH)xThe intermediate undergoes free polymerization at the catalyst surface to produce hydrocarbon products having different numbers of carbon atoms (from one to thirty, and sometimes even up to hundreds of carbon atoms). The whole reaction hydrocarbon product has wide carbon atom number distribution and low selectivity of target products, such as gasoline with the selectivity lower than 50%. The existing literature reports that the dual-function catalyst consisting of oxide and molecular sieve can separate CO activation and C-C coupling on two active centers, thereby breaking the limitation of product selectivity in the traditional Fischer-Tropsch process and preparing low-carbon olefin with high selectivity. However, there remains a need for efficient direct conversion of syngas to liquid fuels, particularly gasoline distillate fuelsFurther study was carried out.
Disclosure of Invention
The invention solves the problems: the invention relates to a catalyst and a method for preparing liquid fuel by directly converting synthesis gas, which solves the problem of insufficient product selectivity in the process of preparing liquid fuel by directly converting synthesis gas.
The technical scheme of the invention is as follows: a catalyst comprises a component I and a component II, wherein the component I and the component II are compounded together in a mechanical mixing mode, the active component of the component I is a metal oxide, and the component II is a molecular sieve with a heteroatom-containing MOR topological structure;
the metal oxide is MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxOne or more than two of them;
the MnOx、ZnOx、CeOx、GaOx、BiOx、InOxHas a specific surface area of 1 to 100m2(ii)/g; the preferred specific surface area is 50 to 100m2/g；
The Mn isaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxHas a specific surface area of 5 to 150m2A preferred specific surface area is from 50 to 150m2/g；
The value range of x is 0.7-3.7, and the value range of a is 0-1; the value range of a + b is 0-1;
in the invention, a, b, (1-a), (1-a-b) and x only represent the relative proportion of the chemical compositions of elements in the metal oxide, and all the metal oxides with the same proportion are regarded as the same metal oxide.
The MOR contains Na atoms, the Na atoms replace H atoms on B acids in the MOR, and the content of the Na atoms accounts for 30-70 mol% of the content of the B acids in the MOR molecular sieve.
The Na atoms may be introduced into the MOR molecular sieve by ion exchange, and the Na precursors may be, but are not limited to, sodium nitrate, sodium carbonate, sodium citrate, sodium chloride, sodium bromide, sodium fluoride, sodium bicarbonate.
Based on the technical scheme, the weight ratio of the active ingredients in the component I to the component II is preferably 0.1-20, and preferably 0.3-8.
Based on the technical scheme, preferably, a dispersant is further added into the component I, the metal oxide is dispersed in the dispersant, and the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more of activated carbon, graphene and carbon nanotubes.
Based on the technical scheme, preferably, the MOR molecular sieve in the component II contains HF and TF type B acid, and the content of the HF and TF type B acid in the MOR accounts for 30-90 mol% of the content of all B acid in the MOR.
Based on the above technical scheme, it is further preferable that in the component i, the content of the dispersant is 0.05 to 90 wt%, preferably 0.05 to 25 wt%, and the balance is the metal oxide.
The total B acid content in the molecular sieve can be quantitatively measured by but not limited to a solid nuclear magnetic resonance or NH3-TPD method, and then the contents of HF and TF B acids are quantitatively calculated according to the sub-peak fitting of the hydroxyl vibration peak of the infrared spectrum.
The invention also provides a method for preparing liquid fuel by directly converting synthesis gas, which takes the synthesis gas as a reaction raw material to carry out conversion reaction on a fixed bed or a moving bed by using any one of the catalysts.
Based on the technical scheme, preferably, the pressure of the synthesis gas is 0.5-10MPa, preferably 1-8 MPa; the reaction temperature is 300-600 ℃, preferably 300-450 ℃; airspeed of 300-10000h-1Preferably 500--1More preferably 500--1(ii) a The synthesis gas is H2Mixed gas of/CO, H2The ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5.
The invention has the following advantages:
1. the technology is different from the traditional Fischer-Tropsch synthesis technology, the synthesis gas can be converted into the liquid fuel with high selectivity, and the gasoline fraction has high selectivity and is not limited by an ASF model.
2. The selectivity of gasoline in the product is high and can reach 50-80%, the selectivity of methane is extremely low and is less than 12%, and the product is easy to separate and has very high application prospect.
3. The active component metal oxide of the component I in the catalyst has higher specific surface area, so that the surface of the metal oxide has more active sites, which is more beneficial to the catalytic reaction.
4. The component II in the catalyst is coupled with the component I to convert the active gas-phase intermediate generated by the component I to obtain liquid fuel, particularly gasoline. The component II can promote the activation and conversion of the component I on the synthesis gas to further improve the conversion rate due to the action of the component II on the balance pulling of the series reaction, and on the other hand, the special pore channel structure of the molecular sieve in the component II is used for promoting the generation of HF and TF type B acid on gasoline molecules through Na ion substitution, so that the selectivity of low-carbon olefin can be effectively inhibited, and more gasoline products can be obtained with high selectivity. Lower olefins are more likely to be produced if Na ion exchanged molecular sieves are not used.
5. The function of the invention can not be realized by separately using the component I or the component II, for example, the selectivity of methane in the product of the component I is very high and the conversion rate is very low, while the component II can hardly activate and convert the synthesis gas, and only the component I and the component II are used for concerted catalysis, the high-efficiency synthesis gas conversion can be realized, and the excellent selectivity can be obtained. The component I can activate the synthesis gas to generate a specific active gas phase intermediate, the intermediate diffuses into the pore canal of the component II through a gas phase, and the molecular sieve with the MOR structure selected by the invention has a special pore canal structure and acidity, so that the active gas phase intermediate generated by the component I can be further activated and converted into olefin. Due to the special pore structure of the component II, the product has special selectivity.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
The metal oxide of the present invention can be obtained by purchasing commercially available metal oxides with a high specific surface area, or can be obtained by the following methods:
preparation of catalyst component I
Synthesizing a ZnO material with a high specific surface by a precipitation method:
(1) 3 parts, 0.446g (1.5mmol) of Zn (NO) are weighed out separately3)2·6H2Adding 0.300g (7.5mmol), 0.480g (12mmol) and 0.720g (18mmol) NaOH into 3 containers in sequence, adding 30ml deionized water into 3 containers, stirring at 70 deg.C for 0.5 hr to mix the solution, and naturally coolingCooling to room temperature. Centrifugally separating the reaction liquid, collecting the precipitate after centrifugal separation, and washing the precipitate for 2 times by using deionized water to obtain a ZnO metal oxide precursor;
(2) roasting: and drying the obtained product in air, and roasting in the atmosphere to obtain the ZnO material with high specific surface. The atmosphere is inert gas, reducing gas or oxidizing gas; the inert gas being N2One or more of He and Ar; the reducing gas being H2One or two of CO and the reducing gas can also contain inert gas; the oxidizing gas being O2、O3、NO2And the oxidizing gas may contain an inert gas. The roasting temperature is 300-700 ℃, and the time is 0.5-12 h.
The purpose of calcination is to decompose the precipitated metal oxide precursor into oxide nanoparticles with high specific surface area at high temperature, and the decomposed oxide surface adsorbed species can be treated cleanly by the high-temperature treatment of calcination.
Specific samples and their preparation conditions are shown in Table 1 below, in which ZnO #4 is a commercially available ZnO single crystal of low specific surface area as a comparative example.
TABLE 1 preparation of ZnO materials and their parametric properties
Figure BDA0001994054490000041
(II) synthesizing MnO materials with high specific surface area by a coprecipitation method:
the preparation process is the same as that of ZnO #2, except that a precursor of Zn is replaced by a corresponding precursor of Mn, which can be one of manganese nitrate, manganese chloride and manganese acetate, wherein the precursor is manganese nitrate, and a corresponding product is defined as MnO; the specific surface area is: 23m2/g。
(III) coprecipitation method for synthesizing CeO with high specific surface area2Materials:
the preparation process is the same as that of ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Ce, which can be one of cerium nitrate, cerium chloride and cerium acetate, and the precursor is nitric acidCerium, corresponding product being defined as CeO2(ii) a The specific surface area is: 92m2/g。
Synthesis of Ga having high specific surface area by coprecipitation method2O3Materials:
the preparation process is the same as that of ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Ga, which can be one of gallium nitrate, gallium chloride and gallium acetate, and the corresponding product is defined as Ga2O3(ii) a The specific surface area is: 55m2/g。
(V) coprecipitation method for synthesizing Bi with high specific surface area2O3Materials:
the preparation process is the same as the ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Bi, and the precursor can be one of bismuth nitrate, bismuth chloride and bismuth acetate, and is bismuth nitrate. The corresponding product is defined as Bi2O3(ii) a The specific surface areas are: 87m2/g。
(VI) Synthesis of In having a high specific surface area by coprecipitation2O3Materials:
the preparation process is the same as that of ZnO #2, except that Zn precursor is replaced by corresponding precursor of In, which can be one of indium nitrate, indium chloride and indium acetate, In this case, the corresponding product is defined as In2O3(ii) a The specific surface area is: 52m2/g
(VII) Synthesis of Mn with high specific surface area by precipitationaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox：
Zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate and ferric nitrate are used as precursors and mixed with ammonium carbonate in water at room temperature (wherein the ammonium carbonate is used as a precipitator, and the feeding proportion is that the ammonium carbonate is excessive or the proportion of ammonium ions and metal ions is 1:1 preferably); and (3) aging the mixed solution, taking out, washing, filtering and drying, and roasting the obtained solid in an air atmosphere to obtain the metal oxide with the high specific surface, wherein specific samples and preparation conditions thereof are shown in the following table 2.
TABLE 2 preparation of high specific surface area metal oxides and their performance parameters
Figure BDA0001994054490000051
Figure BDA0001994054490000061
(VIII) dispersant Cr2O3、Al2O3Or ZrO2Dispersed metal oxide
With dispersant Cr2O3、Al2O3Or ZrO2As carrier, preparing Cr by precipitation deposition2O3、Al2O3Or ZrO2A dispersed metal oxide. Taking the preparation of dispersed ZnO as an example, commercial Cr is used2O3(specific surface area about 5 m)2/g)、Al2O3(specific surface area about 20 m)2/g) or ZrO2(specific surface area about 10 m)2/g) as carrier is pre-dispersed in water, then zinc nitrate is used as raw material, mixed with sodium hydroxide precipitant for precipitation at room temperature, Zn2+In a molar concentration of 0.067M, Zn2+The mol part ratio of the organic silicon compound to the precipitant is 1: 8; then aging at 160 ℃ for 24 hours to obtain Cr2O3、Al2O3Or ZrO2ZnO dispersed as a carrier (the content of the dispersant in the component I is 0.1 wt%, 20 wt%, 85 wt% in sequence). The obtained sample is roasted for 1h at 500 ℃ in the air, and the products are sequentially defined as1-3 of the dispersed oxide, the specific surface area of which is as follows in sequence: 148m2/g，115m2/g，127m2/g。
In the same manner, SiO can be obtained2(specific surface area about 2 m)2/g)、Ga2O3(specific surface area about 10 m)2Per g) or TiO2(specific surface area about 15 m)2(g) MnO oxide dispersed as a support (the content of the dispersant in component I is 5 wt.%, 30 wt.%, 60 wt.% in this order), and the product is defined as dispersed oxide 4 to 6 in this order. The specific surface area is as follows: 97m2/g，64m2/g，56m2/g。
In the same manner, activated carbon (specific surface area about 1000 m) was obtained2Per gram), graphene (specific surface area about 500 m)2Per g) or carbon nanotubes (specific surface area about 300 m)2The ZnO oxide dispersed as a carrier (the content of the dispersant in component I is 5 wt%, 30 wt%, 60 wt% in this order), and the product is defined as a dispersed oxide 7 to 9 in this order. The specific surface area is as follows: 177m2/g，245m2/g，307m2/g。
Preparation of component II (MOR topological structure molecular sieve)
The MOR topological structure is an orthorhombic system, has a one-dimensional through hole structure with oval through holes which are parallel to each other, and comprises 8 circular rings and 12 circular rings which are parallel to each other, wherein 8 circular ring pockets are formed on the side edge of a main hole of each 12 circular ring and communicated with each other;
the determination of the LF class B acid content may be, but is not limited to: the content of all B acids in MOR is quantitatively measured by using a solid nuclear magnetic H spectrum or NH3-TPD, then three peaks of LF, HF and TF are fitted through an OH vibration peak signal of vacuum in-situ infrared, the percentage of LF in all B acids is calculated according to the relative proportion of peak areas, and the content of LF type B acids is calculated according to the product of the content of all B acids in MOR and the percentage of LF in all B acids. The fit and assignment of the three acids is according to the document N.Cherkasov et al/visual Spectroscopy 83(2016) 170-179.
The MOR molecular sieve of component II of the present invention may be a commercially available product (selected from the claimed molecular sieves therein), such as the commercial mordenite zeolite of the southern Kao university catalyst plant; or mordenite available from Shentao catalysts, Inc.;
it may be a self-prepared molecular sieve, and the hydrothermal synthesis is exemplified here.
(I) preparation of MOR molecular sieve by hydrothermal method
The preparation process comprises the following steps:
according to n (SiO)2)/n(Al2O3)＝15、n(Na2O)/n(SiO2)＝0.2、n(H2O)/n(SiO2)＝26。
Mixing aluminum sulfate and sodium hydroxide solution, adding silica sol, stirring for 1h to obtain homogeneous initial gel, transferring the initial gel into a high-pressure synthesis kettle, statically crystallizing at 180 ℃ for 24h, quenching, washing and drying to obtain the mordenite sample.
Taking a mordenite sample, mixing the mordenite sample with 1mol/L ammonium chloride solution, stirring for 3h at 90 ℃, washing, drying, continuously roasting for 2 times at 450 ℃ for 6h to obtain the hydrogen mordenite.
The framework element composition of the molecular sieve with MOR topological structure prepared by the process can be one of Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O; connecting H to O elements of part of the framework, changing the type and proportion of the precursor, specifically referring to Table 3, obtaining hydrogen-type mordenite of different types, which is sequentially defined as MOR 1-6;
TABLE 3 preparation of molecular sieves with MOR topology and their performance parameters
Figure BDA0001994054490000071
Figure BDA0001994054490000081
The mode of incorporation of Na into the MOR molecular sieve of component II of the present invention is exemplified herein by an ion exchange method, but is not limited thereto, and the original MOR molecular sieve used for ion exchange may be in the hydrogen form, also in the ammonium form, etc., and is exemplified herein by an ion exchange method.
(II) preparation of Na/HMOR by ion exchange method
(1) Ion exchange: taking hydrogen-type mordenite as an original MOR molecular sieve, mixing the hydrogen-type mordenite with 0.1mol/L sodium nitrate solution, stirring for 2h at 80 ℃, performing centrifugal separation, washing the non-exchanged ions on the surface of the catalyst with deionized water, drying at 60 ℃ overnight, and then drying in an oven at 110 ℃ to remove water. The salt solution of the target ion for replacement may be nitrate, carbonate, sulfate, acetate, etc., but is not limited to the above salt solution, and here, nitrate is exemplified. The concentration of the salt solution for replacement is 0.001-0.2mol/L, and if necessary, 0.1M dilute nitric acid is adopted to adjust the pH value, the temperature of exchange is room temperature-80 ℃, and the stirring time is 0.5-12 h.
(2) Roasting: and drying the obtained product in the air, roasting in the atmosphere, and roasting at 550 ℃ for 2h to obtain the hydrogen mordenite containing Na atoms. The atmosphere is inert gas, reducing gas or oxidizing gas; the inert gas being N2One or more of He and Ar; the reducing gas being H2One or two of CO and the reducing gas can also contain inert gas; the oxidizing gas being O2、O3、NO2And the oxidizing gas may contain an inert gas. The roasting temperature is 300-700 ℃, the time is 0.5-12h, and the specific results are shown in Table 4.
TABLE 4 preparation of molecular sieves with MOR topology containing heteroatoms and their performance parameters
Figure BDA0001994054490000091
Preparation of catalyst
The component I and the component II in required proportion are added into a container, the purposes of separation, crushing, uniform mixing and the like are realized by utilizing one or more than two of extrusion force, impact force, shearing force, friction force and the like generated by the high-speed movement of the materials and/or the container, the conversion of mechanical energy, heat energy and chemical energy is realized by regulating the temperature and the carrier gas atmosphere, and the interaction among different components is further regulated.
In the mechanical mixing process, the mixing temperature can be set to be 20-100 ℃, and the mixing can be carried out in an atmosphere or directly in air, wherein the atmosphere is selected from any of the following gases:
a) nitrogen and/or inert gas;
b) a mixed gas of hydrogen and nitrogen and/or inert gas, wherein the volume of the hydrogen in the mixed gas is 5-50%;
c) the mixed gas of CO and nitrogen and/or inert gas, wherein the volume of CO in the mixed gas is 5-20%;
d)O2mixed with nitrogen and/or inert gases, in which O2The volume of the inert gas in the mixed gas is 5-20%, and the inert gas is one or more than two of helium, argon and neon.
The mechanical mixing can be one or more of mechanical stirring, ball milling, table mixing and mechanical grinding, and specifically comprises the following steps:
mechanical stirring: in the stirring tank, the component I and the component II are mixed by a stirring rod, and the mixing degree of the component I and the component II can be adjusted by controlling the stirring time (5min-120min) and the stirring speed (30-300 r/min).
Ball milling: the grinding material and the catalyst are rolled in a grinding tank at a high speed to generate strong impact and rolling on the catalyst, so that the effects of dispersing and mixing the component I and the component II are achieved. By controlling the abrasive (the material can be stainless steel, agate and quartz, and the size range is 5mm-15 mm). The ratio of the catalyst to the catalyst (mass ratio range: 20-100: 1).
A shaking table mixing method: premixing the component I and the component II, and filling the mixture into a container; mixing the component I and the component II by controlling the reciprocating oscillation or the circumferential oscillation of the shaking table; the uniform mixing is realized by adjusting the oscillation speed (range: 1-70 r/min) and the time (range: 5min-120 min).
Mechanical grinding method: premixing the component I and the component II, and filling the mixture into a container; under a certain pressure (range: 5 kg-20 kg), the catalyst is ground and moved relatively to the mixed catalyst (speed range: 30-300 r/min) to realize uniform mixing.
Specific catalyst preparations and their parametric characteristics are shown in tables 5 and 6.
TABLE 5 preparation of the catalyst and its parametric characterization
Figure BDA0001994054490000101
Figure BDA0001994054490000111
Figure BDA0001994054490000121
Figure BDA0001994054490000131
TABLE 6 preparation of comparative catalysts and their parametric characterization
Figure BDA0001994054490000132
Figure BDA0001994054490000141
Examples of catalytic reactions
Fixed bed reactions are exemplified, but the catalyst is also suitable for use in moving bed reactors. The device is provided with a gas mass flow meter and an on-line product analysis chromatograph (tail gas of a reactor is directly connected with a quantitative valve of the chromatograph to carry out periodic real-time sampling analysis).
2g of the catalyst of the present invention was placed in a fixed bed reactor, and the air in the reactor was replaced with Ar, followed by H2Raising the temperature to 300 ℃ in the atmosphere, and switching the synthesis gas (H)2The mol ratio of/CO is 0.2-3.5), the pressure of the synthetic gas is 0.5-10MPa, the temperature is raised to the reaction temperature of 300-. The product was analyzed by on-line chromatographic detection.
The reaction performance can be varied by varying the temperature, pressure and space velocity, and the specific results are shown in Table 7. The selectivity of gasoline in the liquid fuel can reach 50-80%, and meanwhile, the selectivity of the byproduct methane is low (< 12%)
TABLE 7 application and reaction Properties of the catalysts
Figure BDA0001994054490000142
Figure BDA0001994054490000151
Figure BDA0001994054490000161
Comparative examples 1-6 correspond to catalysts a-F of the examples, respectively, and it can be seen that excellent gasoline selectivity can be achieved by the Na exchanged sample, whereas the gasoline selectivity is very low for the sample that has not been Na exchanged, with the products being predominantly C2-C4 hydrocarbons.
Comparative example 7 used a catalyst in which the molecular sieve of catalyst a was replaced with a commercial SAPO-34 available from catalyst works of southern kaiki university and exchanged with Na ions.
Comparative example 7 shows that the topology of MOR is critical to modulation of product selectivity, SAPO34 has pore size 3.8A, is suitable for C2-C4 hydrocarbons, and does not selectively yield liquid fuels.
Comparative example 8 the catalyst used was substantially identical to the catalyst C sample except that the MOR3 molecular sieve was ion exchanged with copper nitrate and the product was predominantly lower hydrocarbons with lower gasoline selectivity.
The catalyst used in comparative example 9 was a sample containing only component i ZnO1 but not component ii, the reaction conversion was very low, and the product was mainly composed of by-products such as dimethyl ether and methane, and almost no gasoline was produced.
The catalyst used in comparative example 10 was a component II only molecular sieve, and the catalyst had almost no activity in the case of the sample containing no component I.
Comparative examples 9 and 10 show that the reaction effect is extremely poor with only component I or component II, and the excellent reaction performance of the present invention is not achieved at all.
Comparative example 11, the catalyst used was a commercial MOR with replacement of the molecular sieve for catalyst A by HF and TF type B acids at less than 30%. Although ion exchange is also carried out, the selectivity of gasoline is low, and the selectivity of methane is high, so that the selection of a proper commercial molecular sieve is important.
Comparative example 12, the catalyst used was the molecular sieve of comparative example 4 subjected to Na ion exchange, but the Na content was only 10%, the gasoline selectivity was lower, the methane selectivity was higher, and the requirements of the present invention could not be met.
Comparative example 13 using the catalyst by impregnation method, cobalt nitrate solution was impregnated on the surface of NaMOR1 with Co loading of 10%, calcined at 500 ℃ and then calcined in H2Reducing at 400 ℃ for 2h under the atmosphere to obtain the Co/NaMOR1 catalyst. And the catalytic reaction was evaluated under the conditions. The results show that methane selectivity is high and gasoline selectivity is not ideal. It is stated that the metal oxides according to the invention are not used, but that the invention cannot be realized, for example, with metal active components.
Comparative example 14, similar to catalyst I except that the molecular sieve of catalyst I was the NaMOR3 molecular sieve of the present invention and the molecular sieve of comparative example 14 was the MOR3 molecular sieve treated with 1M KOH at 80 ℃ for 2h, followed by washing and centrifugation to give KMOR 3. As a result, as shown in Table 5, the NaOH and KOH solutions are too basic to damage the molecular sieve skeleton seriously, resulting in obvious decrease of gasoline selectivity and increase of methane selectivity.

Claims (8)

1. A catalyst, characterized by: the catalyst comprises a component I and a component II, wherein the component I and the component II are compounded together in a mechanical mixing mode, the active component of the component I is a metal oxide, and the component II is a molecular sieve with an MOR topological structure;
the metal oxide is MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxOne or more than two of them;
the MnOx、ZnOx、CeOx、GaOx、BiOx、InOxHas a specific surface area of 1 to 100m2(ii)/g; the preferred specific surface area is 50 to 100m2/g；
The Mn isaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxHas a specific surface area of 5 to 150m2A preferred specific surface area is from 50 to 150m2/g；
The value range of x is 0.7-3.7, and the value range of a is 0-1; the value range of a + b is 0-1;
the MOR topological structure molecular sieve contains Na atoms, the Na atoms replace H atoms on B acid in the MOR, and after replacement, the Na atom content accounts for 30-70 mol% of the B acid content in the MOR molecular sieve.
2. The catalyst of claim 1, wherein: the weight ratio of the active ingredient in component I to component II is 0.1 to 20, preferably 0.3 to 8.
3. The catalyst of claim 1, wherein: the component I is also added with a dispersant, the metal oxide is dispersed in the dispersant, and the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more of activated carbon, graphene and carbon nanotubes.
4. The catalyst of claim 1, wherein: the MOR molecular sieve in the component II contains HF and TF type B acid, and the mole content of the HF and the TF type B acid in the MOR topological structure molecular sieve accounts for 30-90% of the content of all B acid in the MOR topological structure molecular sieve.
5. A catalyst according to claim 3, wherein: in the component I, the content of the dispersant is 0.05-90 wt%, preferably 0.05-25 wt%, and the balance is the metal oxide.
6. A method for preparing liquid fuel by directly converting synthesis gas is characterized in that: the method takes synthesis gas as a reaction raw material, and carries out conversion reaction on a fixed bed or a moving bed, and the adopted catalyst is the catalyst of any one of claims 1 to 5.
7. The method of claim 6, wherein: the pressure of the synthesis gas is 0.5-10 MPa; the reaction temperature is 300-600 ℃; airspeed of 300-10000h-1(ii) a The synthesis gas is H2Mixed gas of/CO.
8. The method of claim 6, wherein the pressure of the syngas is 1-8 MPa; the reaction temperature is 300-450 ℃; the space velocity is 500-9000h-1(ii) a Said H2The ratio of/CO is 0.3-2.5.
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