CN110560153A - Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof - Google Patents

Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof Download PDF

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CN110560153A
CN110560153A CN201910906918.5A CN201910906918A CN110560153A CN 110560153 A CN110560153 A CN 110560153A CN 201910906918 A CN201910906918 A CN 201910906918A CN 110560153 A CN110560153 A CN 110560153A
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zeolite
catalyst
aluminum
metal
solution
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CN110560153B (en
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杜涛
房鑫
贾贺
李博宇
王义松
车帅
宋延丽
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Northeastern University China
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/03—Precipitation; Co-precipitation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/30—Ion-exchange
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—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
    • C07C29/151—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
    • C07C29/153—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
    • C07C29/154—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 copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
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Abstract

The inventionRelating to environmental protection and CO2The technical field of hydrogenation catalysis, in particular to an aluminum shared metal-zeolite bifunctional catalyst, which comprises: Cu-MOx‑Al2O3Nanoparticles and nano ZSM-5 zeolite; m is a metal element, and Cu exists in the form of copper metal or copper oxide; the nano ZSM-5 zeolite grows in situ in the Cu-MOx‑Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx‑Al2O3The nanoparticles share Al atoms. The nanometer ZSM-5 zeolite and the CMAl nanometer particles in the bifunctional catalyst share Al atoms, and are tightly combined by taking Al as a medium, so that the distance between two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the two catalyst components is obviously enhanced, and the catalytic performance is optimized. The invention also relates to a preparation method and application of the aluminum-shared metal-zeolite bifunctional catalyst.

Description

Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof
Technical Field
The invention relates to environmental protection and CO2The technical field of hydrogenation catalysis, in particular to a catalyst for CO2An aluminum-shared metal-zeolite bifunctional catalyst for hydrogenation reaction, a preparation method and application thereof.
background
There is evidence that human activities are the major cause of the present global climate crisis, especially excessive emission of CO into the atmosphere2The effect is greatest. Compared with the traditional emission reduction methods such as improving the energy efficiency and developing renewable energy sources, the method directly uses CO through catalytic hydrogenation reaction2The technological route for conversion to lower carbon chemicals (methanol, dimethyl ether, aromatics, etc.) is receiving increasing attention. It can effectively reduce CO2The emission amount can promote the development of industries such as clean energy and chemical engineering, and the like, thereby having wide application prospect.
CO2The conversion process to lower carbon chemicals mainly comprises two reaction steps, namely a reversible Methanol Synthesis (MS) reaction and an irreversible Methanol Synthesis (a-Methanol Synthesis, MS) reactionAlcohol Dehydration (MD) reaction. Wherein, the MS reaction needs to be carried out at high temperature (200-300 ℃) and high pressure (3-10 MPa), and the common catalyst is Cu-ZnO-Al2O3A copper-based catalyst as represented; the MD reaction needs to be carried out at a high temperature (300-350 ℃), and the commonly used catalyst is a solid acid catalyst, such as a zeolite molecular sieve, active alumina and the like. The two-step method is to realize CO2in the traditional method for synthesizing low-carbon chemicals, raw gas firstly passes through a hydrogenation catalyst bed layer to generate methanol, and then passes through a dehydration catalyst bed layer to generate liquid fuel. However, since the reaction conditions of the two-step reaction are different, different reaction beds are often required to be designed and constructed, which leads to increased cost and is not favorable for improving economic benefits. In response to this problem, the skilled person further proposes a solution to the one-step process, where it is desirable to simultaneously perform both the MS and MD reactions in the same reaction bed. This will significantly improve the economics of the process, however, it also places higher demands on the catalyst.
In the prior art, the direct mechanical mixing of the hydrogenation catalyst and the dehydration catalyst (i.e. bifunctional catalysis) is the most common technical solution. The invention patent CN104368378A discloses a method for directly preparing a dimethyl ether catalyst by carbon dioxide hydrogenation, which adopts a mechanical grinding and mixing mode to uniformly mix a copper-based catalyst and HZSM-5 zeolite for preparing dimethyl ether by catalytic hydrogenation. In order to improve the performance of the catalyst, the invention patent CN1356163A discloses a method for directly preparing dimethyl ether by synthesis gas, and a coprecipitation deposition method is adopted to load metal oxide on gamma-alumina, so that the distance between a hydrogenation active component and a dehydration active component is shortened; the invention patent CN102600852A discloses a catalyst for preparing dimethyl ether, a preparation method and application thereof, wherein a precursor of an active component and a precursor of a zirconia-alumina mixed oxide are respectively prepared, then the precursor and the precursor are added into the same solution to be uniformly stirred, and a composite catalyst is obtained after drying, which is beneficial to uniform dispersion of the precursor and the precursor. Furthermore, the invention patent CN102228834A takes one or more of silicon dioxide, active carbon, gamma-alumina and ZSM-5 as a carrier, and adopts a volume step impregnation method to load the active component on the catalyst carrier, and the invention patents CN104148083B and CN107970943A active metal is loaded on the active carbon by the same volume impregnation method to obtain the bifunctional catalyst for unsaturated hydrocarbon hydrogenation reaction. The method increases the specific surface area of the catalyst to a certain extent and optimizes the mass transfer process. In addition, researchers in the field have also developed a series of core-shell catalysts. The invention patent CN103212418A uses methanol to synthesize catalyst CuO-ZnO-Al2O3Dispersing the core in solution containing silicon source and additional aluminum source, and coating a layer of independent SiO on the surface of the original catalyst2-Al2O3And (4) shell layer. The invention patents CN101934232A and CN105170179A adopt a chemical uniform precipitation method to prepare the nuclear shell Cu-ZnO/HZSM-5 by taking copper nitrate, zinc nitrate and an HZSM-5 molecular sieve as raw materials, and the nuclear shell Cu-ZnO/HZSM-5 is used for directly synthesizing dimethyl ether by synthesis gas. Although the core-shell type catalyst exhibits good structural properties, its fully encapsulated morphology is not conducive to product drainage and also tends to cause overheating of the core.
disclosure of Invention
Technical problem to be solved
Aiming at the defects of poor synergistic effect, low target product selectivity and the like of the existing bifunctional catalyst, the invention provides an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, and a preparation method and application thereof.
(II) technical scheme
in order to achieve the purpose, the invention adopts the main technical scheme that:
In one aspect, the present invention provides an aluminum-shared metal-zeolite bifunctional catalyst comprising:
Cu-MOx-Al2O3Nanoparticles and nano ZSM-5 zeolite;
m is a metal element, and Cu exists in the form of copper metal or copper oxide;
The nano ZSM-5 zeolite grows in situ in the Cu-MOx-Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx-Al2O3the nanoparticles share Al atoms.
ZSM-5 molecular sieve has wide application in China, and can increase the content of olefin in gas molecules when used as a catalyst.
In one embodiment of the present invention, the expression of the bifunctional catalyst is: (Cu)xMyAlzO0.5*m*y+1.5*z)·[Hn(AlnSi96-nO192)](ii) a Wherein x, y, z and n are natural numbers, and n is less than 27; wherein, M is Zn, Zr, Mn, Ce or Co, and M is the valence state of the metal ion M.
in one embodiment of the present invention, the Cu-MOx-Al2O3The nanoparticles have an average particle size of not more than 100nm, the ZSM-5 zeolite has an average particle size of not more than 200nm, and the ZSM-5 zeolite is bound to the Cu-MOx-Al2O3The surface of the nanoparticles.
in another aspect, the present invention also provides a method for preparing an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, comprising the steps of:
S1 preparation of Cu-containing composition2+、Mm+And Al3+Mixed metal salt solution of (4);
s2, dripping the metal salt solution obtained in the step S1 into the precipitator solution which is continuously stirred until the pH value of the solution is stabilized between 7 and 8 to obtain a mixed solution;
S3, standing and aging the mixed solution in the S2, and calcining a filter cake obtained after filtering, washing and drying at high temperature to obtain the hydrogenation catalyst Cu-MOx-Al2O3Powder (abbreviated CMAl);
s4 preparation of Cu-MO from S3x-Al2O3Uniformly dispersing the powder in deionized water, sequentially adding a template agent and sodium chloride, and continuously stirring at room temperature;
S5 is carried out by Cu-MO according to the requirement of the preset silicon-aluminum ratio in ZSM-5 zeolitex-Al2O3Aluminum in the powder is the only aluminum source, a proper amount of silicon source is dropwise added into the solution obtained in S4, the solution is stirred for 0.5 to 5 hours at room temperature and then stirred under heating, and after full stirring, the solution is kept stand and aged at room temperature;
S6, transferring the aged mixed solution in the S5 into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days under a heating condition, cooling, filtering, washing and drying to obtain a catalyst precursor;
And S7, calcining the catalyst precursor obtained in the step S6 at high temperature to remove the template agent, then placing the catalyst precursor in an ammonium salt solution for ion exchange for 3-5 times, washing, filtering, drying and then calcining again to obtain the aluminum-shared metal-zeolite bifunctional catalyst (ASMZ).
Preferably, in step S1, the mixed metal salt solution is subjected to ultrasonic treatment for 10-30 min.
Preferably, in step S2, the precipitant solution is kept at a constant temperature of 45-70 ℃.
Preferably, in step S2, the dropping rate of the metal salt solution is 1-5 mL/min.
Preferably, in the step S3, the aging temperature is 45-70 ℃; the calcination temperature of the filter cake is 350-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
Preferably, in step S4, the template agent is one or more selected from the group consisting of, but not limited to, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
Preferably, in step S4, stirring is continued at room temperature for 0.5-10 h.
preferably, in step S5, the stirring under heating means that the temperature is 75-90 ℃ and the stirring time is 1-10 h.
preferably, in step S5, Cu-MO is usedx-Al2O3The aluminum in the powder is the only aluminum source, and a silicon source is added to ensure that the silicon-aluminum ratio is not lower than 5.
Preferably, in step S5, the silicon source includes, but is not limited to, tetraethoxysilane, monodisperse SiO2One or more of silica sol and white carbon black.
preferably, in step S6, the hydrothermal reaction temperature is 120-180 ℃. The lower the hydrothermal reaction temperature is, the longer the reaction time is required; the hydrothermal reaction is preferably carried out with stirring.
Preferably, in step S7, the calcination temperature for removing the template agent is 450-600 ℃, and the calcination atmosphere is air, nitrogen or argon.
preferably, in step S7, the ammonium salt used for ammonium ion exchange includes, but is not limited to, one or more of ammonium chloride, ammonium nitrate and aqueous ammonia.
Preferably, in step S7, the re-calcination temperature is 250-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
In addition, the invention also relates to the application of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst to CO2And (3) carrying out catalytic hydrogenation to prepare methanol and/or dimethyl ether.
(III) advantageous effects
The invention has the beneficial effects that:
The invention provides an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, which is prepared by mixing nano ZSM-5 zeolite and Cu-MO in the bifunctional catalyst based on the prior artx-Al2O3al atoms are shared among the nano particles (abbreviated as CMAl), and the nano particles and the CMAl are tightly combined by taking the Al as a medium, so that the distance between two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the catalyst is obviously enhanced, and the catalytic performance is optimized. At present, no report related to the aluminum shared metal-zeolite bifunctional catalyst is found.
In addition, the invention also provides a method for preparing the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, which can effectively control the sizes of the CMAl catalyst and the ZSM-5 zeolite and realize the controllable growth of the latter on the basis of the former.
Drawings
FIG. 1 is a schematic representation of the microstructure of an aluminum-shared metal-zeolite (ASMZ) dual-function catalyst of the present invention.
Figure 2 is an XRD spectrum of the ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 3 is an SEM photograph of an ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 4 is an EDX spectrum of an ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 5 is a graph of the catalytic performance of the ASMZ dual-function catalyst of example 1 of the present invention as a function of time.
[ description of reference ]
10. A zeolite; 20. CMAl nanoparticles; 21. an Al atom; 22. cu atoms.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The present invention for the first time proposes an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst whose microstructure can be seen in FIG. 1. The dual-function catalyst comprises two parts, wherein one part is a copper 22, metal oxide and alumina heterogeneous composite catalyst, namely Cu-MOx-Al2O3Nanoparticles 20, another part of zeolite 10, and in-situ growth of zeolite 10 in Cu-MOx-Al2O3On the nanoparticles 20 (i.e., CMAl), the aluminum atoms 21 that form the zeolite 10 also form Cu-MOx-Al2O3The aluminum atoms of the nanoparticles 20, i.e., the zeolite 10 and the shared aluminum atoms 21 of the CMAl nanoparticles 20. The two parts of the bifunctional catalyst are tightly combined by the combination point of the aluminum atom 21, so that the distance between the two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the bifunctional catalyst is obviously enhanced, and the catalytic performance is optimized. In the catalyst, Cu is present as copper metal or copper oxide, possibly 0, 1 and 2.
To prepare the aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst, the present invention provides the following preparation:
S1 preparation of Cu-containing alloy2+、Mm+And Al3+Mixing metal salt solution and carrying out ultrasonic pretreatment for 10-30 min.
S2, keeping the temperature of the precipitant solution at 45-70 ℃, and slowly dripping the solution obtained in the step S1 into the precipitant solution under continuous stirring at the dripping speed of 1-5mL/min until the pH value of the solution is stabilized between 7 and 8.
And S3, after the dropwise addition is finished, standing and aging the mixed solution in the S2 at the aging temperature of 45-70 ℃, and calcining the filter cake obtained after filtering, washing and drying at the high temperature of 350-500 ℃, wherein the calcining atmosphere is air, nitrogen or argon, and the calcining time is 4-6 hours, so that the hydrogenation catalyst CMAl is obtained.
s4, uniformly dispersing the CMAl powder obtained in the S3 in deionized water, sequentially adding a template and sodium chloride, and continuously stirring for 1h at room temperature; the template agent includes, but is not limited to, one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
And S5, according to the requirement on the silicon-aluminum ratio of the ZSM-5 zeolite, taking aluminum in CMAl as a unique aluminum source, dropwise adding a proper amount of silicon source into the solution obtained in the S4, stirring for 0.5h at room temperature, then stirring for 1h at the temperature of 75-90 ℃, cooling to room temperature, and standing for aging. The silicon-aluminum ratio of the ZSM-5 zeolite is not less than 5; silicon sources include, but are not limited to, ethyl orthosilicate, monodisperse SiO2One or more of silica sol and white carbon black.
And S6, transferring the aged mixed solution in the S5 to a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days at 120-180 ℃, filtering, washing and drying to obtain a catalyst precursor.
Generally, the hydrothermal reaction temperature is, and the lower the hydrothermal reaction temperature is, the longer the reaction time is required; stirring may be accompanied with hydrothermal reaction.
S7, calcining the catalyst precursor obtained in the step S6 at the temperature of 450-600 ℃ for 4-6 hours to remove the template agent, wherein the calcining atmosphere is air, nitrogen or argon; and then carrying out ion exchange on the calcined product in an ammonium salt solution for 3-5 times, washing, filtering, drying, calcining again at 250-500 ℃, calcining for 4-6h in air, nitrogen or argon atmosphere, and calcining to obtain the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst product. The ammonium salt used for ammonium ion exchange includes, but is not limited to, one or a mixture of ammonium chloride, ammonium nitrate and ammonia water.
To further demonstrate the advantages and technical effects of the aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst of the present invention, reference is made to the following examples.
Preparation example
Example 1
this example provides a specific aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst prepared as follows:
(1) Adding Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O、Al(NO3)3·9H2Dissolving O in deionized water according to the molar ratio of Cu to Zn to Al of 6 to 3 to 1, preparing 100mL of 1mol/L metal salt solution, and carrying out ultrasonic treatment for 30 min;
(2) Mixing Na2CO3Dissolving in deionized water to prepare 250mL of 1mol/L solution; mixing Na2CO3The solution is heated to 55 ℃ in a water bath, and the metal salt solution is dripped dropwise under magnetic stirring until the pH value is stabilized at 7-8.
(3) After complete precipitation, aging at 55 ℃ overnight, filtering, washing, and drying a filter cake sample at 120 ℃ for 12h to obtain a CZAl precursor; the filter cake sample was calcined at 400 ℃ for 4h to give sample CZAl.
(4) Dissolving the CZAl in deionized water, dropwise adding tetrapropylammonium hydroxide, uniformly stirring, adding NaCl, and placing the mixed solution in a room-temperature environment to stir for 1 h.
(5) And (3) dropwise adding ethyl orthosilicate into the mixed solution according to the molar ratio of Si to Al being 20, uniformly mixing, stirring for 0.5h at room temperature, then placing the mixture into an oil bath at the temperature of 80 ℃, stirring for 1h, fully stirring, and standing and aging for 20h at room temperature.
(6) Transferring the obtained solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 48h at 180 ℃; and cooling, suction filtering, washing and drying to obtain the bifunctional catalyst precursor.
(7) Calcining the precursor of the bifunctional catalyst for 5 hours at 550 ℃ in an air atmosphere to remove the template agent; and (3) carrying out ion exchange on the calcined product in 0.2mmol/L ammonium chloride solution for 3 times (the solid-to-liquid ratio is less than 1:100) at 50 ℃, carrying out suction filtration, washing and drying, and calcining for 5 hours at 500 ℃ in air atmosphere to remove ammonium ions, thus obtaining the ASMZ bifunctional catalyst product.
Example 2
This example provides a specific aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst prepared as follows:
(1) adding Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O、Al(NO3)3·9H2Dissolving O in deionized water according to the molar ratio of Cu to Zn to Al of 6 to 3 to 1, preparing 100mL of 1mol/L metal salt solution, and carrying out ultrasonic treatment for 30 min.
(2) mixing Na2CO3Dissolving in deionized water to prepare 250mL of 1mol/L solution; mixing Na2CO3the solution is heated to 55 ℃ in a water bath, and the metal salt solution is dripped dropwise under magnetic stirring until the pH value is stabilized at 7-8.
(3) After complete precipitation, aging at 55 ℃ overnight, filtering, washing, and drying a filter cake sample at 120 ℃ for 12h to obtain a CZAl precursor; the filter cake sample was calcined at 400 ℃ for 4h to give sample CZAl.
(4) Dissolving the CZAl in deionized water, dropwise adding tetrapropylammonium hydroxide, uniformly stirring, adding NaCl, and placing the mixed solution in a room-temperature environment to stir for 1 h.
(5) And (2) dropwise adding ethyl orthosilicate into the mixed solution according to the molar ratio of Si to Al of 10, uniformly mixing, stirring for 0.5h at room temperature, then placing the mixture into an oil bath at the temperature of 80 ℃, stirring for 1h, fully stirring, and standing and aging for 20h at room temperature.
(6) transferring the obtained solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 48h at 180 ℃; and cooling, suction filtering, washing and drying to obtain the bifunctional catalyst precursor.
(7) Calcining the precursor of the bifunctional catalyst for 5 hours at 550 ℃ in an air atmosphere to remove the template agent; and (3) performing ion exchange on the calcined product in 0.2mmol/L ammonium chloride solution for 3 times (the solid-to-liquid ratio is less than 1:100) at 50 ℃, performing suction filtration, washing and drying, and calcining for 5 hours at 500 ℃ in air atmosphere to remove ammonium ions to obtain the ASMZ bifunctional catalyst product, wherein the molar ratio of Si to Al in the product is about 10.0, and the product has a good microstructure.
Activation, characterization and catalytic Performance testing of catalysts
activation of the catalyst
Activation of the ASMZ dual-function catalyst is achieved in a reducing gas atmosphere. First, the bifunctional catalyst powder prepared in example 1-2 was tableted at 60MPa (without adding a binder) to prepare catalyst pellets having a diameter of about 0.5 mm; keeping the temperature of the catalyst pellets at 200-350 ℃ for 2-6 h in a hydrogen atmosphere, and reducing CuO in the catalyst into Cu0(ii) a And naturally cooling the catalyst to room temperature in a reducing gas atmosphere or an inert gas atmosphere to obtain the activated ASMZ bifunctional catalyst. Experiments show that the activated catalyst can be stored for a long time under the anaerobic condition, and can be stored for more than 10 days even in dry air.
Compositional characterization of the catalyst
Inductively coupled plasma atomic emission spectroscopy (ICP) analysis showed that the overall Si element mass content of the ASMZ bifunctional catalyst prepared in example 1 was about 36.2%; x-ray photoelectron spectroscopy (XPS) analysis showed that the ASMZ bifunctional catalyst of example 1 showed about 34.3% of the mass content of the Si element. Both methods have similar values and both show that zeolite content has been present in the ASMZ dual-function catalyst prepared in example 1.
The result of low-temperature nitrogen adsorption and desorption tests shows that the BET specific surface area of the ASMZ dual-function catalyst of example 1 is as high as 260.3m2The/g, about 6.5 times that of the traditional Cu-Zn-Al catalyst, shows that the pore structure of the ASMZ dual-function catalyst is improved significantly.
Referring to fig. 2, the X-ray diffraction (XRD) results show that a distinct ZSM-5 characteristic diffraction peak is present in the ASMZ bifunctional catalyst of example 1, along with a CuO characteristic diffraction peak, indicating that the CZAl catalyst and ZSM-5 zeolite crystal structures are present in the ASMZ bifunctional catalyst, consistent with the expected results.
Referring to fig. 3, a Scanning Electron Microscope (SEM) photograph shows that both CZAl nanoparticles and cubic ZSM-5 zeolite are observed in the ASMZ bifunctional catalyst of example 1, confirming that the two are tightly bound together.
Referring to fig. 4, energy dispersive X-ray spectroscopy (EDX) results show that both copper and silicon are uniformly dispersed in the ASMZ bifunctional catalyst of example 1, but they tend to be dispersed in different regions, indicating that the CZAl catalyst and ZSM-5 zeolite are not fully composited, but instead grow on top of each other, conforming to the target structure illustrated in fig. 1.
In conclusion, the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst prepared by the invention has good structural performance and meets the expected design requirements.
Testing of catalytic Performance of the catalyst
The catalytic performance test of the ASMZ dual-function catalyst in example 1 was conducted in a fixed bed reactor. Single bed CO with 0.55g catalyst at 274 ℃ and 3.0MPa2The conversion rate is about 21.25%, and the total selectivity of methanol (MeOH) and dimethyl ether (DME) can reach about 85.3%, which is superior to the existing catalyst. After continuous reaction for 10 hours at 250 ℃ and 3.0MPa, all performance indexes of the catalyst are not obviously reduced (see figure 5), which shows that the prepared ASMZ bifunctional catalyst has good stability.

Claims (10)

1. An aluminum-shared metal-zeolite bifunctional catalyst, comprising:
Cu-MOx-Al2O3Nanoparticles and nano ZSM-5 zeolite;
m is a metal element, and Cu exists in the form of copper metal or copper oxide;
The nano ZSM-5 zeolite grows in situ in the Cu-MOx-Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx-Al2O3The nanoparticles share Al atoms.
2. The aluminum-shared metal-zeolite bifunctional catalyst of claim 1, wherein the bifunctional catalyst is represented by the formula: (Cu)xMyAlzO0.5*m*y+1.5*z)·[Hn(AlnSi96-nO192)](ii) a Wherein x, y, z and n are natural numbers, and n is less than 27; wherein M is Zn, Zr, Mn, Ce or Co, and M isThe valence state of the metal ion M.
3. The aluminum-shared metal-zeolite bifunctional catalyst of claim 1,
The Cu-MOx-Al2O3the nanoparticles have an average particle size of not more than 100nm, the ZSM-5 zeolite has an average particle size of not more than 200nm, and the ZSM-5 zeolite is bound to the Cu-MOx-Al2O3The surface of the nanoparticles.
4. A method of making an aluminum shared metal-zeolite (ASMZ) dual-function catalyst comprising the steps of:
S1 preparation of Cu-containing composition2+、Mm+And Al3+mixed metal salt solution of (4);
S2, dripping the metal salt solution obtained in the step S1 into the precipitator solution which is continuously stirred until the pH value of the solution is stabilized between 7 and 8 to obtain a mixed solution;
S3, standing and aging the mixed solution in the S2, and calcining a filter cake obtained after filtering, washing and drying at high temperature to obtain the hydrogenation catalyst Cu-MOx-Al2O3Powder;
S4 preparation of Cu-MO from S3x-Al2O3uniformly dispersing the powder in deionized water, sequentially adding a template agent and sodium chloride, and continuously stirring at room temperature;
S5 is carried out by Cu-MO according to the requirement of the preset silicon-aluminum ratio in ZSM-5 zeolitex-Al2O3aluminum in the powder is the only aluminum source, a proper amount of silicon source is dropwise added into the solution obtained in S4, the solution is stirred for 0.5 to 5 hours at room temperature and then stirred under heating, and after full stirring, the solution is kept stand and aged at room temperature;
S6, transferring the aged mixed solution in the S5 into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days under a heating condition, cooling, filtering, washing and drying to obtain a catalyst precursor;
and S7, calcining the catalyst precursor obtained in the step S6 at high temperature to remove the template agent, then placing the catalyst precursor in an ammonium salt solution for ion exchange for 3-5 times, washing, filtering, drying and then calcining again to obtain the aluminum-shared metal-zeolite bifunctional catalyst.
5. The method according to claim 4, wherein the precipitant solution is maintained at a constant temperature of 45-70 ℃ in step S2.
6. The method according to claim 4, wherein in step S3, the aging temperature is 45-70 ℃; the calcination temperature of the filter cake is 350-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
7. The method according to claim 4, wherein in step S4, the template is one or more selected from the group consisting of but not limited to tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
8. The method of claim 4, wherein in step S5, Cu-MO is usedx-Al2O3Aluminum in the powder is the only aluminum source, and a silicon source is added to ensure that the silicon-aluminum ratio is not lower than 5;
the silicon source includes but is not limited to tetraethoxysilane and monodisperse SiO2One or more of silica sol and white carbon black.
9. The method according to claim 4, wherein in step S7,
The calcination temperature for removing the template agent is 450-600 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon;
Ammonium salts for ammonium ion exchange include, but are not limited to, one or more of ammonium chloride, ammonium nitrate and aqueous ammonia;
The calcination temperature is 250-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
10. the aluminum-shared metal-zeolite duplex of any of claims 1-3Use of the catalyst or the aluminium-shared metal-zeolite bifunctional catalyst prepared by the preparation method of any one of claims 4 to 9 for CO2And (3) carrying out catalytic hydrogenation to prepare methanol and/or dimethyl ether.
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