CN108940355B - Alkali modified catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction - Google Patents

Alkali modified catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction Download PDF

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CN108940355B
CN108940355B CN201710382261.8A CN201710382261A CN108940355B CN 108940355 B CN108940355 B CN 108940355B CN 201710382261 A CN201710382261 A CN 201710382261A CN 108940355 B CN108940355 B CN 108940355B
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catalyst
mixed gas
selectivity
reaction
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CN108940355A (en
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潘秀莲
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 the field of direct conversion of carbon monoxide hydrogenation to prepare ethylene, and particularly relates to an alkali-modified catalyst and a method for preparing ethylene by carbon monoxide hydrogenation reaction, wherein a mixed gas of carbon monoxide and hydrogen is used as a reaction raw material, the 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 an organic alkali-modified molecular sieve with an MOR structure; the weight ratio between the active ingredient in the A component and the B component is in the range of 0.1-20, preferably 0.3-8. The reaction process has high product yield and selectivity, the selectivity of C2-C3 olefin is as high as 86-92%, the hydrocarbon product containing more than 4C atoms is less than 7%, the selectivity of the byproduct methane is extremely low (< 5%), the selectivity of ethylene and the space-time yield are obviously improved, the selectivity reaches 75-85%, and the method has good application prospect.

Description

Alkali modified catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction
Technical Field
The invention belongs to the field of preparation of low-carbon olefin high-value chemicals by carbon monoxide hydrogenation, and particularly relates to an alkali-modified catalyst and a method for preparing ethylene by carbon monoxide hydrogenation.
Background
Ethylene is a very important basic chemical raw material, is one of the chemical products with the largest yield in the world, and the ethylene industry is the core of the petrochemical industry and plays an important role in national economy. The lower olefin is an olefin having 4 or less carbon atoms. The low-carbon olefin represented by ethylene and propylene is a very important basic organic chemical raw material, and with the rapid growth of the economy of China, the ethylene industry of China develops rapidly and occupies an important position in the ethylene market of the world. For a long time, the market of low-carbon olefins is in short supply. At present, the petrochemical route of naphtha and light diesel oil cracking or the ethane cracking technology are mainly adopted for producing ethylene, and because petroleum in China depends on import for a long time, the energy safety in China has higher risk, and the development of the petroleum-independent ethylene production technology is urgently needed. The method comprises the following steps of (1) converting coal, natural gas, biomass, other renewable materials and the like into a mixed gas of carbon monoxide and hydrogen, namely synthesis gas, wherein the proportion of the carbon monoxide to the hydrogen in the synthesis gas is different along with different raw materials; the synthesis gas is taken as a raw material, and after the proportion of carbon monoxide and hydrogen is adjusted to a proper value, the carbon monoxide and the hydrogen are directly prepared into the low-carbon olefin with the carbon atom number less than or equal to 4 through the Fischer-Tropsch synthesis reaction under the action of a proper catalyst, so that the olefin can be produced in one step, and the route provides an alternative scheme for producing ethylene by a naphtha cracking technology. The process does not need to further prepare olefin from the synthesis gas through methanol or dimethyl ether like an indirect process, simplifies the process flow and greatly reduces the investment.
The direct preparation of low-carbon olefin by Fischer-Tropsch synthesis is one of the research hotspots for directly producing olefin by synthesis gas. In patent CN1083415A published by institute of chemical and physical sciences in the chinese academy of sciences, a group IIA alkali metal oxide such as MgO or an iron-manganese catalyst system supported by a high-silicon zeolite molecular sieve (or phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, so that high activity (90% of CO conversion) and high selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction pressure of 1.0-5.0 Mpa and a reaction temperature of 300-400 ℃ in the preparation of low-carbon olefin from synthesis gas. In patent ZL03109585.2 filed by Beijing university of chemical industry, a vacuum impregnation method is adopted to prepare a Fe/activated carbon catalyst taking manganese, copper, zinc, silicon, potassium and the like as additives for the reaction of preparing low-carbon olefin from synthesis gas, and under the condition of no circulation of raw material gas, the conversion rate of CO is 96 percent, and the selectivity of the low-carbon olefin in hydrocarbon is 68 percent. The catalyst reported above adopts metallic iron or iron carbide as active component, the reaction follows the chain growth reaction mechanism of metal surface, the selectivity of the product low carbon olefin is low, especially the selectivity of single product such as ethylene is lower than 30%. In 2016, Sunrichan researchers and Chongxian researchers at Shanghai high research institute reported a preferential exposure [101 ]]And [020]The manganese-assisted cobalt carbide-based catalyst realizes the selectivity of low-carbon olefin of 60.8 percent and the selectivity of methane of 5 percent under the CO conversion rate of 31.8 percent. But the ethylene single selectivity was less than 20%. Alumina-loaded ZnCr was reported by the institute of chemical and physical research, the university of Chinese academy of sciences and the Panele team2O4Oxide and multi-stage pore SAPO-34 molecular sieve composite bifunctional catalyst (Jianao et al, Science 3)51(2016)1065-1068), the selectivity of the low-carbon olefin of 80 percent is realized when the CO conversion rate is 17 percent, but the selectivity of the ethylene is lower than 30 percent. In their patent 201610600945.6, the use of a dual-function catalyst containing oxygen vacancies in combination with a MOR molecular sieve for the one-step olefin production of syngas increased the selectivity to ethylene to 30-75%, but the use of this technique was hindered by the presence of a large amount of hydrocarbons with carbon numbers in excess of 3 as by-products. The invention further modulates the acidity characteristic of the MOR molecular sieve to further reduce the selectivity of the methane byproduct and further reduce the selectivity of the hydrocarbon products above C4.
Disclosure of Invention
The invention solves the problems: the invention overcomes the defects of the prior art and provides a base modified catalyst and a method for preparing ethylene by carbon monoxide hydrogenation reaction, the catalyst can catalyze the carbon monoxide hydrogenation to directly convert into low-carbon olefin with high selectivity, the selectivity of C2-C3 olefin is as high as 86-92%, the selectivity of single product ethylene is as high as 75-85%, the selectivity of methane is lower than 5%, and the selectivity of C4 and above hydrocarbons is lower than 7%.
The technical scheme of the invention is as follows: a catalyst is prepared by compounding a component A and a component B in a mechanical mixing mode, wherein the active component of the component A is a metal oxide, and the component B is a molecular sieve with an MOR topological structure, and is characterized in that: in the component B, the molecular sieve with MOR topological structure is modified by using an organic base, and the organic base is a heterocyclic compound.
The heterocyclic compound can be furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine and acridine. The heterocyclic compound may have one or two or more substituents selected from methyl, ethyl, amino and nitro. Meta, para substitution is preferred. The heterocyclic compound can prevent organic base molecules from entering 8-ring pore channels, and selectively occupy the B acid sites of 12 rings. And the use of meta-para-substituted molecules can avoid the problems of weak contact between organic base and B acid and weak adsorption caused by steric hindrance effect.
The weight ratio of the active ingredients in the component A to the component B is 0.1-20 times, the weight ratio is preferably 0.3-8, the components cooperate to enable the reaction to effectively proceed, and too much or too little of the components is harmful to the reaction.
The metal oxide is composed of crystal grains having a size of 5 to 30nm, and a large number of oxygen vacancies are present in the range of a depth of 0.3nm from the crystal grain surface to the crystal grain interior direction, i.e., the molar amount of oxygen atoms is 80% or less of the theoretical stoichiometric oxygen molar content, preferably the molar amount of oxygen atoms is 80 to 10%, more preferably 60 to 10%, most preferably 50 to 10% of the theoretical stoichiometric oxygen molar content; surface oxygen vacancies are defined as (1-molar amount of oxygen atoms to theoretical stoichiometric oxygen molar content), corresponding to oxygen vacancy concentrations of preferably 20-90%, more preferably 40-90%, and most preferably 50-90%, with too few oxygen vacancies being detrimental to CO activation and too many being liable to result in excessive hydrogenation reducing olefin selectivity.
The component A is also added with a dispersant which is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more than two of the metal oxides are dispersed in the dispersant, the content of the dispersant in the component A is 0.05-90wt%, preferably 0.05-25wt%, and the rest is the metal oxide, and the inert dispersant can help the dispersion of the active component and improve the utilization efficiency of the active component.
The MOR topological structure is an orthorhombic system, has a one-dimensional pore channel structure of oval through pore channels which are parallel to each other, and comprises 8 circular ring pockets and 12 circular ring one-dimensional pore channels.
The framework element composition of the molecular sieve with MOR topological structure can be one or more than two 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.
The preparation process of the metal oxide comprises the following steps: soaking metal oxide in one or more of etching agents such as oleic acid, urotropine, ethylenediamine, ammonia water, hydrazine hydrate and the like; heating the suspension at 100-150 deg.C for 30-90 min, taking out, washing and filtering to obtain metal with large amount of surface oxygen holesAn oxide material; drying and reducing the filtered substance 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 mixed gas is 100/10-0/100, and the treatment is carried out for 0.5-5 hours at the temperature of 20-350 ℃.
The method for modifying the organic alkali comprises the steps of firstly controlling the temperature on a vacuum line to carry out dehydration and degassing treatment on a molecular sieve sample at the temperature of 350-500 ℃ and under the pressure of 1Pa-10-5Pa, time is 4-24 h, the degassed molecular sieve is further exposed in organic alkali atmosphere of 10Pa-100kPa or organic alkali atmosphere diluted by inert gas, the adsorption temperature is controlled to be between room temperature and 300 ℃, and inorganic gas is used for purging at 200-330 ℃ for 30min-12h to obtain the organic alkali modified molecular sieve.
The mechanical mixing can be carried out by one or more than two of mechanical stirring, ball milling, shaking table mixing and mechanical grinding.
A process for preparing ethylene by directly converting the mixture of CO and hydrogen features that the mixture of CO and hydrogen is used as raw material and the carbon dioxide can be used in a fixed or moving bed for high-selectivity reaction to generate ethylene.
The pressure of the mixed gas is 0.5-10MPa, preferably 1-8MPa, and more preferably 2-8 MPa; the reaction temperature is 300-600 ℃, preferably 300-450 ℃; airspeed of 300-10000h-1Preferably 500--1More preferably 500--1Higher space-time yields can be obtained.
The mixed gas H for reaction2Higher space-time yields and selectivities are achieved with a/CO molar ratio of from 0.2 to 3.5, preferably from 0.3 to 2.5. The synthesis gas may also contain CO2In which CO is2The volume concentration in the synthesis gas is 0.1-50%.
The bifunctional composite catalyst is used for directly converting synthesis gas into ethylene or C2-C3 olefin by one-step method, wherein the selectivity of the C2-C3 olefin is as high as 86-92%, the selectivity of the ethylene is 75-85%, meanwhile, the selectivity of the byproduct methane is extremely low (< 5%), and the selectivity of the C4 and above hydrocarbons is lower than 7%.
The invention has the following advantages:
(1) the invention is different from the traditional technology (MTO for short) for preparing low-carbon olefin by methanol, and realizes the one-step direct conversion of synthesis gas to prepare ethylene.
(2) The single ethylene product in the product has high selectivity which can reach 75-85%, and the space-time yield is high (the olefin yield is as high as 1.42 mmol/h.g), and the product is easy to separate and has good application prospect.
(3) The catalyst of the invention is different from the catalyst of the patent applications 201610600945.6 and 201710129620.9 in that the component B in the catalyst is modified by heterocyclic organic alkali, the selectivity of the single component ethylene obtained by catalytic synthesis gas conversion is up to 75-85%, the methane selectivity is lower than 5%, and the selectivity of hydrocarbons above C4 is greatly inhibited, while the reaction result of the catalyst of the invention in the 201610600945.6 and 201710129620.9 is wider, and the methane and the hydrocarbons above C4 are more, so the condition can not be met.
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 component A
Synthesizing a ZnO material with a polar surface by an etching method:
(1) 4 parts, 0.446g (1.5mmol) of Zn (NO) are weighed out separately3)2·6H2And O, respectively weighing 0.300g (7.5mmol), 0.480g (12mmol), 0.720g (18mmol) and 1.200g (30mmol) of NaOH in 4 containers, sequentially adding the weighed materials into the 4 containers, respectively weighing 30ml of deionized water, adding the weighed materials into the 4 containers, and stirring for more than 0.5h to uniformly mix the solution. Heating to 160 deg.C, and reactingThe reaction time is 20 hours, and the precipitate is decomposed 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;
the product, 0.480g (12mmol) of NaOH used therein, was subjected to the following treatment:
(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 5wt% 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 reducing
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 surface oxygen vacancies are defined as (1-molar amount of oxygen atoms to theoretical stoichiometric oxygen molar content).
TABLE 1 preparation of ZnO materials and their parametric properties
Figure BDA0001305425930000051
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, ZnO4 having no oxygen vacancies on the surface, which was not etched in the step (2), and metallic Zn 5 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 that of the product (1) corresponding to the amount of 0.480g (12mmol) of NaOH and the product (3) in the step (A), except that the precursor of Zn is replaced by the corresponding precursor of Mn, which can be one of manganese nitrate, manganese chloride and manganese acetate, and is manganese nitrate.
The etching treatment process is the same as the preparation process of the product ZnO 3 in the step (2) in the step (I), and a catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 67%;
the corresponding product is defined as MnO 1;
(III) Synthesis of CeO with polar surface by etching2Materials: the preparation process is the same as that of the product (1) corresponding to the amount of 0.480g (12mmol) of NaOH and the product (3) in the step (A), except that the precursor of Zn is replaced by the corresponding precursor of Ce, and the precursor of Zn can be one of cerium nitrate, cerium chloride and cerium acetate, and is cerium nitrate.
The etching treatment process is the same as the preparation process of the product ZnO 3 in the step (2) in the step (I), and a catalyst with a large number of surface oxygen vacancies is synthesized; surface oxygen vacancies 56%;
the corresponding product was defined as CeO 1;
(IV) 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
Figure BDA0001305425930000061
(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, which can be one of ferric nitrate, ferric chloride and ferric citrate or one of cobalt nitrate, cobalt chloride and cobalt acetate, here, ferric nitrate and cobalt nitrate.
The etching treatment process is the same as the preparation process of the product ZnO 3 in the step (2) in the step (I), and a catalyst with a large number of surface oxygen vacancies is synthesized; 77% and 51% of surface oxygen vacancies;
the corresponding products are defined as spinel 6, spinel 7;
(VI) Cr2O3、Al2O3Or ZrO2Dispersed metal oxide
With Cr2O3、Al2O3Or ZrO2As carrier, preparing Cr by precipitation deposition2O3、Al2O3Or ZrO2A dispersed 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 0.1M, Zn2+Mole with precipitantThe part ratio is 1: 6; then aging at 120 deg.C for 24 hr to obtain Cr2O3、Al2O3Or ZrO2ZnO oxide dispersed as a carrier.
The etching process is the same as the preparation process of the product ZnO 3 in the step (2) in the step (I), and a catalyst with a large number of surface oxygen vacancies is synthesized (the content of the dispersant in the component A is 0.2 wt%, 10 wt% and 90wt% in sequence); 25%, 30% and 65% of surface oxygen vacancies; the post-treatment process is the same as that of the step (3) in the step (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 carrier (the content of the dispersant in the catalyst A is 7 wt%, 30 wt% and 60 wt% in this order), surface oxygen vacancies 22%, 47% and 68%; the corresponding product is defined as dispersed oxide 4-6 from top to bottom.
Preparation of component II and component B (molecular sieve with MOR topological structure)
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 arranged on the side edge of a main hole of each 12 circular ring and communicated with each other.
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 a mordenite sample, wherein the label of the mordenite sample is Na-MOR.
Mixing Na-MOR with 1mol/L ammonium chloride solution, stirring at 90 ℃ for 3h, washing, drying, continuously roasting at 450 ℃ for 6h for 4 times to obtain hydrogen-type 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;
the O element of partial skeleton is connected with H, and the corresponding products are sequentially defined as MOR 1-8;
TABLE 3 preparation of molecular sieves with MOR topology and their performance parameters
Figure BDA0001305425930000081
Dehydrating and degassing the prepared molecular sieve under vacuum at 400 deg.C and 10 deg.C-4And after Pa and 10 hours, cooling to 300 ℃, introducing organic base gas of 200Pa into the vacuum cavity, balancing for 10 hours, and desorbing for 1 hour at the same temperature.
MOR1 was used sequentially: furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine and acridine to obtain MOR 9-21.
To illustrate the modification of the substituent-containing heterocyclic compounds, MOR22 was obtained by subjecting MOR2 to 1-methylfuran; MOR3 was treated with 1-methylpyrrole to give MOR 23; MOR4 was treated with 3, 5-lutidine to give MOR 24; MOR5 was treated with 4-ethylpyridine to give MOR 25; MOR6 was treated with 3-methylquinoline to give MOR 26; MOR7 was treated with 4-methylindole to give MOR 27; MOR8 was treated with 5-methylacridine to give MOR 28.
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 inert gas, b) hydrogen with nitrogen and/or inert gasA mixture of natural gases, wherein the volume of hydrogen in the mixture is 5-50%, c) a mixture of CO and nitrogen and/or inert gases, 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 A component and the B component are mixed by a stirring rod, and the mixing degree and the relative distance of the A component and the B component 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 A component and the B component are dispersed and mixed. The particle size and relative distance of the catalyst can be adjusted by controlling the proportion (mass ratio range: 20-100:1) of the abrasive (material can be stainless steel, agate and quartz, size range: 5mm-15mm) and the catalyst.
A shaking table mixing method: premixing the component A and the component B, and filling the mixture into a container; mixing the component A and the component B 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 component A and the component 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 4.
TABLE 4 preparation of the catalyst and its parametric characterization
Figure BDA0001305425930000091
Figure BDA0001305425930000101
Figure BDA0001305425930000111
Figure BDA0001305425930000121
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. The selectivity of ethylene and propylene in the product is up to 83-90%, and the conversion rate of the raw material is 10-60%; due to the effective synergistic effect of the molecular sieve and the oxide, the generation of a large amount of methane is avoided, the selectivity of the methane is lower than 5 percent, and the selectivity of ethylene reaches 75-85 percent.
TABLE 5 use of the catalyst and its Effect
Figure BDA0001305425930000122
Figure BDA0001305425930000131
Figure BDA0001305425930000141
The catalyst adopted in the comparative example 3 is component A metal ZnCo + MOR26, the mole ratio of ZnCo is 1:1, ZnCo and 1 are mixed according to the mass ratio of 1:1, the rest parameters and the mixing process are the same as the catalyst C.
Comparative example 4 the catalyst used was surface oxygen-free-cavity TiO2+ MOR27, the remaining parameters and the mixing were equivalent to catalyst C.
The reaction results of comparative examples 5 and 6 show that MOR post-treatment with organic base has a significant effect on the regulation of catalytic performance, and compared with a catalyst regulated without organic base, the regulated catalyst further reduces the selectivity of methane and hydrocarbons above C4, and has higher space-time yield and ethylene selectivity.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.

Claims (19)

1. A catalyst is composed of a component A and a component B, wherein the component A and the component B are compounded together in a mechanical mixing mode, the active component of the component A is a metal oxide, and the component B is a molecular sieve with an MOR topological structure, and is characterized in that: in the component B, the molecular sieve with the MOR topological structure is modified by using an organic base, and the organic base is a heterocyclic compound; the heterocyclic compound is furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine and/or acridine;
the metal oxide is MnO or MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One or more than two of them;
the framework element composition of the MOR topological structure molecular sieve is one or more than two 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;
the method for modifying the organic base comprises the following steps: firstly, the temperature is controlled on a vacuum line to carry out dehydration and degassing treatment on a molecular sieve sample at the temperature of 350--5 Pa, time is 4-24 h, the degassed molecular sieve is further exposed in organic alkali atmosphere of 10Pa-100kPa or organic alkali atmosphere diluted by inert gas, the adsorption temperature is controlled to be between room temperature and 300 ℃, and inorganic gas is used for purging at 200-330 ℃ for 30min-12h to obtain the organic alkali modified molecular sieve.
2. The catalyst of claim 1, wherein: the heterocyclic compound is furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine and/or acridine with one or more than two substituents of methyl, ethyl, amino and nitro.
3. The catalyst of claim 2, wherein: the heterocyclic compound is furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine and/or acridine with one or more substituents of methyl, ethyl, amino and nitro at meta-position and/or para-position.
4. The catalyst of claim 1, wherein: in the active components of the component A, the metal oxides are MnO and MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One or more than two of them.
5. The catalyst of claim 1, wherein: in the active components of the component A, the metal oxides are MnO and MnCr2O4、MnAl2O4, MnZrO4、CeO2、CoAl2O4、FeAl2O4One or more than two of them.
6. The catalyst of claim 1, wherein: the weight ratio of the active component in the component A to the component B is 0.1-20.
7. The catalyst of claim 1, wherein: the weight ratio of the active component in the component A to the component B is 0.3-8.
8. The catalyst of claim 1, wherein: the metal oxide has surface oxygen vacancies in the range of 0.3nm in depth from the surface of the crystal grains to the inner part of the crystal grains, and the percentage content of the surface oxygen vacancies is more than 20 percent.
9. The catalyst of claim 8, wherein: the percentage content of the surface oxygen vacancies is 20-90%.
10. The catalyst of claim 8, wherein: the percentage content of the surface oxygen vacancies is 40-90%.
11. The catalyst of claim 8, wherein: the percentage content of the surface oxygen vacancies is 50-90%.
12. The catalyst of any one of claims 1 to 11, wherein: the component A is also added with a dispersant, and the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more than two of the components, the metal oxide is dispersed in the dispersant, the content of the dispersant in the component A is 0.05 to 90 weight percent, and the rest is the metal oxide.
13. The catalyst of claim 12, wherein: the component A is also added with a dispersant, and the content of the dispersant in the component A is 0.05-25 wt%.
14. A method for preparing ethylene by carbon monoxide hydrogenation reaction is characterized in that: the method takes the mixed gas of carbon monoxide and hydrogen as reaction raw materials, and carries out conversion reaction on a fixed bed or a moving bed to obtain a low-carbon olefin product with ethylene as the main component, wherein the adopted catalyst is the catalyst in any one of claims 1 to 13.
15. The method of claim 14, wherein: the pressure of the mixed gas is 0.5-10 MPa; the reaction temperature is 300-600 ℃; airspeed of 300-10000h-1。
16. The method of claim 15, wherein: the pressure of the mixed gas is 1-8 MPa; the reaction temperature is 300-400 ℃; the space velocity is 500--1。
17. The method of claim 15, wherein: the pressure of the mixed gas is 2-8 MPa; the space velocity is 500-6000h-1。
18. The method according to claim 14 or 15, characterized in that: the mixed gas contains H2Mixed gas with CO, H2The mol ratio of/CO is 0.2-3.5; the mixed gas also contains CO2In which CO is2The volume concentration in the mixed gas is 0.1-50%.
19. The method of claim 18, wherein: the mixed gas contains H2Mixed gas with CO, H2The mol ratio of/CO is 0.3-2.5.
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