CN108970638B

CN108970638B - Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas

Info

Publication number: CN108970638B
Application number: CN201710407762.7A
Authority: CN
Inventors: 潘秀莲; 焦峰; 包信和
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2017-06-02
Filing date: 2017-06-02
Publication date: 2021-01-19
Anticipated expiration: 2037-06-02
Also published as: CN108970638A

Abstract

The invention belongs to the field of preparation of liquid fuel and co-production of low-carbon olefin by synthesis gas, and particularly relates to a method for preparing liquid fuel and co-production of low-carbon olefin by direct conversion of a catalyst and synthesis gas. The synthesis gas is used as a reaction raw material, and the reaction is carried out on a fixed bed or a moving bed, the catalyst contains a component A and a component B, the component A is an active metal oxide, and the active component B is a molecular sieve with one or more than two structures of TON, MTT and MRE; the weight ratio of the catalyst A to the catalyst B is 0.1-20. The pressure of the synthesis gas is 0.1-10MPa, the reaction temperature is 300-^‑1. The reaction mainly produces gasoline with high octane number and coproduces low-carbon olefin, and the selectivity of byproduct methane is low (<10 percent) and has good application prospect.

Description

Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas

Technical Field

The invention belongs to the field of preparation of liquid fuel and co-production of low-carbon olefin by synthesis gas, and particularly relates to a method for preparing liquid fuel and co-production of low-carbon olefin by direct conversion of a catalyst and 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, more than 60% of petroleum consumption depends on import every year, a replaceable process route is sought, and a method for preparing low-carbon olefin from coal, biomass and other non-oil-based carbon resources is developed and utilized, so that the method has important social and strategic meanings.

The brief technical route of taking coal as a raw material, obtaining synthesis gas (namely mixed gas of CO and H2) by gasification, converting the synthesis gas into methanol, preparing gasoline from the methanol by dimethyl ether is mature and is industrialized, and the route provides an important new route for preparing liquid fuel from carbon resources such as coal, natural gas and the like. However, if direct conversion of the synthesis gas can be achieved without methanolationThe direct route for preparing the dimethyl ether by methanol dehydration can simplify the process flow, reduce unit operation and reduce investment and energy consumption. The traditional Fischer-Tropsch route can realize the direct conversion of synthesis gas to prepare liquid fuel, but is limited by the reaction mechanism of the synthesis gas, namely 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 methylene (CH)₂) Intermediate with the evolution of water molecules. The methylene intermediates undergo free-radical polymerization at the catalyst surface by migratory insertion reactions to produce hydrocarbon products having varying 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%.

Light Olefins (Light Olefins), mainly including ethylene, propylene and butylene, are the cornerstones of modern chemical industry, and are currently produced mainly by naphtha cracking. The process technology of a plurality of reactors with multiple steps for obtaining synthesis gas by coal gasification and then converting the synthesis gas into methanol or dimethyl ether and converting the methanol or dimethyl ether into low-carbon olefin is relatively mature, and industrialization is already realized. In order to simplify the reaction process and shorten the process route, people modify and improve the traditional Fischer-Tropsch reaction catalyst, such as an Fe-based catalyst, and add additives with different compositions, such as alkali metal K, Na and transition metals Mn and Cu, so that the selectivity of the low-carbon olefin can be effectively improved. German Ruhr chemical company develops multi-component assistant promoted Fe-Zn-Mn-K catalyst for synthesizing low-carbon olefin [12]. Report that Fe-Mn-K/AC catalyst prepared by taking ferric oxalate as precursor is used in airspeed of 600h by Zhang Jingchang, Beijing chemical university and the like^-115bar and 320 ℃, the conversion rate of CO is up to 97 percent, C₂ ^＝-C₄ ^＝The selectivity in hydrocarbon is 68% [ Zhangchang, Weiguobin, Caoweiang, catalysis 24(2003)259-]Over C predicted by ASF distribution model₂-C₄The selectivity of the hydrocarbon. The carrier of the catalyst also plays an important role in modifying the selectivity of the product through the interaction with Fe species. Dutch deJong lessonThe subject group recently reported Carbon Nanofibers (CNF) and alpha-Al₂O₃Using ferric ammonium citrate as carrier to prepare 12 wt% Fe catalyst at low pressure (1bar), 350 deg.C and H₂The reaction is carried out for 15 hours under the condition that the CO is 1, the conversion rate of the CO is 0.5-1.0%, and the selectivity of the low-carbon olefin in the hydrocarbon is 60% [ H.M.T.Galvis, J.H.Bitter, C.B.Hhare, M.Ruitenbeek, A.L.Dugulan, K.P.de Jong, Science 335(2012) 838]. The same catalyst is in

H₂1/CO, 20bar, space velocity 1500h^-1In the following, conversion rates of 70 to 88% were obtained, with FTY of 2.98X 10 respectively^-5mol CO/gFes and 1.35X 10^-5mol CO/gFe·s，CO₂The selectivity of (b) is 42-46%, wherein the selectivity of the lower olefins in the hydrocarbon is 52-53%. Subsequently, they found that the trace amount of 0.03% S and about 0.2% Na in the catalyst had significant promoting effects on the reactivity and selectivity of low-carbon olefins [ h.m.t.galvis, a.c.j.koeken, j.h.bitter, t.davidia, m.ruitenbeek, a.i.dugulan, k.p.de Jong, j.catal.303(2013) 22-30%]. Systematic intensive research on the activated carbon carrier by the university of Chinese academy of sciences has revealed that the product on the activated carbon-supported iron catalyst deviates from the ASF distribution [ Shenchou, Linnaughout, octogen, Lidongbai, Feichou 19(1991)289 and 297; mahiping, Dingyueje, Rohonogen, etc., catalytic bulletin 22(2001) 279-282-]. In addition, the preparation method and process of the catalyst, such as roasting process, reduction condition, etc., can directly influence the dispersion and size of active components, thereby modulating the activity of reaction and the selectivity of products. The Beijing university of chemical industry adopts a supercritical fluid combination technology (i.e. a method of chemical precipitation, gel-like, supercritical drying) to highly disperse the active component Fe and the auxiliary agent, so as to prepare the nanoscale Fe-based catalyst, wherein the conversion rate of CO is more than 96 percent, and the selectivity of the low-carbon olefin in the hydrocarbon is more than 54 percent [ the Beijing university of chemical industry, a nano catalyst for preparing the low-carbon olefin from the synthesis gas and a preparation method thereof: china, 101396662[ P ]].2009-04-01]。

To this end, researchers have sought to couple multiple processesAnd a number of attempts have been made. Xu et Al mixed CuO-ZnO-Al2O3 with ZSM-5 to obtain a catalyst, the product obtained in the syngas conversion reaction being mainly dimethyl ether [ m.xu, j.h.lunsford, d.w.goodman, a.bhattacharyya, appl.catal.a.general 149(1997) 289; D.Mao, W.Yang, J.Xia, B.Zhang, Q.Song, Q.Chen, J.Cat.230 (2005)140]. Erena et Al mix a multi-component metal compound such as CuO/ZnO/Al2O3 with a ZSM-5 molecular sieve to catalyze the conversion of synthesis gas to obtain a product mainly comprising gasoline [ J.Erena, J.M.Arandes, J.Bilbao, A.G.Gayubo, H.I.De Lasa, Chemical Engineering Science 2000,55, 1845; J.Erena, J.M.Arandes, R.Garona, A.G.Gayubo, J.Bilbao, Journal of Chemical Technology and Biotechnology 2003,78,161]. Park et Al passed through a dual bed reactor, first over the first reactor Fe-Cu-Al catalyst at 300 deg.C, 10atm, GHSV 3600h^-1Then making it pass through ZSM-5 cracking catalyst bed layer at 500 deg.C of second reactor to make a large quantity of C₅₊Cracking the product into low-carbon olefin, wherein the selectivity of the low-carbon hydrocarbon in the obtained hydrocarbon product is 52%, and the selectivity of the low-carbon olefin in the total product is 28% [ J.L.park, Y.J.Lee, K.W.Jun, J.W.Bae, N.Viswanadham, Y.H.Kim, J.Ind.Eng.Chem.15(2009) 847-853-]。

Disclosure of Invention

Aiming at the problems, the invention provides a catalyst and a method for preparing liquid fuel and co-producing low-carbon olefin by directly converting synthesis gas, the catalyst can catalyze the synthesis gas to directly convert the synthesis gas to generate the liquid fuel and co-produce the low-carbon olefin, and the selectivity of gasoline fraction can reach 50-80%.

The technical scheme of the invention is as follows:

the catalyst is a composite catalyst A + B, the active component of the component A is active metal oxide, and the component B is a molecular sieve with one or more than two structures of TON, MTT or MRE; the active metal oxide is MnO or MnCr₂O₄、MnAl₂O₄、MnZrO₄、ZnO、ZnCr₂O₄、ZnAl₂O₄、CeO₂、CoAl₂O₄、FeAl₂O₄One or more than two of them.

The catalyst component A is preferably MnO or Cr₂O₃、MnCr₂O₄、MnAl₂O₄,MnZrO₄、ZnAl₂O₄、CeO₂、CoAl₂O₄、FeAl₂O₄One or more than two of them; more preferably MnO and Cr₂O₃、MnCr₂O₄、MnAl₂O₄,MnZrO₄、CeO₂、CoAl₂O₄、FeAl₂O₄One or more than two of them;

the molecular sieve with one or more than two structures of TON, MTT or MRE in the catalyst component B contains 10-element pore opening one-dimensional pore canals and consists of H, O, Si and Al; the component B can also contain one or more than two dispersants of Al2O3, graphite, SiO2, ZrO2, TiO2, Cr2O3, Ga2O3, CaO, MgO, CeO2, In2O3 and SnO2, and the content of the dispersant is 0-50 wt%.

The spacing between the active metal oxide of component A and the geometric centre of the particles of component B is between 20nm and 10mm, preferably between 50nm and 1mm, more preferably between 100nm and 0.5 mm.

The weight ratio between the active ingredient in component A and component B is in the range of 0.1-20 times, preferably 0.3-5.

The active metal oxide is composed of crystal grains having a size of 5 to 30nm, and a large number of oxygen vacancies are present in a depth of 0.3nm from the surface of the crystal grains to the inside of the crystal grains, and the surface oxygen vacancy percentage concentration is defined as (100% by mole of oxygen atoms as a percentage of the theoretical stoichiometric oxygen mole content) with the oxygen vacancy concentration being preferably 20 to 90%, more preferably 40 to 90%, and most preferably 50 to 90%, based on 100% by mole of the theoretical stoichiometric oxygen mole content.

A dispersant is also added in the catalyst A, and the dispersant is Al₂O₃、Cr₂O₃、ZrO₂、TiO₂One or two of the active metal oxides are dispersed in a dispersant, the content of the dispersant in the catalyst A is 10-90wt%, and the balance is the active metal oxide.

A method for preparing liquid fuel and co-producing low-carbon olefin by directly converting synthesis gas takes the synthesis gas as a reaction raw material to carry out conversion reaction on a fixed bed or a moving bed.

The pressure of the synthesis gas is 0.1-10MPa, preferably 1-8MPa, and more preferably 2-8 MPa; the reaction temperature is 300-600 ℃, preferably 300-500 ℃; space velocity of 300-^-1。

The synthesis gas for the reaction is H₂a/CO mixture, which may also contain other gases; the other gas comprising CO₂，N₂Ar, He, methane, ethane, ethylene; the content of other gases is 0.1-10%; wherein H₂The ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5. The liquid fuel is mainly gasoline, mainly contains high-octane-value isomeric hydrocarbons, and simultaneously co-produces low-carbon olefin, wherein the low-carbon olefin is C2-C4 olefin containing 2 to 4 carbon atoms, and comprises one or more of ethylene, propylene and butylene.

The invention has the following advantages:

1. the technology is different from the traditional technology (MTG for short) for preparing gasoline from methanol, and realizes the one-step direct conversion of the synthesis gas into liquid fuel and low-carbon olefin.

2. The selectivity of gasoline fraction in the product is high and can reach 50-80%, and the rest product is mainly low-carbon olefin with high added value, and the selectivity of the low-carbon olefin can reach 10-30%.

3. Compared with the traditional Fischer-Tropsch synthesis technology, the gasoline composition mainly contains high-octane-value isomeric hydrocarbons, the straight-chain hydrocarbons have low selectivity, and the oil product quality is high; and the selectivity of the byproduct methane is low and is lower than 10 percent.

4. The preparation process of the composite catalyst in the patent is simple and has mild conditions; and the reaction process has very high product yield and selectivity, and has very good application prospect.

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.

Example 1

Preparation of catalyst A

Synthesizing a ZnO material with a polar surface by an etching method:

(1) 0.446g (1.5mmol) of Zn (NO) was weighed₃)₂·6H₂O and 0.480g (12mmol) of NaOH, then 30ml of deionized water is measured and added, and the solution is stirred for more than 0.5h to be uniformly mixed. Heating to 160 ℃, reacting for 20h, and decomposing the precipitate into zinc oxide; naturally cooling 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 ZnO oxide;

(2) adopting an etching agent such as oleic acid, urotropine, ethylenediamine, ammonia water, hydrazine hydrate and the like, ultrasonically mixing the etching agent with ZnO oxide at normal temperature, soaking the ZnO oxide in the etching agent solution, and allowing the etching agent and zinc oxide to form a complex or direct reduction reaction; and heating the suspended matter, taking out, washing and filtering to obtain the nano ZnO material with a large number of surface oxygen cavities.

In table 1: the mass ratio of the catalyst to the etchant is 1: 3. The mass ratio of the oleic acid to the urotropine is 1:1, no solvent is used, the mass ratio of the oleic acid to 5 wt% of hydrazine hydrate is 95:5, and no solvent is used; specific process conditions including etchant, temperature, process time and atmosphere type are shown in table 1 below.

(3) Drying or drying and reduction:

centrifuging or filtering the obtained product, washing with deionized water, drying or drying and reducing in an atmosphere of inert gas or a mixture of inert gas and reducing atmosphere, wherein the inert gas is N₂One or more of He and Ar, and reducing atmosphere is H₂And one or more than two of CO, wherein the volume ratio of the inert gas to the reducing gas in the drying and reducing mixed gas is 100/10-0/100, the temperature of the drying and reducing treatment is 350 ℃, and the time is 4 hours. Thus obtaining the ZnO material with the surface rich in oxygen vacancies. Specific samples and their preparation conditions are shown in table 1 below. Wherein the surface oxygen vacancy concentration is defined as (100% -molar amount of oxygen atoms to theoretical stoichiometric molar amount of oxygen content%).

TABLE 1 preparation of ZnO materials and their parametric properties

The surface oxygen vacancy is the distance range from the surface of the crystal grain to the depth of the inner direction of the crystal grain, and the oxygen atom molar quantity accounts for the percentage of the theoretical stoichiometric oxygen molar content;

as comparative examples, ZnO 9 having no oxygen vacancies on the surface, which was not etched in the step (2), and metallic Zn 10 in which Zn was completely reduced;

(II) synthesizing a MnO material with a polar surface by an etching method: the preparation process is the same as the above (I), except that the precursor of Zn is replaced by the corresponding precursor of Mn, which is one of manganese nitrate, manganese chloride and manganese acetate.

The etching treatment process is the same as the preparation process of the products ZnO3, ZnO 5 and ZnO8 in the step (2) in the step (I), and the catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 56%, 36%, 27%;

the corresponding product is defined as MnO 1-3;

(III) synthesizing CeO with polar surface by etching method₂Materials: the preparation process is the same as the above (I), except that the precursor of Zn is replaced by the corresponding precursor of Ce, and the precursor is one of cerium nitrate, cerium chloride and cerium acetate.

The etching treatment process is the same as the preparation process of the products ZnO3, ZnO4 and ZnO8 in the step (2) in the step (I), and the catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 67%, 38%, 25%;

the corresponding product is defined as CeO 1-3;

(IV) synthesizing Cr with polar surface by etching method₂O₃Materials:

the preparation process is the same as the above (I), except that the precursor of Zn is replaced by the corresponding precursor of Cr, which is one of chromium nitrate, chromium chloride and chromium acetate.

The etching treatment process is the same as the preparation process of the products ZnO3, ZnO4 and ZnO8 in the step (2) in the step (I), and the catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 45%, 29%, 20%;

the corresponding product is defined as Cr₂O₃ 1-3；

(V) synthesizing nano ZnCr with high specific surface area and high surface energy₂O₄、ZnAl₂O₄、MnCr₂O₄、MnAl₂O₄,MnZrO₄Spinel:

zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate and zirconium nitrate are used as precursors and are mixed with urea in water at room temperature; and aging the mixed solution, taking out, washing, filtering and drying, and roasting the obtained solid in an air atmosphere to obtain the spinel oxide growing along the (110) crystal face direction. The sample is also processed by an etching method to synthesize a catalyst with a large number of surface oxygen vacancies; the etching treatment and the post-treatment processes are the same as those in (2) and (3) in the step (a), and the sample has large specific surface area and many surface defects and can be applied to catalytic synthesis gas conversion.

Specific samples and their preparation conditions are shown in table 2 below. Likewise, surface oxygen vacancies are defined as (1-molar amount of oxygen atoms to theoretical stoichiometric oxygen molar content).

TABLE 2 preparation of spinel materials and their Property parameters

(V) synthesizing nano FeAl with high specific surface area and high surface energy₂O₄、CoAl₂O₄Spinel: the preparation process is the same as (2) in the fourth step, except that the precursor of Zn is replaced by the corresponding precursor of Fe or Co, and the precursor is one of ferric nitrate, ferric chloride and ferric citrate or one of cobalt nitrate, cobalt chloride and cobalt acetateAnd (4) seed preparation.

Synthesizing a catalyst with a large number of surface oxygen vacancies in the etching treatment process as described in the preparation process of the products ZnO3 and ZnO 5 in the step (2) in the step (I); 77% and 51% of surface oxygen vacancies;

the corresponding products are defined as spinel 6, spinel 7;

(VI) Cr₂O₃、Al₂O₃Or ZrO₂Dispersed active metal oxide

With Cr₂O₃、Al₂O₃Or ZrO₂As carrier, preparing Cr by precipitation deposition₂O₃、Al₂O₃Or ZrO₂Dispersed active metal oxide. Taking the preparation of dispersed ZnO oxide as an example, commercial Cr is used₂O₃、Al₂O₃Or ZrO₂The carrier is pre-dispersed in the base solution, and then zinc nitrate is adopted as the raw material to be mixed with sodium hydroxide precipitator 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 oxide dispersed as a carrier (the content of the dispersant in the catalyst A was 0.1 wt%, 10 wt%, 90wt% in this order).

The etching process is the same as the preparation process of the products ZnO3, ZnO 5 and ZnO8 in the step (2) in the step (I), and the catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 65%, 30%, 25%; the post-treatment process is the same as that in 3) in the (a);

the corresponding product is defined as dispersed oxide 1-3 from top to bottom;

cr can be obtained in the same manner as described above₂O₃、Al₂O₃Or ZrO₂MnO oxide dispersed as a support (the content of the dispersant in the catalyst A is 5 wt%, 30 wt%, 60 wt% in this order), surface oxygen vacancies 62%, 27%, 28%; the corresponding product is defined as dispersed oxide 4-6 from top to bottom.

Secondly, preparing the molecular sieve with the AEL topological structure, namely the component B:

1) the preparation process comprises the following steps:

the following steps: the preparation method of one or more than two molecular sieves of TON, MTT or MRE is disclosed in the following references:

TON or MTT or MRETON: KOH (2.39g in 10.89g water), aluminum sulfate (1.06g in 10.89g water), octanediamine (6.23g in 43.6g water), silica sol (28.5g in 16.14g water), in a ratio of 8.9K 2O/1.0 Al2O 3/90 SiO 2/3K 2 SO 4/27.3DAO/3588H 2O, was added to the beaker and stirred for 12 hours, then placed in a tetrafluoroethylene-lined hydrothermal kettle at 160 deg.C for 3.5 days, spin-crystallized at 37 rpm. And after the product is centrifugally washed, dried and roasted, carrying out ion exchange on 1M ammonium nitrate solution at 70 ℃ for 2h, and then, centrifugally washing, drying and roasting again to obtain the product.

MTT: 0.5g of aluminum sulfate is dissolved in 60.75g of water, and 4.5g of white carbon black is added after 0.26g of NaOH and 2.4g of pyridine are added. Stirring for 2 hr, transferring to hydrothermal kettle with tetrafluoroethylene lining at 160 deg.C, and crystallizing for 3 days. And after the product is centrifugally washed, dried and roasted, carrying out ion exchange on 1M ammonium nitrate solution at 70 ℃ for 2h, and then, centrifugally washing, drying and roasting again to obtain the product.

MRE: PMBr2 as a template, 0.22g of aluminum nitrate was dissolved in 17.93g of water, 0.64g of 50 wt% sodium hydroxide was added, and 1.24g of the template was added. Finally, 4.96g TEOS (tetraethyl orthosilicate) is added and stirred for 2h, and then the mixture is transferred into a 45ml hydrothermal kettle and is rotated and crystallized at the temperature of 160 ℃ for 7 days at the speed of 37 rpm. After quenching, the product is centrifugally washed, dried and roasted. And similarly, after ion exchange is carried out for 2h at 70 ℃ by using 1M ammonium nitrate solution, the product is obtained by centrifuging, washing, drying and roasting again.

Preparation of catalyst

The component A and the component B 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 the atmosphere or directly in the air, wherein the atmosphere is as follows: a) nitrogen and/or inertnessGas, b) a mixture of hydrogen and nitrogen and/or an inert gas, wherein the volume of hydrogen in the mixture is 5-50%, c) a mixture of CO and nitrogen and/or an inert gas, wherein the volume of CO in the mixture 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.

Mechanical stirring: in the stirring tank, the components A and B are mixed by a stirring rod, and the mixing degree and the relative distance of the components A and B 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 components A and B are dispersed and mixed. By controlling the abrasive (the material can be stainless steel, agate and quartz, and the size range is 5mm-15 mm). The particle size and relative distance of the catalyst can be adjusted according to the proportion of the catalyst (mass ratio range: 20-100: 1).

A shaking table mixing method: premixing the components A and B, and filling the mixture into a container; the components A and B are mixed by controlling the reciprocating oscillation or the circumferential oscillation of the shaking table; by adjusting the oscillation speed (range: 1-70 rpm) and time (range: 5min-120min), uniform mixing is achieved and the relative distance is adjusted.

Mechanical grinding method: premixing the components A and B, and filling the mixture into a container; under a certain pressure (range: 5 kg-20 kg), the mixed catalyst is relatively moved by the grinder (speed range: 30-300 r/min), so as to adjust the particle size and relative distance of the catalyst and realize uniform mixing.

Specific catalyst preparations and their parametric characteristics are shown in table 6.

TABLE 5 preparation of the catalyst and its parametric characterization

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).

The catalyst of the present invention is placed in a fixed bed reactor, the air in the reactor is replaced with Ar, and then H is added₂Raising 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.

1. The reaction performance can be varied by varying the temperature, pressure and space velocity. The selectivity of gasoline fraction in the product is high and can reach 50-80%, and the rest product is mainly low-carbon olefin with high added value, and the selectivity of the low-carbon olefin can reach 10-30%.

Compared with the traditional Fischer-Tropsch synthesis technology, the selectivity of the byproduct methane is extremely low and is lower than 10 percent; the gasoline composition mainly comprises high-octane-value isomeric hydrocarbons and aromatic hydrocarbons, straight-chain hydrocarbons have low selectivity, and the oil product quality is high.

TABLE 6 use of the catalysts and their effectiveness

The ZnO in the catalyst of comparative example 1 has no oxygen vacancies and thus has a very low activity.

The ZnO in the catalyst of comparative example 2 was completely reduced to the metallic state, resulting in high selectivity of methane in the product.

The catalyst adopted in the comparative example 3 is a component A of ZnCo metal, a component B of TON, and the molar ratio of ZnCo is 1:1, the mass ratio of ZnCo to TON is 1:1, the rest parameters and the mixing process are the same as the catalyst A.

The catalyst used in comparative example 4 was MgO with no oxygen holes on the surface, component B was MRE, and the other parameters and mixing process were the same as catalyst A.

Comparative example 5 used a catalyst in which the molecular sieve was a commercial SAPO-34 available from southern kaiki university catalyst plant.

The catalyst used in comparative example 6 was a small pore molecular sieve having LEV structure.

The catalyst used in comparative example 7 had a distance between the metal oxide and the molecular sieve of 30mm, and the remaining parameters and mixing were the same as for catalyst a.

In the catalyst adopted in the comparative example 8, the metal oxide is positioned in the pore channel of the molecular sieve, the metal oxide and the molecular sieve are in close contact, and the rest parameters are the same as those of the catalyst A.

Comparative example 9 a carbon nanotube-confined iron catalyst with an iron loading of 10%, 270 ℃, 51bar, 14000h^-1Wherein the selectivity of the C5+ product in hydrocarbons is 29%.

The reaction results show that:

the first description is as follows:

the reaction results of comparative examples 5 and 6 show that the topology is critical to the modulation of product selectivity, with SAPO34 having pore sizes

Is suitable for the generation of C2-C4 hydrocarbons, wherein the C3 hydrocarbon products are the most; and LEV is also an 8-membered ring with an orifice size of

The cage size is smaller than sapo34 and therefore the methane in the product is very high.

The molecular sieves used in the method are all 10 circular ring orifices and have one-dimensional pore channel structures, the advantages of molecular sieves with other structures are shown, the products are mainly gasoline fractions, and the content of isoparaffin is high. And simultaneously co-producing low-carbon olefin.

And II, explanation:

The results of the reactions of comparative examples 7 and 8 show that both distances far and too close result in very high methane selectivity, which is detrimental to the formation of gasoline fractions.

From the above table, it can be seen that the structure of the molecular sieve, including the topological structure, and the distance matching between the metal oxide and the molecular sieve are very important, and directly affect the selectivity of gasoline fraction and low-carbon olefin.

Claims

1. A catalyst, characterized by: the catalyst is a composite catalyst A + B, the component A is an active metal oxide, and the component B is a molecular sieve with one or more than two structures of TON, MTT and MRE; the active metal oxide is MnO or Cr₂O₃、MnCr₂O₄、MnAl₂O₄、MnZrO₄、ZnO、ZnCr₂O₄、ZnAl₂O₄、CeO₂、CeZr₂O₄、CoAl₂O₄、FeAl₂O₄One or more than two of them;

the catalyst component B is a 10-element orifice one-dimensional pore channel, has one or more than two molecular sieves in TON, MTT and MRE structures, and is composed of H, O, Si and Al; the distance between the active metal oxide of the component A and the geometric center of the particle of the component B is between 20nm and 10 mm; the active metal oxide consists of crystal grains of 5-30nm in size, and has a large number of oxygen vacancies in the range of 0.3nm in depth from the surface of the crystal grains to the inside of the crystal grains, wherein the percentage concentration of surface oxygen vacancies is defined as 100% based on the theoretical stoichiometric oxygen molar content as 100%, the molar amount of oxygen atoms is the percentage of the theoretical stoichiometric oxygen molar content, and the concentration of oxygen vacancies is 20-90%.

2. The catalyst of claim 1, wherein: component B also contains Al₂O₃Graphite, SiO₂，ZrO₂，TiO₂，Cr₂O₃，Ga₂O₃，CaO，MgO，CeO₂，In₂O₃，SnO₂One or more than two dispersants, wherein the content of the dispersant is 0-50 wt%.

3. The catalyst of claim 1, wherein: the catalyst component A is MnO and Cr₂O₃、MnCr₂O₄、MnAl₂O₄、MnZrO₄、ZnAl₂O₄、CeO₂、CeZr₂O₄、CoAl₂O₄、FeAl₂O₄One or more than two of them.

4. The catalyst of claim 1, wherein: the catalyst component A is MnO and Cr₂O₃、MnCr₂O₄、MnAl₂O₄、MnZrO₄、CeO₂、CoAl₂O₄、FeAl₂O₄One or more than two of them.

5. The catalyst of claim 1, wherein: the spacing between the active metal oxide of component A and the geometric center of the particles of component B is between 50nm and 1 mm.

6. The catalyst of claim 1, wherein: the weight ratio of the component A to the component B is 0.1-20 times.

7. The catalyst of claim 1, wherein: the weight ratio of the component A to the component B is 0.3-5 times.

8. The catalyst of claim 1, wherein: the oxygen vacancy concentration is 40-90%.

9. A catalyst according to claim 1 or 2, wherein: a dispersant is also added in the catalyst A, and the dispersant is Al₂O₃、Cr₂O_3、ZrO₂、TiO₂One or two of the active metal oxides are dispersed in a dispersant, the content of the dispersant in the catalyst A is 10-90wt%, and the balance is the active metal oxide.

10. A method for preparing liquid fuel and co-producing low-carbon olefin by directly converting synthesis gas is characterized by comprising the following steps: the synthesis gas is used as reaction raw material, conversion reaction is carried out on a fixed bed or a moving bed, and the adopted catalyst is the catalyst of any one of claims 1 to 9.

11. The method of claim 10, wherein: the pressure of the synthesis gas is 0.1-10 MPa; the reaction temperature is 300-600 ℃; space velocity of 300-^-1。

12. The method of claim 11, wherein: the pressure of the synthesis gas is 1-8 MPa; the reaction temperature is 300-500 ℃.

13. A method according to claim 10 or 11, characterized by: the reaction is carried out by synthesisGas is H₂a/CO mixture, further comprising other gases; the other gases comprising CO₂，N₂Ar, He, methane, ethane, ethylene; the volume content of other gases is 0.1-10%; h₂The ratio of/CO is 0.2-3.5.

14. A method according to claim 10 or 11, characterized by: h₂The ratio of/CO is 0.3-2.5.