CN116550373A - For CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof - Google Patents

For CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof Download PDF

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CN116550373A
CN116550373A CN202310550208.XA CN202310550208A CN116550373A CN 116550373 A CN116550373 A CN 116550373A CN 202310550208 A CN202310550208 A CN 202310550208A CN 116550373 A CN116550373 A CN 116550373A
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catalyst
molecular sieve
zsm
roasting
supported
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成康
吴恭立
刘素含
韩瑶瑶
张庆红
王野
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Xiamen University
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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Abstract

For CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof, comprising nuclear shell catalyst for synthesizing methanol and methanol aromatic structureThe catalyst is formed by taking a CuZn-based or supported Pd-based catalyst as a core and taking an inert SSZ-13 molecular sieve or AlPO-34 molecular sieve as a shell; the methanol aromatization catalyst comprises one of a supported Zn/ZSM-5 molecular sieve, a supported Ga/ZSM-5 molecular sieve and an H-MCM-22 molecular sieve. The invention controls the diffusion paths of reactant micromolecules and product macromolecules through the inert molecular sieve shell, and ensures the full conversion of olefin intermediates. The preparation method is simple and has CO/CO 2 High conversion, liquid fuel (C) 5+ Hydrocarbons) and aromatic hydrocarbon, and the catalyst stability is good, and shows excellent application prospect.

Description

For CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof
Technical Field
The invention relates to CO/CO 2 In the field of catalytic conversion, in particular to a catalyst for CO/CO 2 An integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and a preparation method thereof.
Background
With the rapid development of national economy, liquid fuel (C 5+ Hydrocarbons) and aromatics will increase year by year. At present, the production of liquid fuels such as gasoline, diesel oil and aviation fuel oil and aromatic hydrocarbons depends on petroleum resources. The energy structure of our country is characterized by "rich coal, lean oil, little gas", the external dependence of petroleum and natural gas is high. With the gradual exhaustion of global petroleum resources, the utilization of non-oil-based carbon resources and even CO with abundant reserves is urgently needed 2 Clean carbon-based liquid fuels and chemicals are produced. Non-oil-based carbon resources such as coal and biomass are complex in composition, difficult to directly chemically convert, and often produce liquid fuels and chemicals by syngas indirect processes. With the rapid development of renewable energy sources, CO is converted by green hydrogen 2 Conversion to liquid fuels and chemicals will also become viable.
CO/CO at present 2 The process of hydrogenation to produce liquid fuels and chemicals is mainly through two indirect paths: (1) Preparing linear hydrocarbon by Fischer-Tropsch synthesis reaction, and preparing liquid fuel and chemicals by hydrocracking or reforming reaction; (2) CO/CO 2 Hydrogenation to prepare methanol, and preparing hydrocarbon from methanol by molecular sieve catalyst A compound. However, the Fischer-Tropsch synthesis reaction products are wide in distribution and difficult to separate, and the methanol indirect method has complex path process and high energy consumption. In CO/CO 2 And H 2 Has important significance for directly synthesizing high-quality liquid fuel and aromatic hydrocarbon from raw materials. Currently, metal (oxide) -molecular sieve bifunctional catalysts are widely used for CO/CO 2 Hydrogenation to prepare liquid fuel and aromatic hydrocarbon. However, this route must use complex metal oxides with a relatively low hydrogenation capacity, such as ZnZrO x 、ZnCrO x 、InZrO x 、ZnGaO x Isocatalytic CO/CO 2 Hydrogenation is methanol, and needs to be carried out under high temperature, the reaction activity is limited, the water gas shift reaction or the reverse water gas shift reaction is strong, the selectivity of the target product liquid fuel and aromatic hydrocarbon is low, and CO 2 The selectivity of byproducts such as/CO is higher. Once the Cu-based catalyst with high activity at low temperature is used as a methanol synthesis component, the low-carbon olefin intermediate generated on the molecular sieve is saturated by hydrogenation and cannot generate a target product. It remains a challenging problem to design catalysts that perform catalytic reactions at low temperatures to produce liquid fuels and aromatics with higher efficiency.
The CuZn-based catalyst and Pd-based catalyst have stronger hydrogenation capability and can be used as CO/CO 2 Low-temperature high-efficiency catalyst for preparing methanol by hydrogenation. But less useful in metal-molecular sieve dual-function catalysts and the main product is a low value saturated alkane (C) 1 -C 4 ) This is because the hydrogenation capacity of the active metals CuZn and Pd is strong, and the low-carbon olefin intermediates for producing liquid fuels and aromatics are preferentially hydrogenated and saturated. Furthermore, neither CO nor CO 2 The methanol is prepared by hydrogenation, and the methanol is limited by thermodynamic equilibrium, so that the conversion rate is difficult to break through by 15%.
Disclosure of Invention
The present invention has for its object to solve the above problems in the prior art, to provide a method for CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof, and the catalyst has CO/CO 2 High conversion rate, high selectivity of liquid fuel and aromatic hydrocarbon, strong carbon deposition resistance and low selectivity of byproducts such as methane.
In order to achieve the above purpose, the invention adopts the following technical scheme:
for CO/CO 2 The integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion comprises a core-shell catalyst for methanol synthesis and a methanol aromatization catalyst, wherein the core-shell catalyst takes a CuZn-based or supported Pd-based catalyst as a core, an inert SSZ-13 molecular sieve or an AlPO-34 molecular sieve as a shell, the CuZn-based catalyst is a CuZnM catalyst modified by a modification element M, and the molar percentage of the components is n (Cu+Zn): n (M) =9-1, and n (Cu): n (Zn) =0.1-10; the mass percentage of metal Pd in the supported Pd-based catalyst is 1% -20%; the methanol aromatization catalyst comprises one of a supported Zn/ZSM-5 molecular sieve, a supported Ga/ZSM-5 molecular sieve and an H-MCM-22 molecular sieve; the mass percentage of metal Zn in the supported Zn/ZSM-5 molecular sieve is 0.05% -10%; the mass percentage of metal Ga in the supported Ga/ZSM-5 molecular sieve is 0.05% -10%. The eight-membered ring molecular sieve of the shell layer on the core-shell catalyst only has the function of regulating and controlling the diffusion of reactant molecules and product molecules, and does not need Acidic sites, therefore, base treatment of SSZ-13 molecular sieves.
The supported Zn/ZSM-5 molecular sieve is prepared from Na-type ZSM-5 molecular sieve through six steps of ammonium exchange, drying, roasting, metal zinc loading, drying and roasting, and the acidity on the ZSM-5 molecular sieve is regulated and controlled by the supported zinc, so that the product selectivity and the reaction activity are improved; the Ga/ZSM-5 molecular sieve is prepared from Na-type ZSM-5 molecular sieve through six steps of ammonium exchange, drying, roasting, gallium loading, drying and roasting, and the acidity on the ZSM-5 molecular sieve is regulated and controlled by gallium loading, so that the product selectivity and the reaction activity are improved; the H-MCM-22 molecular sieve is obtained by carrying out ammonium exchange, drying and roasting on the MCM-22 molecular sieve.
One of the above is used for CO/CO 2 The preparation method of the integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion comprises the following steps:
1) Preparation of CuZnM catalyst: dissolving metal salt in deionized water to prepare a metal salt solution A of Cu+Zn and a metal salt solution B of M, carrying out coprecipitation on the solution A, the solution B and a precipitator under the condition of heating and stirring, and obtaining a CuZnM catalyst after aging, filtering, washing, drying and roasting;
2) Preparing a supported Pd-based catalyst: under the stirring condition, dropwise adding the mixture of ammonia water and ethanol into a metal salt solution corresponding to a carrier oxide, aging, centrifugally separating, washing 3-5 times by deionized water, drying and roasting; dissolving the prepared metal oxide carrier in deionized water, performing ultrasonic treatment, adding Pd precursor solution, stirring at room temperature, and adding new NaBH 4 Continuously stirring the solution, centrifugally separating, collecting the precipitate, washing, drying and roasting to obtain the supported Pd-based catalyst;
3) Soaking a CuZnM catalyst or a supported Pd-based catalyst in silica sol or alumina sol, placing the soaked catalyst particles in a container filled with an inert SSZ-13 molecular sieve or an AlPO-34 molecular sieve, then oscillating for a plurality of times until the catalyst particles are completely wrapped by the molecular sieve, and drying and roasting to obtain a core-shell catalyst;
4) Physically mixing the core-shell catalyst obtained in the step 3) with a methanol aromatization molecular sieve catalyst to obtain the catalyst for CO/CO 2 An integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion.
In the step 1), the metal salt is one of nitrate/halide/sulfate, and the precipitant is one of ammonia water/ammonium carbonate/oxalic acid/sodium carbonate/sodium bicarbonate; the heating temperature is 65-75 ℃, and the pH is controlled to be 6.8-7.8; the aging temperature is 80-90 ℃ and the aging time is 1-2 h; washing with deionized water for 3-5 times; the drying temperature is 80-110 ℃ and the drying time is 12-18 h; the roasting temperature is 380-500 ℃ and the roasting time is 3-8 h.
In the step 2), the metal salt solution corresponding to the carrier oxide is one or more of nitrate/acetate/halide/sulfate, and the precursor solution of Pd is any one of zinc acetate, zinc nitrate, zinc sulfate or zinc chloride; the aging temperature is 80-90 ℃, the aging time is 1-2 h, the drying temperature is 80-110 ℃, the drying time is 12-18 h, the roasting temperature is 350-550 ℃, and the roasting time is 3-8 h; the mass content of the metal Pd in the catalyst is 1-20%.
The SSZ-13 molecular sieve needs to be subjected to alkali treatment to poison an acid site, and the method comprises the following steps: dispersing SSZ-13 molecular sieve in 0.1-0.15 mol/L NaOH solution for acid poisoning, stirring for 15-30 min at 80-95 ℃, centrifugally separating, washing the obtained solid with deionized water, and finally drying to obtain the non-acidic SSZ-13 molecular sieve.
The preparation of the H-MCM-22 molecular sieve is as follows: placing the MCM-22 molecular sieve in 0.1-1.5M ammonium nitrate solution, carrying out ammonium exchange for 2-3H at 80-95 ℃, repeating for 3-4 times, drying for 12-18H at 80-110 ℃, and roasting for 3-8H at 380-500 ℃ to obtain the H-MCM-22 molecular sieve.
The treatment steps of the methanol aromatization catalyst Zn/ZSM-5 molecular sieve comprise the following steps:
a) Carrying out ammonium exchange on the Na-type ZSM-5 molecular sieve for 3-4 times, drying and roasting to obtain an H-ZSM-5 molecular sieve;
b) Carrying out loading, drying and roasting of a metal active component Zn on the H-ZSM-5 molecular sieve to obtain Zn/ZSM-5;
in the step a), the concentration of the ammonium nitrate solution for ammonium exchange is 0.1-1.5M, the required temperature is 80-95 ℃, the time is 2-3 h, the roasting temperature is 380-500 ℃, and the time is 3-8 h; in the step b), the metal active component Zn is introduced into the obtained H-ZSM-5 molecular sieve by adopting an ion exchange method or an isovolumetric impregnation method, and the mass content of the metal Zn in the catalyst is 0.05-10%. The temperature required for drying is 80-110 ℃, the time is 12-18 h, the roasting temperature is 380-500 ℃ and the time is 3-8 h.
The precursor of the methanol aromatization catalyst Zn/ZSM-5 molecular sieve is any one of zinc acetate, zinc nitrate, zinc sulfate or zinc chloride.
The treatment steps of the methanol aromatization catalyst Ga/ZSM-5 molecular sieve comprise the following steps:
a) Carrying out ammonium exchange on the Na-type ZSM-5 molecular sieve for 3-4 times, drying and roasting to obtain an H-ZSM-5 molecular sieve;
b) Loading, drying and roasting the metal active component Ga on the H-ZSM-5 molecular sieve to obtain Ga/ZSM-5;
In the step a), the concentration of the ammonium nitrate solution for ammonium exchange is 0.1-1.5M, the required temperature is 80-95 ℃, the time is 2-3 h, the roasting temperature is 380-500 ℃, and the time is 3-8 h; in the step b), metal active component Ga is introduced into the obtained H-ZSM-5 molecular sieve by adopting an ion exchange method or an isovolumetric impregnation method, and the mass content of the metal Ga in the catalyst is 0.05-10%. The temperature required for drying is 80-110 ℃, the time is 12-18 h, the roasting temperature is 380-500 ℃ and the time is 3-8 h.
The precursor of the methanol aromatization catalyst Ga/ZSM-5 molecular sieve is any one of gallium nitrate, gallium sulfate or gallium chloride.
The Na-type ZSM-5 molecular sieve is synthesized by adopting a hydrothermal synthesis method, and the synthesis steps comprise the following steps:
a) At room temperature, sequentially dissolving an aluminum source, a silicon source, a template agent and a mineralizing agent in deionized water, and uniformly mixing under the stirring condition to prepare mixed gel;
b) Aging the mixed gel prepared in the step a) for 12 hours at room temperature, and transferring the aged mixed gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining for sealing and crystallization;
c) And b) cooling the product obtained after crystallization in the step b), filtering to remove mother liquor, washing the solid product to be neutral by deionized water, and drying and roasting to obtain the Na-type ZSM-5 molecular sieve.
In the step a), the aluminum source is one or more of aluminum sulfate, aluminum nitrate, sodium metaaluminate and aluminum isopropoxide; the silicon source is one or more of tetraethyl orthosilicate, sodium silicate, silica sol and water glass; the template agent is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium bromide, n-butylamine and hexanediol; the mineralizing agent is sodium hydroxide.
The crystallization temperature in the step b) is 120-220 ℃ and the crystallization time is 24-120 h; the drying temperature in the step c) is 80-110 ℃, the drying time is 12-18 h, the roasting temperature is 500-600 ℃, and the roasting time is 5-8 h.
The molar ratio of the components of the mixed gel in step a) is n (Na 2 O):n(SiO 2 ):n(Al 2 O 3 ) N (template agent) n (H) 2 O)＝10.7:x:1.0:5.7:1130(x＝50,100,200,240,300,400)。
The application of the catalyst is used for CO/CO 2 Before the reaction, introducing reducing gas or protecting gas into fixed bed reactor with catalyst, pretreating catalyst, introducing raw material gas, and making CO/CO under a certain pressure and temp 2 Hydrogenation to produce liquid fuel and aromatic hydrocarbon.
The reducing gas is hydrogen-argon mixed gas containing 5% of hydrogen, and the protective gas is nitrogen or argon; the pretreatment temperature is 250-350 ℃, the treatment time is 1-2 h, the reaction temperature is 280-400 ℃, the reaction pressure is 2-7 MPa, and the space velocity of raw material gas is 1000-10000 mL h -1 g -1 ，n(H 2 ) N (CO) =1 to 3 or n (H) 2 ):n(CO 2 )＝1～4。
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. according to the invention, a physical coating method is adopted to wrap a molecular sieve membrane without acidity outside CuZn-based catalyst particles or supported Pd-based catalyst particles with stronger hydrogenation capability, a core-shell catalyst is constructed, the core-shell catalyst and a methanol aromatization catalyst such as Zn/ZSM-5 and the like are physically mixed to obtain a bifunctional catalyst, and the coupling between the methanol synthesis reaction and the methanol aromatization reaction is realized.
2. The core-shell catalyst of the invention utilizes the molecular sieve membrane with the orifice size larger than CO/CO 2 /H 2 Kinetic diameters of the reactants and methanol intermediates are less than C 5+ The dynamic diameter characteristics of hydrocarbon and aromatic hydrocarbon ensure that reactant molecules can diffuse into the nucleus to generate methanol intermediate, diffuse into a molecular sieve area to fully react to generate liquid fuel and aromatic hydrocarbon products, and pull CO/CO 2 Conversion, breakthroughThermodynamic limitations of methanol synthesis. And the design of the bifunctional catalyst is carried out through molecular sieve modification, so that the content of liquid fuel and aromatic hydrocarbon in the product is regulated.
3. The invention uses molecular sieve membrane on the core-shell catalyst to prevent the low-carbon olefin produced after the dehydration of methanol from contacting with the core, and inhibits the low-carbon olefin from diffusing into the high-activity CuZn-based catalyst and the supported Pd-based catalyst to generate byproducts such as low-carbon alkane and the like by the synergistic pulling action of the difunctional active components, thereby realizing the unidirectional diffusion of the intermediate product low-carbon olefin on the catalyst and having stronger reaction activity under the low-temperature condition.
4. The catalyst has excellent catalytic performance, and can obviously improve CO/CO by utilizing the synergistic pulling action among the difunctional active components 2 The conversion rate of (2) realizes the adjustment of the content of liquid fuel and aromatic hydrocarbon in the product by controlling the reaction conditions such as temperature and the like, and has methane and CO 2 Low selectivity of CO, liquid fuel and aromatic hydrocarbon selectivity as high as 85 percent.
5. The invention aims to overcome the defect of the prior method for CO/CO 2 The dual-function catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation usually needs to use a composite metal oxide component with weaker hydrogenation capability, limits further improvement of reaction activity, needs to be carried out under high temperature conditions, provides a new solution idea for the problems, and further widens the application prospect of the molecular sieve membrane in the field of C1 chemistry.
Drawings
FIG. 1 is an acid-poisoned SSZ-13 molecular sieve, cuZnAlO x Catalyst and core-shell catalyst CuZnAlO x SEM characterization of SSZ-13 catalyst.
FIG. 2 is a view of CuZnAlO of the present invention x Schematic of different combinations of catalyst and Zn/ZSM-5 catalyst.
FIG. 3 is a schematic diagram of the CO/CO system of the present invention 2 And the catalytic performance diagram of the integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
The invention relates to a method for CO/CO 2 The integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion uses CuZn-based or supported Pd-based catalyst as core, inert eight-membered ring SSZ-13 molecular sieve and AlPO-34 molecular sieve as shell, and the eight-membered ring molecular sieve of upper shell layer of core-shell catalyst only has the function of regulating and controlling diffusion of reactant molecules and intermediate product molecules, and does not needAn acidic site, thus subjecting the SSZ-13 molecular sieve to a base treatment; the CuZn-based catalyst is a CuZnM catalyst modified by a modification element M, and the molar percentage of the components is n (Cu+Zn): n (M) =9-1, n (Cu): n (Zn) =0.1-10; the mass percentage of metal Pd in the supported Pd-based catalyst is 1-20%. In addition, zn/ZSM-5 molecular sieve catalysts for methanol aromatization coupled with core-shell catalysts require the acidity on the ZSM-5 molecular sieve to be controlled by the supported zinc. Ga/ZSM-5 molecular sieve catalyst for methanol aromatization coupled with core-shell catalyst requires the acidity on ZSM-5 molecular sieve to be controlled by supported gallium. The MCM-22 molecular sieve catalyst for methanol aromatization, which is coupled with the core-shell catalyst, needs to be subjected to ammonium exchange, drying and roasting to obtain the H-MCM-22 molecular sieve catalyst.
The preparation method of the catalyst comprises the following steps:
(1) Preparing a mixed metal salt solution A of Cu+Zn with the molar ratio of n (Cu) to n (Zn) =0.1-10, and the total concentration is 0.45-0.9 mol/L; a metal salt solution B of M with a molar ratio of n (Cu+Zn) n (M) =9-1 is arranged, and the concentration is 0.05-0.1 mol/L; preparing a precipitant solution, wherein the concentration is the same as that of the metal salt solution B. And simultaneously adding the metal salt solution A, the metal salt solution B and the precipitant solution into 100mL of deionized water under the stirring condition of 65-75 ℃ for coprecipitation, controlling the pH value to be 6.8-7.8, stirring in a water bath for 2h, and aging for 1-2 h at 80-90 ℃. Filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an oven at 80-110 ℃ for 12-18 h, and roasting the precipitate at 380-500 ℃ for 3-8 h.
(2) Dissolving metal salt corresponding to an oxide carrier in ethanol water solution with the volume ratio of 1:3 to prepare a metal salt solution with the concentration of 0.1-0.5 mol/L; preparing a mixed solution of ammonia water and ethanol with the same volume as the metal salt solution and the volume ratio of 1:3, and dripping the mixed solution into the metal salt solution dropwise under the stirring condition. Aging the obtained mixture for 1-3 h at 80-90 ℃, centrifugally separating, washing with deionized water for 3-5 times, drying for 12-18 h at 80-110 ℃, and roasting for 3-6 h at 350-550 ℃; dispersing the prepared oxide carrier in deionized water, then ultrasonic treating for 0.5-2 h, adding Pd precursor solution to make m (Pd) [ m (Pd) +m (oxide carrier) ]=1 to 20%, stirring for 1 to 3 hours at room temperature, and dropwise adding excessive newly-prepared NaBH 4 Continuously stirring the solution for 2-3 h, centrifugally separating, collecting precipitate, washing 3-5 times with deionized water, drying at 80-110 ℃ for 12-18 h, and roasting at 350-550 ℃ for 3-6 h to obtain the supported Pd-based catalyst;
(3) Dispersing SSZ-13 molecular sieve in 0.1-0.15 mol/L NaOH solution, stirring at 80-95 ℃ for 15-30 min, centrifuging, washing the obtained solid with deionized water, and drying in an oven at 70-80 ℃ for 12-18 h to obtain alkali-treated SSZ-13 molecular sieve.
(4) At room temperature, sequentially dissolving an aluminum source, a silicon source, a template agent and a mineralizing agent in deionized water, uniformly mixing under stirring to prepare mixed gel, wherein the molar ratio of each component in the mixed gel is n (Na 2 O):n(SiO 2 ):n(Al 2 O 3 ) N (template agent) n (H) 2 O) =10.7:x:1.0:5.7:1130 (x= 50,100,200,240,300,400). Aging the prepared mixed gel for 12 hours at room temperature, transferring the mixed gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing, and crystallizing at 120-220 ℃ for 24-120 hours. Cooling the crystallized product, filtering to eliminate mother liquid, washing the solid product with deionized water to neutrality, drying in 80-110 deg.c oven for 12-18 hr, and roasting in muffle furnace for 5-8 hr at 500-600 deg.c to obtain Na type ZSM-5 molecular sieve.
(5) The Na-type ZSM-5 molecular sieve is treated by six steps of ammonium exchange, drying, roasting, loading of metallic zinc, drying and roasting, and the modified methanol aromatization Zn/ZSM-5 molecular sieve is obtained.
(6) And (3) treating the Na-type ZSM-5 molecular sieve through six steps of ammonium exchange, drying, roasting, gallium loading, drying and roasting to obtain the modified methanol aromatization Ga/ZSM-5 molecular sieve.
(7) The commercial MCM-22 molecular sieve is placed in 0.1-1.5M ammonium nitrate solution, ammonium exchange is carried out for 2-3H at 80-95 ℃, the process is repeated for 3-4 times, then the product is dried for 12-18H at 80-110 ℃, and finally the product is placed in a muffle furnace and baked for 3-8H at 380-500 ℃ to obtain the H-MCM-22 molecular sieve for aromatization of methanol.
(8) Tabletting and forming a CuZn-based or supported Pd-based catalyst to form particles with the size of 10-20 meshes, soaking a certain amount of catalyst particles in silica sol or alumina sol, placing the soaked catalyst particles in a round-bottom flask filled with an inert SSZ-13 molecular sieve or AlPO-34 molecular sieve, oscillating at a certain frequency, repeating for a plurality of times until the catalyst particles are completely wrapped by the molecular sieve, and drying the obtained core-shell catalyst in an oven at 70-80 ℃ for 12-18 hours. Roasting in a muffle furnace at 450-550 ℃ for 5-8 h to obtain the core-shell catalyst.
The obtained core-shell catalyst is physically mixed with Zn/ZSM-5 molecular sieve or Ga/ZSM-5 molecular sieve or H-MCM-22 molecular sieve, and the catalyst for CO/CO is obtained 2 An integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation.
The invention catalyzes CO/CO 2 The reaction performance evaluation of the liquid fuel and aromatic hydrocarbon reaction by hydrogenation is carried out on a high-temperature high-pressure fixed bed continuous flow reactor, and the reaction tail gas is detected by gas chromatography on-line analysis. The catalyst is pretreated and activated for 1 to 2 hours at the temperature of 250 to 350 ℃ by one of hydrogen diluted by argon and pure hydrogen/nitrogen before the reaction. Cooling to room temperature after pretreatment, and carrying out CO/CO 2 Reaction evaluation of liquid fuel and aromatic hydrocarbon by hydrogenation, wherein the reaction temperature is 280-400 ℃, the reaction pressure is 2-7 MPa, and the space velocity of raw materials is 1000-10000 mL h -1 g -1 ，n(H 2 ) N (CO) =1 to 3 or n (H) 2 ):n(CO 2 )＝1～4. The reaction products were analyzed on-line using gas chromatography and quantitative analysis of the products was performed using TCD and FID detectors.
Example 1
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 10-20 meshes x The catalyst particles are used for preparing core-shell catalysts.
Weighing 0.1g of formed (10-20 meshes) CuZnAlO x Soaking the catalyst particles in silica sol or alumina sol, and soaking the soaked CuZnAlO x Placing the particles in a round bottom flask containing an acidic SSZ-13 molecular sieve, oscillating at a certain frequency, repeating for several times until CuZnAlO x The catalyst particles were completely encapsulated with molecular sieves and the resulting core-shell catalysts were dried in an oven at 80 ℃ for 14h. Roasting in a muffle furnace at 500 ℃ for 2 hours to obtain CuZnAlO x @ SSZ-13 core-shell catalyst.
Taking CuZnAlO x The @ SSZ-13 core-shell catalyst was loaded into a quartz reactor tube with 0.4g of 5% Zn/ZSM-5 molecular sieve in physical admixture at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ) N (CO) =1, the feed gas pressure in the reactor is 4MPa, and the reaction space velocity GHSV=2000 mL h -1 g -1 At 5 DEG Cmin -1 And (3) heating the mixture to 300 ℃ to start the evaluation of the liquid fuel and the aromatic hydrocarbon by the hydrogenation of the carbon monoxide. The evaluation results of the catalyst are shown in Table 1.
Example 2
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 10-20 meshes x The catalyst particles are used for preparing core-shell catalysts.
Weighing 0.1g of formed (10-20 meshes) CuZnAlO x Soaking the catalyst particles in silica sol or alumina sol, and soaking the soaked CuZnAlO x Placing the particles in a round bottom flask containing an acidic SSZ-13 molecular sieve, oscillating at a certain frequency, repeating for several times until CuZnAlO x The catalyst particles were completely encapsulated with molecular sieves and the resulting core-shell catalysts were dried in an oven at 80 ℃ for 14h. Roasting in a muffle furnace at 500 ℃ for 2 hours to obtain CuZnAlO x @ SSZ-13 core-shell catalyst.
Taking CuZnAlO x The @ SSZ-13 core-shell catalyst was loaded into a quartz reactor tube with 0.4g 5% Ga/ZSM-5 molecular sieve in physical admixture at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ) N (CO) =1, the feed gas pressure in the reactor is 4MPa, and the reaction space velocity GHSV=2000 mL h -1 g -1 At 5 ℃ for min -1 And (3) heating the mixture to 350 ℃ to start the evaluation of the liquid fuel and the aromatic hydrocarbon by the hydrogenation of the carbon monoxide. The evaluation results of the catalyst are shown in Table 1.
As shown in figure 1, (a) non-acidic SSZ-13 molecular sieve, (b) CuZnAlO from left to right x Catalyst (c) CuZnAlO prepared in example 1 x SEM image of SSZ-13 core-shell catalyst. Scanning Electron Microscopy (SEM) was used to characterize the particle size and microscopic morphology of the catalyst, and SEM testing performed in the present invention was performed on a Hitachi S-4800 scanning electron microscope with an electron gun acceleration voltage of 20kV. Before the characterization test, a small amount of ground sample powder is fully dispersed in a proper amount of absolute ethyl alcohol, ultrasonic oscillation is carried out for 5min, after the sample is uniformly dispersed, a small amount of suspension liquid is dripped on a silicon wafer, and the silicon wafer is dried and then observed. From the characterization of FIG. 1, it can be seen that CuZnAlO x The @ SSZ-13 catalyst is of a typical core-shell structure, and the structure is stable, so that the catalyst can be ensured to stably run under the reaction condition; the morphology of the SSZ-13 molecular sieve is not obviously changed before and after acid poisoning, which indicates that the alkali treatment of the SSZ-13 molecular sieve has less influence on the morphology of the molecular sieve.
Comparative example 1
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 30-60 meshes x Catalyst particles.
Weighing 0.1g of formed (30-60 meshes) CuZnAlO x The catalyst particles were loaded into a quartz reactor tube with 0.4g of 5% Zn/ZSM-5 molecular sieve in physical admixture at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ) N (CO) =1, the feed gas pressure in the reactor is 4MPa, and the reaction space velocity GHSV=2000 mL h -1 g -1 At 5 ℃ for min -1 Is heated to 300 ℃ and starts to perform CuZnAlO x Evaluation of liquid fuel and aromatic hydrocarbon by catalyzing carbon monoxide hydrogenation with a catalyst and a 5% Zn/ZSM-5 molecular sieve in a physical mixing mode. The evaluation results of the catalyst are shown in Table 1.
Comparative example 2
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 30-60 meshes x Catalyst particles.
Weighing 0.1g of formed (30-60 meshes) CuZnAlO x The catalyst particles and 0.4g of 5% Zn/ZSM-5 molecular sieve are packed in a quartz reaction tube in a layered manner under normal pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ):n(CO) =1, the feed gas pressure in the reactor was brought to 4MPa, the reaction space velocity ghsv=2000 mL h -1 g -1 At 5 ℃ for min -1 Is heated to 300 ℃ and starts to perform CuZnAlO x And (3) evaluating the catalyst and 5% Zn/ZSM-5 molecular sieve to prepare liquid fuel and aromatic hydrocarbon by catalyzing the hydrogenation of carbon monoxide in a layered bed mode. The evaluation results of the catalyst are shown in Table 1.
Comparative example 3
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 10-20 meshes x The catalyst particles are used for preparing core-shell catalysts. Weighing 0.1g of formed (10-20 meshes) CuZnAlO x Soaking the catalyst particles in silica sol or alumina sol, and soaking the soaked CuZnAlO x Placing the particles into a round bottom flask containing Zn/ZSM-5 molecular sieve, oscillating at a certain frequency, repeating for several times until CuZnAlO x The catalyst particles were completely encapsulated with molecular sieves and the resulting core-shell catalysts were dried in an oven at 80 ℃ for 14h. Roasting in a muffle furnace at 500 ℃ for 2 hours to obtain CuZnAlO x @ Zn/ZSM-5 core-shell catalyst.
CuZnAlO is added with x The @ Zn/ZSM-5 core-shell catalyst was loaded into a quartz reactor tube at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction is evaluated, and the raw material gas is filledn(H 2 ) N (CO) =1, the feed gas pressure in the reactor is 4MPa, and the reaction space velocity GHSV=2000 mL h -1 g -1 At 5 ℃ for min -1 And (3) heating the mixture to 300 ℃ to start the evaluation of the liquid fuel and the aromatic hydrocarbon by the hydrogenation of the carbon monoxide. The evaluation results of the catalyst are shown in Table 1.
Comparative example 4
8.6mmol of In (NO) 3 ) 3 ·xH 2 O and 0.32mmol Mn (NO) 2 ) 2 ·4H 2 O was dissolved in 32mL of an aqueous ethanol solution having a volume ratio of 1:3 to prepare a metal salt solution. Preparing a mixed solution of ammonia water and ethanol with the same volume and the volume ratio of 1:3, and dripping the mixed solution into the metal salt solution dropwise under the stirring condition. Aging the obtained mixture at 80 ℃ for 1h, centrifugally separating, washing with deionized water for 3-5 times, drying overnight at 80 ℃, and roasting at 350 ℃ for 3h to prepare In 2 O 3 -MnO; in is to 2 O 3 After dispersion of MnO in deionized water, the mixture was sonicated for 0.5h and 0.056g Pd (NO) 3 ) 2 The solution (18.09 wt%) was stirred at room temperature for 1h and excess fresh NaBH was added dropwise 4 Stirring the solution for 2 hours, centrifugally separating, collecting precipitate, washing 3-5 times with deionized water, drying overnight at 80 ℃, roasting for 3 hours at 350 ℃ to obtain supported 1% Pd/In 2 O 3 -MnO catalyst. Tabletting under 20kN, shaping, selecting 1% Pd/In with granularity of 10-20 mesh 2 O 3 -MnO catalyst particles for the preparation of core shell catalysts.
Weighing 0.1g of molded (10-20 meshes) 1% Pd/In 2 O 3 Soaking MnO catalyst particles In silica sol or alumina sol, and soaking 1% Pd/In 2 O 3 The MnO particles are placed In a round-bottomed flask equipped with an SSZ-13 molecular sieve free of acidity and are subjected to shaking at a frequency, repeated a number of times up to 1% Pd/In 2 O 3 The MnO catalyst particles were completely encapsulated by molecular sieves and the resulting core shell catalyst was dried in an oven at 80℃for 14h. Roasting In a muffle furnace at 500 ℃ for 2h to obtain 1% Pd/In 2 O 3 -MnO@SSZ-13 core-shell catalyst.
Taking 1%Pd/In 2 O 3 the-MnO@SSZ-13 core-shell catalyst was physically mixed with 0.4g of 5% Zn/ZSM-5 molecular sieve in a quartz reaction tube at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ):n(CO 2 ) =3, the feed gas pressure in the reactor was brought to 4MPa, the reaction space velocity ghsv=2000 mL h -1 g -1 At 5 ℃ for min -1 The temperature rise rate of the catalyst is raised to 300 ℃, and evaluation of liquid fuel and aromatic hydrocarbon prepared by carbon dioxide hydrogenation is started. The evaluation results of the catalyst are shown in Table 2.
Comparative example 5
8.6mmol of In (NO) 3 ) 3 ·xH 2 O and 0.32mmol Mn (NO) 2 ) 2 ·4H 2 O was dissolved in 32mL of an aqueous ethanol solution having a volume ratio of 1:3 to prepare a metal salt solution. Preparing a mixed solution of ammonia water and ethanol with the same volume and the volume ratio of 1:3, and dripping the mixed solution into the metal salt solution dropwise under the stirring condition. Aging the obtained mixture at 80 ℃ for 1h, centrifugally separating, washing with deionized water for 3-5 times, drying overnight at 80 ℃, and roasting at 350 ℃ for 3h to prepare In 2 O 3 -MnO; in is to 2 O 3 After dispersion of MnO in deionized water, the mixture was sonicated for 0.5h and 0.056g Pd (NO) 3 ) 2 The solution (18.09 wt%) was stirred at room temperature for 1h and excess fresh NaBH was added dropwise 4 Stirring the solution for 2 hours, centrifugally separating, collecting precipitate, washing 3-5 times with deionized water, drying overnight at 80 ℃, roasting for 3 hours at 350 ℃ to obtain supported 1% Pd/In 2 O 3 -MnO catalyst. Tabletting under 20kN, shaping, selecting 1% Pd/In with granularity of 10-20 mesh 2 O 3 -MnO catalyst particles for the preparation of core shell catalysts.
Weighing 0.1g of molded (10-20 meshes) 1% Pd/In 2 O 3 Soaking MnO catalyst particles In silica sol or alumina sol, and soaking 1% Pd/In 2 O 3 -MnO particles are placed in a container with no acidityIn a round bottom flask of SSZ-13 molecular sieve, shaking at a certain frequency, repeating for a plurality of times until 1% Pd/In 2 O 3 The MnO catalyst particles were completely encapsulated by molecular sieves and the resulting core shell catalyst was dried in an oven at 80℃for 14h. Roasting In a muffle furnace at 500 ℃ for 2h to obtain 1% Pd/In 2 O 3 -MnO@SSZ-13 core-shell catalyst.
1% Pd/In 2 O 3 the-MnO@SSZ-13 core-shell catalyst was physically mixed with 0.4g of 5% Ga/ZSM-5 molecular sieve in a quartz reaction tube at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ):n(CO 2 ) =3, the feed gas pressure in the reactor was brought to 4MPa, the reaction space velocity ghsv=2000 mL h -1 g -1 At 5 ℃ for min -1 The temperature rise rate of (2) is increased to 350 ℃, and evaluation of liquid fuel and aromatic hydrocarbon prepared by carbon dioxide hydrogenation is started. The evaluation results of the catalyst are shown in Table 2.
Comparative example 6
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 10-20 meshes x The catalyst particles are used for preparing core-shell catalysts.
Weighing 0.1g of formed (10-20 meshes) CuZnAlO x Catalytic reactionSoaking the agent particles in silica sol or aluminum sol, and soaking the soaked CuZnAlO x Placing the particles in a round bottom flask containing an acidic SSZ-13 molecular sieve, oscillating at a certain frequency, repeating for several times until CuZnAlO x The catalyst particles were completely encapsulated with molecular sieves and the resulting core-shell catalysts were dried in an oven at 80 ℃ for 14h. Roasting in a muffle furnace at 500 ℃ for 2 hours to obtain CuZnAlO x @ SSZ-13 core-shell catalyst.
Taking CuZnAlO x The @ SSZ-13 core-shell catalyst was loaded into a quartz reactor tube with 0.4g of 5% Zn/ZSM-5 molecular sieve in physical admixture at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ):n(CO):n(CO 2 ) Raw material gas pressure in the reactor was brought to 4MPa, reaction space velocity ghsv=2000 mL h=76:14:10 -1 g -1 At 5 ℃ for min -1 And (3) heating the mixture to 300 ℃ to start the evaluation of the liquid fuel and aromatic hydrocarbon prepared by hydrogenating the carbon dioxide-rich synthetic gas. The results of the catalyst evaluation are shown in Table 3.
Comparative example 7
Weigh 54mmol Cu (NO) 3 ) 2 ·3H 2 O and 18mmol Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 100mL of deionized water to prepare a metal salt solution A, and 8mmol of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL deionized water to prepare a metal salt solution B, and Na with the same concentration as the solution B is prepared 2 CO 3 A solution. Adding a metal salt solution A, a metal salt solution B and a precipitant solution into 100mL of deionized water at 70 ℃ under stirring to perform coprecipitation, controlling the pH value to 7.0, aging the obtained mixture at 80 ℃ for 1.5h after stirring in a water bath for 2h, filtering to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, drying the obtained precipitate in an 80 ℃ oven for 14h, and roasting at 500 ℃ for 5h to obtain CuZnAlO x Tabletting the catalyst under 20kN, forming, and selecting CuZnAlO with granularity of 10-20 meshes x The catalyst particles are used for preparing core-shell catalysts.
Weighing 0.1g of formed (10-20 meshes) CuZnAlO x Soaking the catalyst particles in silica sol or alumina sol, and soaking the soaked CuZnAlO x Placing the particles in a round bottom flask containing an acidic SSZ-13 molecular sieve, oscillating at a certain frequency, repeating for several times until CuZnAlO x The catalyst particles were completely encapsulated with molecular sieves and the resulting core-shell catalysts were dried in an oven at 80 ℃ for 14h. Roasting in a muffle furnace at 500 ℃ for 2 hours to obtain CuZnAlO x @ SSZ-13 core-shell catalyst.
Taking CuZnAlO x The @ SSZ-13 core-shell catalyst was loaded into a quartz reactor tube with 0.4g 5% Ga/ZSM-5 molecular sieve in physical admixture at atmospheric pressure and 5%H 2 The pretreatment of the catalyst was carried out under an Ar atmosphere. At 5 ℃ for min -1 The temperature is programmed to rise to 400 ℃, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. Then, the reaction was evaluated, and a raw material gas n (H) 2 ):n(CO):n(CO 2 ) Raw material gas pressure in the reactor was brought to 4MPa, reaction space velocity ghsv=2000 mL h=76:14:10 -1 g -1 At 5 ℃ for min -1 And (3) heating the mixture to 350 ℃ to start the evaluation of the liquid fuel and aromatic hydrocarbon prepared by hydrogenating the carbon dioxide-rich synthetic gas. The results of the catalyst evaluation are shown in Table 3.
TABLE 1
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TABLE 2
TABLE 3 Table 3
In order from left to right as shown in FIG. 2, in CuZnAlO x Core-shell catalyst (CZA@SSZ-13) taking inert SSZ-13 molecular sieve as shell and CuZnAlO as core x Through physical mixing with Zn/ZSM-5 molecular sieveCatalysts assembled in a combined manner (CZA+Zn/ZSM-5), cuZnAlO x Catalyst assembled with Zn/ZSM-5 molecular sieve in bed layer mode (CZA Zn/ZSM-5) and CuZnAlO x The catalyst is a core-shell catalyst with an inert SSZ-13 molecular sieve as a shell and an integrated catalyst (CZA@SSZ-13+Zn/ZSM-5) assembled by a physical mixing mode. The preparation method of the catalyst comprises the following steps:
(1) CuZnAlO synthesis by coprecipitation method x Sieving it, and collecting 10-20 meshes of CuZnAlO x The catalyst particles are soaked in silica sol, and are placed in a round-bottom flask together with an acidic SSZ-13 molecular sieve, and are mixed in an oscillating way to form the core-shell catalyst CZA@SSZ-13.
(2) CuZnAlO synthesis by coprecipitation method x Sieving the mixture, and taking 30-60 meshes of CuZnAlO x The catalyst particles are synthesized into ZSM-5 molecular sieve by hydrothermal synthesis, active component Zn is loaded by ion exchange method to obtain Zn/ZSM-5 molecular sieve, cuZnAlO is added x And (3) placing the catalyst particles and the Zn/ZSM-5 molecular sieve in a round bottom flask, and shaking uniformly to obtain the catalyst CZA+Zn/ZSM-5 assembled in a physical mixing mode.
(3) CuZnAlO synthesis by coprecipitation method x Sieving the mixture, and taking 30-60 meshes of CuZnAlO x The catalyst particles are synthesized into ZSM-5 molecular sieve by hydrothermal synthesis, active component Zn is loaded by ion exchange method to obtain Zn/ZSM-5 molecular sieve, and CuZnAlO is prepared by quartz cotton x The catalyst particles are separated from Zn/ZSM-5 molecular sieve to obtain the catalyst CZA Zn/ZSM-5 assembled in a layered mode.
(4) CuZnAlO synthesis by coprecipitation method x Sieving it, and collecting 10-20 meshes of CuZnAlO x The catalyst particles are soaked in silica sol, and are placed in a round-bottom flask together with an acidic SSZ-13 molecular sieve, and are mixed in an oscillating way to form the core-shell catalyst. Synthesizing a ZSM-5 molecular sieve by utilizing a hydrothermal synthesis method, loading active component Zn by utilizing an ion exchange method to obtain a Zn/ZSM-5 molecular sieve, and placing the core-shell catalyst and the Zn/ZSM-5 molecular sieve in a round-bottom flask to shake uniformly to obtain the integrated catalyst CZA@SSZ-13+Zn/ZSM-5 assembled in a physical mixing mode.
As shown in FIGS. 2 to 3According to the invention, a core-shell catalyst is constructed by wrapping CuZn-based catalyst particles or supported Pd-based catalyst particles with stronger hydrogenation capability by a physical coating method, and a dual-function catalyst is constructed by physically mixing the core-shell catalyst for methanol synthesis and the methanol aromatization catalyst such as Zn/ZSM-5 under the optimal reaction condition, so that efficient coupling between the methanol synthesis reaction and the methanol aromatization reaction is realized. Reactant molecules (CO/CO) 2 /H 2 ) First diffuse into the core and react on CuZn-based or supported Pd-based catalyst to form methanol (CH) 3 OH), then methanol molecules are diffused to a Zn/ZSM-5 methanol aromatization catalyst through a shell layer of an acidic molecular sieve pore channel to carry out methanol aromatization reaction, and a molecular sieve membrane is used for preventing low-carbon olefin generated after methanol dehydration from contacting with a hydrogenation catalyst in a core, so that the low-carbon olefin is prevented from being diffused into a high-activity CuZn-based catalyst and a supported Pd-based catalyst to generate byproducts such as low-carbon alkane through the synergistic pulling action of the bifunctional active components, and the unidirectional diffusion of an intermediate product low-carbon olefin on the catalyst is realized, so that the catalyst has stronger reaction activity under a low-temperature condition. The invention aims to overcome the defect of the prior method for CO/CO 2 The dual-function catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation usually needs to use a composite metal oxide component with weaker hydrogenation capability, limits further improvement of reaction activity, needs to be carried out under high temperature conditions, provides a new solution idea for the problems, and further widens the application prospect of the molecular sieve membrane in the field of C1 chemistry.

Claims (10)

1. For CO/CO 2 The integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion is characterized in that: comprises a core-shell catalyst for methanol synthesis and a methanol aromatization catalyst;
the core-shell catalyst takes a CuZn-based or supported Pd-based catalyst as a core, an inert SSZ-13 molecular sieve or an AlPO-34 molecular sieve as a shell, and the CuZn-based catalyst is a CuZnM catalyst modified by an element M, and the molar percentage of the components is n (Cu+Zn): n (M) =9-1, n (Cu): n (Zn) =0.1-10; the mass percentage of metal Pd in the supported Pd-based catalyst is 1% -20%; the SSZ-13 molecular sieve is an alkali-treated SSZ-13 molecular sieve;
the methanol aromatization catalyst comprises one of a supported Zn/ZSM-5 molecular sieve, a supported Ga/ZSM-5 molecular sieve and an H-MCM-22 molecular sieve; the mass percentage of metal Zn in the supported Zn/ZSM-5 molecular sieve is 0.05% -10%; the mass percentage of metal Ga in the supported Ga/ZSM-5 molecular sieve is 0.05% -10%.
2. A process for CO/CO according to claim 1 2 The integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion is characterized in that: the modification element M of the CuZnM catalyst is one or more than one of Al, si, ce, zr, re; the carrier of the supported Pd-based catalyst is In 2 O 3 、ZnO、MnO、CeO 2 、ZrO 2 One or more of them.
3. A method according to any one of claims 1 to 2 for CO/CO 2 The preparation method of the integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion is characterized by comprising the following steps:
1) Preparation of CuZnM catalyst: dissolving metal salt in deionized water to prepare a metal salt solution A of Cu+Zn and a metal salt solution B of M, carrying out coprecipitation on the solution A, the solution B and a precipitator under the condition of heating and stirring, and obtaining a CuZnM catalyst after aging, filtering, washing, drying and roasting;
2) Preparing a supported Pd-based catalyst: under the stirring condition, dropwise adding the mixture of ammonia water and ethanol into a metal salt solution corresponding to the carrier oxide, and then aging, centrifugal separation, washing, drying and roasting; dissolving the prepared metal oxide carrier in deionized water, performing ultrasonic treatment, adding Pd precursor solution, stirring at room temperature, and adding new NaBH 4 Continuously stirring the solution, centrifugally separating, collecting the precipitate, washing, drying and roasting to obtain the supported Pd-based catalyst;
3) Soaking a CuZnM catalyst or a supported Pd-based catalyst in silica sol or alumina sol, placing the soaked catalyst particles in a container filled with an inert SSZ-13 molecular sieve or an AlPO-34 molecular sieve, then oscillating for a plurality of times until the catalyst particles are completely wrapped by the molecular sieve, and drying and roasting to obtain a core-shell catalyst;
4) Physically mixing the core-shell catalyst obtained in the step 3) with a methanol aromatization molecular sieve catalyst to obtain the catalyst for CO/CO 2 An integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion.
4. A method of preparation as claimed in claim 3, wherein: in the step 3), the inert SSZ-13 molecular sieve needs to be subjected to alkali treatment to poison an acid site, and the method comprises the following steps: dispersing SSZ-13 molecular sieve in 0.1-0.15 mol/L NaOH solution for acid poisoning, stirring for 15-30 min at 80-95 ℃, centrifugally separating, washing the obtained solid with deionized water, and finally drying to obtain the non-acidic SSZ-13 molecular sieve.
5. A method of preparation as claimed in claim 3, wherein: the supported Zn/ZSM-5 molecular sieve is prepared by six steps of ammonium exchange, drying, roasting, metal zinc loading, drying and roasting of a Na-type ZSM-5 molecular sieve; the supported Ga/ZSM-5 molecular sieve is prepared by six steps of ammonium exchange, drying, roasting, gallium loading, drying and roasting of the Na-type ZSM-5 molecular sieve; the H-MCM-22 molecular sieve is obtained by carrying out ammonium exchange, drying and roasting on a Na-type MCM-22 molecular sieve.
6. The preparation method as claimed in claim 5, wherein the Na-type ZSM-5 molecular sieve is synthesized by a hydrothermal synthesis method, and the steps include:
a) At room temperature, dissolving an aluminum source, a silicon source, a template agent and a mineralizer reagent in deionized water, and stirring to prepare mixed gel;
b) Aging the mixed gel obtained in the step a) at room temperature, and sealing and crystallizing;
c) And b) cooling the product obtained after crystallization in the step b), filtering to remove mother liquor, washing the solid product to be neutral by deionized water, and drying and roasting to obtain the Na-type ZSM-5 molecular sieve.
7. The method of manufacturing according to claim 6, wherein: the aluminum source in the step a) is one or more of aluminum sulfate, aluminum nitrate, sodium metaaluminate and aluminum isopropoxide; the silicon source in the step a) is one or more of tetraethyl orthosilicate, sodium silicate, silica sol and water glass; the template agent in the step a) is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium bromide, n-butylamine and hexanediol; the mineralizer reagent in step a) is sodium hydroxide.
8. The method of manufacturing according to claim 6, wherein: the crystallization temperature in the step b) is 120-220 ℃ and the crystallization time is 24-120 h; the roasting temperature in the step c) is 500-600 ℃ and the roasting time is 5-8 h.
9. Use of a catalyst according to any one of claims 1 to 2 or a catalyst prepared by a method according to any one of claims 3 to 8, characterized in that: the catalyst is used for CO/CO 2 Before the reaction, introducing reducing gas or protecting gas into fixed bed reactor with catalyst, pretreating catalyst, introducing raw material gas, and making CO/CO under a certain pressure and temp 2 Hydrogenation to produce liquid fuel and aromatic hydrocarbon.
10. The use according to claim 9, wherein: the reducing gas is hydrogen-argon mixed gas, and the protective gas is nitrogen or argon; the pretreatment temperature is 250-350 ℃, the treatment time is 1-2 h, the reaction temperature is 280-400 ℃, the reaction pressure is 2-7 MPa, and the space velocity of raw material gas is 1000-10000 mL h -1 g -1 ，n(H 2 ) N (CO) =1 to 3 or n (H) 2 ):n(CO 2 )＝1～4。
CN202310550208.XA 2023-05-16 2023-05-16 For CO/CO 2 Integrated catalyst for preparing liquid fuel and aromatic hydrocarbon by hydrogenation selective conversion and preparation method thereof Pending CN116550373A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117282432A (en) * 2023-08-28 2023-12-26 中国科学院大连化学物理研究所 Catalyst for synthesizing green methanol by biomass gasification coupling renewable energy source hydrogen production and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117282432A (en) * 2023-08-28 2023-12-26 中国科学院大连化学物理研究所 Catalyst for synthesizing green methanol by biomass gasification coupling renewable energy source hydrogen production and preparation method and application thereof

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