WO2021056572A1 - Aluminum shared metal-zeolite bifunctional catalyst, and preparation method and application - Google Patents

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

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WO2021056572A1
WO2021056572A1 PCT/CN2019/109216 CN2019109216W WO2021056572A1 WO 2021056572 A1 WO2021056572 A1 WO 2021056572A1 CN 2019109216 W CN2019109216 W CN 2019109216W WO 2021056572 A1 WO2021056572 A1 WO 2021056572A1
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zeolite
aluminum
catalyst
metal
dual
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French (fr)
Chinese (zh)
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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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东北大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the technical field of environmental protection and CO 2 hydrogenation catalysis, in particular to an aluminum shared metal-zeolite dual-functional catalyst capable of catalyzing CO 2 hydrogenation reaction, and a preparation method and application thereof.
  • the conversion process of CO 2 to low-carbon chemicals mainly includes two reaction steps, namely the reversible methanol synthesis (MS) reaction and the irreversible methanol dehydration (MD) reaction.
  • MS reversible methanol synthesis
  • MD irreversible methanol dehydration
  • the MS reaction needs to be carried out at high temperature (200 ⁇ 300°C) and high pressure (3 ⁇ 10MPa).
  • the commonly used catalyst is a copper- based catalyst represented by Cu-ZnO-Al 2 O 3 ;
  • the MD reaction needs to be carried out at high temperature (300 ⁇ 350°C), the commonly used catalysts are solid acid catalysts, such as zeolite molecular sieves, activated alumina, etc.
  • the two-step method is a traditional method for CO 2 synthesis of low-carbon chemicals.
  • the feed gas first passes through the hydrogenation catalyst bed to generate methanol, and then passes through the dehydration catalyst bed to generate liquid fuel.
  • the reaction conditions of the two-step reaction are not the same, it is often necessary to design and build different reaction beds, which leads to increased costs and is not conducive to improving economic benefits.
  • those skilled in the art have further proposed a one-step solution, expecting to complete both MS and MD reactions in the same reaction bed. This will significantly improve the economics of the process, but it also places higher demands on the catalyst.
  • the invention patent CN104368378A discloses a method for directly preparing dimethyl ether catalyst by hydrogenation of carbon dioxide.
  • the copper-based catalyst and HZSM-5 zeolite are uniformly mixed by means of mechanical grinding and mixing to prepare dimethyl ether by catalytic hydrogenation.
  • the invention patent CN1356163A discloses a method for directly preparing dimethyl ether from synthesis gas.
  • the metal oxide is supported on ⁇ -alumina by the co-precipitation deposition method, which shortens the hydrogenation active components and dehydration activity.
  • invention patent CN102600852A discloses a catalyst for preparing dimethyl ether and its preparation method and application.
  • the precursor of the active component and the precursor of the zirconia-alumina mixed oxide are prepared separately, and the two Add them to the same solution and stir evenly, and get a composite catalyst after drying, which helps to disperse the two evenly.
  • the invention patent CN102228834A uses one or more of silica, activated carbon, ⁇ -alumina and ZSM-5 as the carrier, and uses the volumetric stepwise impregnation method to load the active components on the catalyst carrier.
  • the invention patent CN104148083B , CN107970943A also adopts equal volume impregnation method to load active metals on activated carbon to obtain a dual-functional catalyst for the hydrogenation of unsaturated hydrocarbons. This method increases the specific surface area of the catalyst to a certain extent and optimizes the mass transfer process.
  • researchers in this field have also developed a series of core-shell catalysts.
  • the invention patent CN103212418A uses the methanol synthesis catalyst CuO-ZnO-Al 2 O 3 as the core, which is dispersed in a solution containing a silicon source and an additional aluminum source, and a separate SiO 2 -Al 2 O 3 shell is wrapped on the surface of the procatalyst Floor.
  • the invention patents CN101934232A and CN105170179A adopt a chemical uniform precipitation method using copper nitrate, zinc nitrate and HZSM-5 molecular sieve as raw materials to prepare core-shell Cu-ZnO/HZSM-5 for direct synthesis of dimethyl ether from syngas.
  • the core-shell type catalyst exhibits good structural properties, its completely wrapped form is not conducive to the discharge of the product, and it is also easy to cause the core to overheat.
  • the present invention proposes an aluminum shared metal-zeolite (ASMZ) dual-functional catalyst, and a preparation method and application thereof.
  • ASMZ aluminum shared metal-zeolite
  • the main technical solutions adopted by the present invention include:
  • the present invention provides an aluminum shared metal-zeolite dual-functional catalyst, which comprises:
  • M is a metal element, and Cu exists in the form of copper metal or copper oxide;
  • the nano ZSM-5 zeolite is grown in situ on the surface of the Cu-MO x -Al 2 O 3 nanoparticles, and the nano ZSM-5 zeolite and the Cu-MO x -Al 2 O 3 nanoparticles share Al atoms .
  • ZSM-5 molecular sieve has been widely used in China. When used as a catalyst, it can increase the content of olefins in gas molecules.
  • the average particle size of the Cu-MO x -Al 2 O 3 nanoparticles is not greater than 100 nm
  • the average particle size of the ZSM-5 zeolite is not greater than 200 nm
  • the ZSM-5 zeolite is bound to the Cu -MO x -Al 2 O 3 nanoparticle surface.
  • the present invention also provides a method for preparing aluminum shared metal-zeolite (ASMZ) bifunctional catalyst, which includes the following steps:
  • S6 Transfer the aged mixed solution in S5 to an autoclave, hydrothermally react for 2-4 days under heating conditions, and obtain a catalyst precursor after cooling, filtering, washing, and drying;
  • step S1 ultrasonic treatment is performed on the mixed metal salt solution, and the ultrasonic treatment time is 10-30 min.
  • step S2 the precipitant solution is kept at a constant temperature at a set temperature, and the set temperature is 45-70°C.
  • the dropping rate of the metal salt solution is 1-5 mL/min.
  • the aging temperature is 45-70°C; the calcination temperature of the filter cake is 350-500°C, the calcination time is 4-6 hours, and the calcination atmosphere is air, nitrogen or argon.
  • the template agent is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia and pyridine.
  • step S4 continuous stirring is performed at room temperature for 0.5-10 h.
  • step S5 stirring under heating means that the temperature is 75-90° C., and the stirring time is 1-10 h.
  • step S5 the aluminum in the Cu-MO x -Al 2 O 3 powder is used as the only aluminum source, and the silicon source is added so that the silicon-to-aluminum ratio is not less than 5.
  • the silicon source includes but is not limited to one or more of tetraethyl orthosilicate, monodisperse SiO 2 , silica sol, and white carbon black.
  • the temperature of the hydrothermal reaction is 120-180°C.
  • the calcination temperature for removing the template agent is 450-600° C.
  • the calcination is 4-6 hours
  • the calcination atmosphere is air, nitrogen or argon.
  • the ammonium salt used for ammonium ion exchange includes but is not limited to one or more of ammonium chloride, ammonium nitrate and ammonia.
  • the calcination temperature is 250-500° C.
  • the calcination time is 4-6 hours
  • the calcination atmosphere is air, nitrogen or argon.
  • the present invention also relates to the application of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst to the catalytic hydrogenation of CO 2 to prepare methanol and/or dimethyl ether.
  • ASMZ aluminum shared metal-zeolite
  • the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst provided by the present invention combines nano-ZSM-5 zeolite and Cu-MO x -Al 2 O 3 nanoparticles (abbreviated as CMAl) share Al atoms and use Al as a medium to closely combine the two, which greatly shortens the distance between the two catalyst components in the traditional dual-function catalyst, thereby significantly enhancing its synergistic effect and optimizing catalytic performance.
  • CMAl Cu-MO x -Al 2 O 3 nanoparticles
  • the present invention also provides a method for preparing the aluminum shared metal-zeolite (ASMZ) dual-function catalyst, which can effectively control the size of the CMAl catalyst and the ZSM-5 zeolite, and realize the controllable growth of the latter on the basis of the former.
  • the preparation method has simple process and high yield, and is suitable for large-scale production.
  • Figure 1 is a schematic diagram of the microstructure of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst of the present invention.
  • ASMZ aluminum shared metal-zeolite
  • Figure 2 is the XRD spectrum of the ASMZ bifunctional catalyst in Example 1 of the present invention.
  • Figure 3 is an SEM photograph of the ASMZ dual-functional catalyst in Example 1 of the present invention.
  • Figure 4 is the EDX spectrum of the ASMZ dual-function catalyst in Example 1 of the present invention.
  • Fig. 5 is a curve of the catalytic performance of the ASMZ dual-function catalyst in Example 1 of the present invention over time.
  • the present invention proposes for the first time an aluminum-sharing metal-zeolite (ASMZ) dual-function catalyst, and its microstructure can be seen in Figure 1.
  • the dual-function catalyst includes two parts, one part is a heterogeneous composite catalyst of copper 22, metal oxide and alumina, namely Cu-MO x -Al 2 O 3 nanoparticles 20, and the other part is zeolite 10, and zeolite 10 is in situ Growing on Cu-MO x -Al 2 O 3 nanoparticles 20 (ie CMAl), the aluminum atoms 21 forming zeolite 10 are also aluminum atoms forming Cu-MO x -Al 2 O 3 nanoparticles 20, that is, zeolite 10 and CMAl The nanoparticles 20 share aluminum atoms 21.
  • ASMZ aluminum-sharing metal-zeolite
  • the two parts are tightly combined with the aluminum atom 21 bonding point, which greatly shortens the distance between the two catalyst components in the traditional dual-function catalyst, thereby significantly enhancing its synergistic effect and optimizing catalytic performance.
  • Cu exists in the form of copper metal or copper oxide, which may be 0, 1 and 2 valence.
  • the present invention provides the following preparation method:
  • the mixed solution in S2 is allowed to stand and age at a temperature of 45-70°C, and then the filter cake obtained after filtration, washing and drying is calcined at a high temperature of 350-500°C.
  • the calcining atmosphere is Air, nitrogen or argon, the calcination time is 4-6h, and the hydrogenation catalyst CMAl is obtained.
  • templating agents include but are not limited to tetrapropylammonium hydroxide, tetrapropylammonium bromide, One or more of tetraethylammonium hydroxide, ethylenediamine, ammonia and pyridine.
  • silica-aluminum ratio of ZSM-5 zeolite using the aluminum in CMAl as the only aluminum source, add an appropriate amount of silicon source dropwise to the solution obtained in S4, stir at room temperature for 0.5h, and then heat to 75 ⁇ Stir for another 1 hour at 90°C, then stand for aging after cooling down to room temperature.
  • the silicon-to-aluminum ratio of ZSM-5 zeolite is not less than 5; silicon sources include but are not limited to one or more of ethyl orthosilicate, monodisperse SiO 2 , silica sol and white carbon black.
  • S6 Transfer the aged mixed solution in S5 to an autoclave, and hydrothermally react at 120-180°C for 2-4 days, filter, wash, and dry to obtain a catalyst precursor.
  • the hydrothermal reaction temperature is, and the lower the hydrothermal reaction temperature, the longer the required reaction time; the hydrothermal reaction can be accompanied by stirring.
  • 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.
  • ASMZ aluminum-sharing metal-zeolite
  • This embodiment provides a specific aluminum-sharing metal-zeolite (ASMZ) dual-functional catalyst, which is prepared as follows:
  • This embodiment provides a specific aluminum-sharing metal-zeolite (ASMZ) dual-functional catalyst, which is prepared as follows:
  • the activation of the ASMZ bifunctional catalyst is realized in a reducing gas atmosphere.
  • the dual-functional catalyst powder prepared in Example 1-2 was tableted at 60 MPa (without adding a binder) to form catalyst pellets with a diameter of about 0.5 mm; the catalyst pellets were heated at 200-350°C under hydrogen.
  • the CuO in the catalyst is reduced to Cu 0 ; the catalyst is naturally cooled to room temperature in a reducing gas atmosphere or an inert gas atmosphere to obtain an activated ASMZ bifunctional catalyst.
  • the activated catalyst can be stored for a long time under anaerobic conditions, even in dry air, it can be stored for more than 10 days.
  • ICP Inductively coupled plasma atomic emission spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • the results of the low-temperature nitrogen adsorption and desorption test show that the BET specific surface area of the ASMZ bifunctional catalyst of Example 1 is as high as 260.3m 2 /g, which is about 6.5 times that of the traditional copper-zinc-aluminum catalyst, indicating that the pore structure of the ASMZ bifunctional catalyst has been obtained. Significantly improved.
  • X-ray diffraction (XRD) results show that the ASMZ dual-functional catalyst of Example 1 has obvious characteristic diffraction peaks of ZSM-5 and the characteristic diffraction peaks of CuO at the same time, indicating that CZAl is also present in the ASMZ dual-functional catalyst.
  • the crystal structure of the catalyst and ZSM-5 zeolite are consistent with the expected results.
  • the aluminum shared metal-zeolite (ASMZ) dual-functional catalyst prepared by the present invention has good structural properties and meets the expected design requirements.
  • the catalytic performance test of the ASMZ bifunctional catalyst in Example 1 was carried out in a fixed bed reactor.
  • the reaction temperature is 274°C and the reaction pressure is 3.0MPa
  • the single-bed CO 2 conversion rate achieved by using 0.55g catalyst is about 21.25%
  • the total selectivity of methanol (MeOH) and dimethyl ether (DME) can reach 85.3% Around, better than existing catalysts.
  • the performance indicators did not decrease significantly (see Figure 5), indicating that the prepared ASMZ bifunctional catalyst has good stability.

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Abstract

The present invention relates to the technical fields of environmental protection and CO2 hydrogenation catalysis, and particularly provides an aluminum shared metal-zeolite bifunctional catalyst. The bifunctional catalyst comprises Cu-MOx-Al2O3 nanoparticles 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 on the surfaces of the Cu-MOx-Al2O3 nanoparticles in situ, and the nano-ZSM-5 zeolite and the Cu-MOx-Al2O3 nanoparticles share Al atoms. The nano-ZSM-5 zeolite and the CMAl nanoparticles in the bifunctional catalyst share the Al atoms, and are tightly combined by taking Al as a medium, so that a distance between two catalyst components in a conventional bifunctional catalyst is greatly shortened, thereby remarkably enhancing the synergistic effect of the two catalyst components and optimizing the catalytic performance. The present invention further relates to a preparation method and an application of the aluminum shared metal-zeolite bifunctional catalyst.

Description

一种铝共享金属-沸石双功能催化剂及制备方法和应用Aluminum shared metal-zeolite dual-function catalyst and preparation method and application thereof 技术领域Technical field
本发明涉及环保及CO 2加氢催化技术领域，尤其是一种可催化CO 2加氢反应的铝共享金属-沸石双功能催化剂及制备方法和应用。 The invention relates to the technical field of environmental protection and CO 2 hydrogenation catalysis, in particular to an aluminum shared metal-zeolite dual-functional catalyst capable of catalyzing CO 2 hydrogenation reaction, and a preparation method and application thereof.
背景技术Background technique
有证据表明，人类活动是导致目前全球气候危机的主要原因，其中尤以过度向大气中排放CO 2影响最大。与提高能源效率和开发可再生能源等传统减排方法相比，通过催化加氢反应直接将CO 2转化成低碳化学品(甲醇，二甲醚，芳香烃等)的技术路线正受到越来越多的关注。它既能有效降低CO 2的排放量，又能促进清洁能源和化学工程等产业的发展，因而具有广阔的应用前景。 Evidence shows that human activities are the main cause of the current global climate crisis, and the excessive emission of CO 2 into the atmosphere has the greatest impact. Compared with traditional emission reduction methods such as improving energy efficiency and developing renewable energy, the technical route of directly converting CO 2 into low-carbon chemicals (methanol, dimethyl ether, aromatic hydrocarbons, etc.) through catalytic hydrogenation is becoming more and more popular. The more attention. It can not only effectively reduce CO 2 emissions, but also promote the development of clean energy and chemical engineering industries, so it has broad application prospects.
CO 2向低碳化学品的转化过程主要包括两个反应步骤，即可逆的甲醇加氢合成(Methanol Synthesis，MS)反应和不可逆的甲醇脱水(Methanol Dehydration，MD)反应。其中，MS反应需要在高温(200～300℃)、高压(3～10MPa)下进行，常用的催化剂是以Cu-ZnO-Al 2O 3为代表的铜基催化剂；MD反应需要在高温(300～350℃)下进行，常用的催化剂为固体酸催化剂，如沸石分子筛、活性氧化铝等。两步法是实现CO 2合成低碳化学品的传统方法，原料气先经过加氢催化剂床层生成甲醇，再经过脱水催化剂床层生成液体燃料。但由于两步反应的反应条件并不相同，往往需要设计建造不同的反应床，导致成本增加，不利于提高经济效益。针对这一问题，本领域技术人员进一步提出了一步法的解决思路，期望在同一个反应床中同时完成MS和MD两个反应。这将显著提高该工艺的经济性，然而也对催化剂提出了更高的要求。 The conversion process of CO 2 to low-carbon chemicals mainly includes two reaction steps, namely the reversible methanol synthesis (MS) reaction and the irreversible methanol dehydration (MD) reaction. Among them, the MS reaction needs to be carried out at high temperature (200～300℃) and high pressure (3～10MPa). The commonly used catalyst is a copper- based catalyst represented by Cu-ZnO-Al 2 O 3 ; the MD reaction needs to be carried out at high temperature (300 ～350℃), the commonly used catalysts are solid acid catalysts, such as zeolite molecular sieves, activated alumina, etc. The two-step method is a traditional method for CO 2 synthesis of low-carbon chemicals. The feed gas first passes through the hydrogenation catalyst bed to generate methanol, and then passes through the dehydration catalyst bed to generate liquid fuel. However, because the reaction conditions of the two-step reaction are not the same, it is often necessary to design and build different reaction beds, which leads to increased costs and is not conducive to improving economic benefits. In response to this problem, those skilled in the art have further proposed a one-step solution, expecting to complete both MS and MD reactions in the same reaction bed. This will significantly improve the economics of the process, but it also places higher demands on the catalyst.
现有技术中，直接机械混合加氢催化剂和脱水催化剂(即双功能催化)是最常用的技术方案。发明专利CN104368378A公开了一种二氧化碳加氢直接制备二甲醚催化剂的方法，采用机械研磨混合的方式将铜基 催化剂和HZSM-5沸石混合均匀，用以催化加氢制备二甲醚。为提高催化剂性能，发明专利CN1356163A公开了一种由合成气直接制备二甲醚的方法，采用共沉淀沉积法将金属氧化物负载于γ-氧化铝上，缩短了加氢活性组分和脱水活性组分之间的距离；发明专利CN102600852A公开了一种制备二甲醚的催化剂及其制备方法和应用，分别制备活性组分的前驱体和氧化锆-氧化铝混合氧化物前驱体，再将二者加入同一溶液中搅拌均匀，干燥后得到复合型催化剂，有助于二者的均匀分散。进一步地，发明专利CN102228834A以二氧化硅、活性炭、γ-氧化铝和ZSM-5中的一种或多种作为载体，采用体积分步浸渍法将活性组分负载于催化剂载体上，发明专利CN104148083B、CN107970943A同样采取等体积浸渍法将活性金属负载于活性炭上，得到用于不饱和烃类加氢反应的双功能催化剂。该方法从一定程度上增加了催化剂的比表面积，优化了传质过程。此外，本领域研究人员还开发了一系列核壳型催化剂。发明专利CN103212418A以甲醇合成催化剂CuO-ZnO-Al 2O 3为内核，将其分散于加入了硅源和额外铝源的溶液中，在原催化剂表面包裹一层独立的SiO 2-Al 2O 3壳层。发明专利CN101934232A、CN105170179A采用化学均匀沉淀法以硝酸铜、硝酸锌和HZSM-5分子筛为原料，制得核壳状Cu-ZnO/HZSM-5，用于合成气直接合成二甲醚。虽然核壳型催化剂表现出良好的结构性能，但其完全包裹的形态不利于产物的排出，还容易导致核心过热。 In the prior art, direct mechanical mixing of hydrogenation catalysts and dehydration catalysts (ie, dual-function catalysis) is the most commonly used technical solution. The invention patent CN104368378A discloses a method for directly preparing dimethyl ether catalyst by hydrogenation of carbon dioxide. The copper-based catalyst and HZSM-5 zeolite are uniformly mixed by means of mechanical grinding and mixing to prepare 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 from synthesis gas. The metal oxide is supported on γ-alumina by the co-precipitation deposition method, which shortens the hydrogenation active components and dehydration activity. The distance between the components; invention patent CN102600852A discloses a catalyst for preparing dimethyl ether and its preparation method and application. The precursor of the active component and the precursor of the zirconia-alumina mixed oxide are prepared separately, and the two Add them to the same solution and stir evenly, and get a composite catalyst after drying, which helps to disperse the two evenly. Furthermore, the invention patent CN102228834A uses one or more of silica, activated carbon, γ-alumina and ZSM-5 as the carrier, and uses the volumetric stepwise impregnation method to load the active components on the catalyst carrier. The invention patent CN104148083B , CN107970943A also adopts equal volume impregnation method to load active metals on activated carbon to obtain a dual-functional catalyst for the hydrogenation of unsaturated hydrocarbons. This method increases the specific surface area of the catalyst to a certain extent and optimizes the mass transfer process. In addition, researchers in this field have also developed a series of core-shell catalysts. The invention patent CN103212418A uses the methanol synthesis catalyst CuO-ZnO-Al 2 O 3 as the core, which is dispersed in a solution containing a silicon source and an additional aluminum source, and a separate SiO 2 -Al 2 O 3 shell is wrapped on the surface of the procatalyst Floor. The invention patents CN101934232A and CN105170179A adopt a chemical uniform precipitation method using copper nitrate, zinc nitrate and HZSM-5 molecular sieve as raw materials to prepare core-shell Cu-ZnO/HZSM-5 for direct synthesis of dimethyl ether from syngas. Although the core-shell type catalyst exhibits good structural properties, its completely wrapped form is not conducive to the discharge of the product, and it is also easy to cause the core to overheat.
发明内容Summary of the invention
(一)要解决的技术问题(1) Technical problems to be solved
针对现有双功能催化剂协同效果差、目标产物选择性低等不足，本发明提出了一种铝共享金属-沸石(ASMZ)双功能催化剂及制备方法和应用。Aiming at the disadvantages of the existing dual-functional catalysts such as poor synergistic effect and low target product selectivity, the present invention proposes an aluminum shared metal-zeolite (ASMZ) dual-functional catalyst, and a preparation method and application thereof.
(二)技术方案(2) Technical solution
为了达到上述目的，本发明采用的主要技术方案包括：In order to achieve the above objectives, the main technical solutions adopted by the present invention include:
一方面，本发明提供一种铝共享金属-沸石双功能催化剂，其包含：In one aspect, the present invention provides an aluminum shared metal-zeolite dual-functional catalyst, which comprises:
Cu-MO x-Al 2O 3纳米微粒和纳米ZSM-5沸石； Cu-MO x -Al 2 O 3 nano particles and nano ZSM-5 zeolite;
M为金属元素，Cu以铜金属或铜氧化物形式存在；M is a metal element, and Cu exists in the form of copper metal or copper oxide;
所述纳米ZSM-5沸石原位生长在所述Cu-MO x-Al 2O 3纳米微粒的表面，且所述纳米ZSM-5沸石与Cu-MO x-Al 2O 3纳米微粒共享Al原子。 The nano ZSM-5 zeolite is grown in situ on the surface of the Cu-MO x -Al 2 O 3 nanoparticles, and the nano ZSM-5 zeolite and the Cu-MO x -Al 2 O 3 nanoparticles share Al atoms .
ZSM-5分子筛在国内已有广泛的用途，用作催化剂时可增加气体分子中烯烃的含量。ZSM-5 molecular sieve has been widely used in China. When used as a catalyst, it can increase the content of olefins in gas molecules.
在本发明一个实施例中，所述双功能催化剂的表达式为：(Cu xM yAl zO 0.5*m*y+1.5*z)·[H n(Al nSi 96-nO 192)]；其中x、y、z、n为自然数，且n＜27；其中，M＝Zn、Zr、Mn、Ce或Co，m为金属离子M的价态。 In an embodiment of the present invention, the expression of the dual-function catalyst is: (Cu x M y Al z O 0.5*m*y+1.5*z )·[H n (Al n Si 96-n O 192 ) ]; where x, y, z, n are natural numbers, and n<27; where M=Zn, Zr, Mn, Ce or Co, and m is the valence state of the metal ion M.
在本发明一个实施例中，所述Cu-MO x-Al 2O 3纳米微粒的平均粒径不大于100nm，ZSM-5沸石的平均粒径不大于200nm，ZSM-5沸石结合在所述Cu-MO x-Al 2O 3纳米微粒表面。 In an embodiment of the present invention, the average particle size of the Cu-MO x -Al 2 O 3 nanoparticles is not greater than 100 nm, the average particle size of the ZSM-5 zeolite is not greater than 200 nm, and the ZSM-5 zeolite is bound to the Cu -MO x -Al 2 O 3 nanoparticle surface.
另一方面，本发明还提供一种铝共享金属-沸石(ASMZ)双功能催化剂的制备方法，其包括如下步骤：On the other hand, the present invention also provides a method for preparing aluminum shared metal-zeolite (ASMZ) bifunctional catalyst, which includes the following steps:
S1:配制含有Cu 2+、M m+和Al 3+的混合金属盐溶液； S1: Prepare a mixed metal salt solution containing Cu 2+ , M m+ and Al 3+;
S2:将S1得到的金属盐溶液，向被持续搅拌的沉淀剂溶液中滴入，直至溶液pH值稳定在7-8之间，得到混合溶液；S2: Drop the metal salt solution obtained by S1 into the precipitant solution that is continuously stirred until the pH value of the solution stabilizes between 7-8 to obtain a mixed solution;
S3:使S2中的混合溶液静置老化，再将过滤、洗涤、烘干后得到的滤饼在高温下煅烧，得到加氢催化剂Cu-MO x-Al 2O 3粉末(缩写为CMAl)； S3: Allow the mixed solution in S2 to stand and age, and then calcinate the filter cake obtained after filtration, washing, and drying at high temperature to obtain hydrogenation catalyst Cu-MO x -Al 2 O 3 powder (abbreviated as CMAl);
S4:将S3得到的Cu-MO x-Al 2O 3粉末均匀分散在去离子水中，依次加入模板剂和氯化钠，室温下连续搅拌； S4: Disperse the Cu-MO x -Al 2 O 3 powder obtained from S3 uniformly in deionized water, add template and sodium chloride sequentially, and stir continuously at room temperature;
S5:根据预设的ZSM-5沸石中硅铝比的需求，以Cu-MO x-Al 2O 3粉末中的铝为唯一铝源，向S4得到的溶液中逐滴加入适量硅源，在室温下搅拌0.5h-5h后再在加热下搅拌，经充分搅拌后，于室温下静置老化； S5: According to the requirements of the preset ratio of silicon to aluminum in the ZSM-5 zeolite, the aluminum in the Cu-MO x -Al 2 O 3 powder is used as the only aluminum source, and an appropriate amount of silicon source is added dropwise to the solution obtained by S4. Stir at room temperature for 0.5h-5h, then stir under heating, after fully stirring, stand still at room temperature for aging;
S6:将S5中老化后的混合溶液转移至高压反应釜中，在加热条件下水热反应2-4天，冷却、过滤、洗涤、干燥后得到催化剂前驱体；S6: Transfer the aged mixed solution in S5 to an autoclave, hydrothermally react for 2-4 days under heating conditions, and obtain a catalyst precursor after cooling, filtering, washing, and drying;
S7:高温下煅烧S6得到的催化剂前驱体以去除模板剂，然后置于铵盐溶液中离子交换3-5次，洗涤、过滤、干燥后再次煅烧，得到铝共享金属-沸石双功能催化剂(ASMZ)。S7: The catalyst precursor obtained by calcining S6 at high temperature to remove the template is then placed in an ammonium salt solution for ion exchange 3-5 times, washed, filtered, dried and then calcined again to obtain an aluminum shared metal-zeolite dual-functional catalyst (ASMZ ).
优选地，步骤S1中，对混合金属盐溶液进行超声处理，超声处理时间为10-30min。Preferably, in step S1, ultrasonic treatment is performed on the mixed metal salt solution, and the ultrasonic treatment time is 10-30 min.
优选地，步骤S2中，所述沉淀剂溶液恒温在设定温度，设定温度为45～70℃。Preferably, in step S2, the precipitant solution is kept at a constant temperature at a set temperature, and the set temperature is 45-70°C.
优选地，步骤S2中，金属盐溶液的滴加速度为1-5mL/min。Preferably, in step S2, the dropping rate of the metal salt solution is 1-5 mL/min.
优选地，步骤S3中，老化温度为45～70℃；滤饼的煅烧温度为350～500℃，煅烧时间为4-6h，煅烧气氛为空气、氮气或氩气。Preferably, in step S3, the aging temperature is 45-70°C; the calcination temperature of the filter cake is 350-500°C, the calcination time is 4-6 hours, and the calcination atmosphere is air, nitrogen or argon.
优选地，步骤S4中，模板剂为包括但不限于四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、乙二胺、氨水和吡啶在的一种或几种。Preferably, in step S4, the template agent is one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia and pyridine.
优选地，步骤S4中，室温下连续搅拌0.5-10h。Preferably, in step S4, continuous stirring is performed at room temperature for 0.5-10 h.
优选地，步骤S5中，加热下搅拌是指温度在75-90℃，搅拌时间为1-10h。Preferably, in step S5, stirring under heating means that the temperature is 75-90° C., and the stirring time is 1-10 h.
优选地，步骤S5中，以Cu-MO x-Al 2O 3粉末中的铝为唯一铝源，加入硅源使硅铝比不低于5。 Preferably, in step S5, the aluminum in the Cu-MO x -Al 2 O 3 powder is used as the only aluminum source, and the silicon source is added so that the silicon-to-aluminum ratio is not less than 5.
优选地，步骤S5中，所述硅源包括但不限于正硅酸乙酯、单分散SiO 2、硅溶胶、及白炭黑中的一种或几种。 Preferably, in step S5, the silicon source includes but is not limited to one or more of tetraethyl orthosilicate, monodisperse SiO 2 , silica sol, and white carbon black.
优选地，步骤S6中，水热反应的温度为120-180℃。水热反应温度越低，所需反应时间越长；优选在进行水热反应的同时伴随搅拌的操作。Preferably, in step S6, the temperature of the hydrothermal reaction is 120-180°C. The lower the hydrothermal reaction temperature, the longer the required reaction time; preferably, the operation of stirring is accompanied by the hydrothermal reaction.
优选地，步骤S7中，去除模板剂的煅烧温度为450-600℃，煅烧4-6h，煅烧气氛为空气、氮气或氩气。Preferably, in step S7, the calcination temperature for removing the template agent is 450-600° C., the calcination is 4-6 hours, and the calcination atmosphere is air, nitrogen or argon.
优选地，步骤S7中，用于铵离子交换的铵盐包括但不限于氯化铵、硝酸铵和氨水在的一种或几种。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 ammonia.
优选地，步骤S7中，再次煅烧温度为250-500℃，煅烧时间为4-6h，煅烧气氛为空气、氮气或氩气。Preferably, in step S7, the calcination temperature is 250-500° C., the calcination time is 4-6 hours, and the calcination atmosphere is air, nitrogen or argon.
此外，本发明还涉及将上述铝共享金属-沸石(ASMZ)双功能催化剂应用于CO 2催化加氢，制备甲醇和/或二甲醚。 In addition, the present invention also relates to the application of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst to the catalytic hydrogenation of CO 2 to prepare methanol and/or dimethyl ether.
(三)有益效果(3) Beneficial effects
本发明的有益效果是：The beneficial effects of the present invention are:
本发明提供的铝共享金属-沸石(ASMZ)双功能催化剂，在现有技术基础上，使该双功能催化剂中的纳米ZSM-5沸石与Cu-MO x-Al 2O 3纳米微粒(缩写为CMAl)间共享Al原子，以Al为媒介使二者紧密结合，大大缩短了传统双功能催化剂中两种催化剂成分的间距，从而显著增强了其协同效应、优化了催化性能。目前，尚未见到关于铝共享型金属-沸石双功能催化剂的相关报道。 The aluminum shared metal-zeolite (ASMZ) bifunctional catalyst provided by the present invention combines nano-ZSM-5 zeolite and Cu-MO x -Al 2 O 3 nanoparticles (abbreviated as CMAl) share Al atoms and use Al as a medium to closely combine the two, which greatly shortens the distance between the two catalyst components in the traditional dual-function catalyst, thereby significantly enhancing its synergistic effect and optimizing catalytic performance. At present, there are no reports about aluminum sharing metal-zeolite dual-functional catalysts.
此外，本发明还提供了制备上述铝共享金属-沸石(ASMZ)双功能催化剂的方法，能够有效控制CMAl催化剂和ZSM-5沸石的尺寸，实现后者在前者基础上的可控生长，本发明的制备方法过程简单、产率高，适用于大规模生产。In addition, the present invention also provides a method for preparing the aluminum shared metal-zeolite (ASMZ) dual-function catalyst, which can effectively control the size of the CMAl catalyst and the ZSM-5 zeolite, and realize the controllable growth of the latter on the basis of the former. The preparation method has simple process and high yield, and is suitable for large-scale production.
附图说明Description of the drawings
图1为本发明的铝共享金属-沸石(ASMZ)双功能催化剂微观结构的示意图。Figure 1 is a schematic diagram of the microstructure of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst of the present invention.
图2为本发明实施例1中ASMZ双功能催化剂的XRD谱图。Figure 2 is the XRD spectrum of the ASMZ bifunctional catalyst in Example 1 of the present invention.
图3为本发明实施例1中ASMZ双功能催化剂的SEM照片。Figure 3 is an SEM photograph of the ASMZ dual-functional catalyst in Example 1 of the present invention.
图4为本发明实施例1中ASMZ双功能催化剂的EDX光谱图。Figure 4 is the EDX spectrum of the ASMZ dual-function catalyst in Example 1 of the present invention.
图5为本发明实施例1中ASMZ双功能催化剂催化性能随时间变化曲线。Fig. 5 is a curve of the catalytic performance of the ASMZ dual-function catalyst in Example 1 of the present invention over time.
【附图标记说明】[Description of Reference Signs]
10、沸石；20、CMAl纳米微粒；21、Al原子；22、Cu原子。10. Zeolite; 20. CMAl nanoparticles; 21. Al atoms; 22. Cu atoms.
具体实施方式detailed description
为了更好的解释本发明，以便于理解，下面结合附图，通过具体实 施方式，对本发明作详细描述。In order to better explain the present invention and facilitate understanding, the present invention will be described in detail below with reference to the accompanying drawings and through specific implementation manners.
本发明首次提出一种共享铝的金属-沸石(ASMZ)双功能催化剂，其微观结构可参见图1所示。该双功能催化剂包括两部分，一部分为铜22、金属氧化物、氧化铝多相复合催化剂，即Cu-MO x-Al 2O 3纳米微粒20，另一方部分为沸石10，且沸石10原位生长于Cu-MO x-Al 2O 3纳米微粒20上(即CMAl)，形成沸石10的铝原子21也是形成Cu-MO x-Al 2O 3纳米微粒20的铝原子，即沸石10与CMAl纳米微粒20的共享铝原子21。本发明的双功能催化剂，两个部分以铝原子21结合点使二者紧密结合，大大缩短了传统双功能催化剂中两种催化剂成分的间距，从而显著增强了其协同效应、优化了催化性能。在催化剂中，Cu以铜金属或铜氧化物形式存在，可能为0价、1价和2价。 The present invention proposes for the first time an aluminum-sharing metal-zeolite (ASMZ) dual-function catalyst, and its microstructure can be seen in Figure 1. The dual-function catalyst includes two parts, one part is a heterogeneous composite catalyst of copper 22, metal oxide and alumina, namely Cu-MO x -Al 2 O 3 nanoparticles 20, and the other part is zeolite 10, and zeolite 10 is in situ Growing on Cu-MO x -Al 2 O 3 nanoparticles 20 (ie CMAl), the aluminum atoms 21 forming zeolite 10 are also aluminum atoms forming Cu-MO x -Al 2 O 3 nanoparticles 20, that is, zeolite 10 and CMAl The nanoparticles 20 share aluminum atoms 21. In the dual-function catalyst of the present invention, the two parts are tightly combined with the aluminum atom 21 bonding point, which greatly shortens the distance between the two catalyst components in the traditional dual-function catalyst, thereby significantly enhancing its synergistic effect and optimizing catalytic performance. In the catalyst, Cu exists in the form of copper metal or copper oxide, which may be 0, 1 and 2 valence.
为了制备所述共享铝的金属-沸石(ASMZ)双功能催化剂，本发明提供如下的制备方法：In order to prepare the aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst, the present invention provides the following preparation method:
S1、配制含有Cu 2+、M m+和Al 3+的混合金属盐溶液，并超声预处理10-30min。 S1. Prepare a mixed metal salt solution containing Cu 2+ , M m+ and Al 3+ , and ultrasonically pretreat it for 10-30 min.
S2、将沉淀剂溶液恒温在45-70℃，在持续搅拌下缓慢向沉淀剂溶液中滴入S1得到的溶液，滴加速率为1～5mL/min，直至溶液pH值稳定在7-8之间。S2. Keep the precipitant solution at a constant temperature of 45-70°C, and slowly drop the solution obtained from S1 into the precipitant solution under continuous stirring. The drip rate is 1～5mL/min, until the pH value of the solution stabilizes at 7-8. between.
S3、滴加结束后，使S2中的混合溶液静置老化，老化温度45-70℃，再将过滤、洗涤、烘干后得到的滤饼在350-500℃的高温下煅烧，煅烧气氛为空气、氮气或氩气，煅烧时间为4-6h，得到加氢催化剂CMAl。S3. After the dripping, the mixed solution in S2 is allowed to stand and age at a temperature of 45-70°C, and then the filter cake obtained after filtration, washing and drying is calcined at a high temperature of 350-500°C. The calcining atmosphere is Air, nitrogen or argon, the calcination time is 4-6h, and the hydrogenation catalyst CMAl is obtained.
S4、将S3得到的CMAl粉末均匀分散在去离子水中，依次加入模板剂和氯化钠，室温下连续搅拌1h；模板剂包括但不限于四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、乙二胺、氨水和吡啶中的一种或几种。S4. Disperse the CMAl powder obtained from S3 uniformly in deionized water, add templating agent and sodium chloride successively, and continuously stir at room temperature for 1 h; templating agents include but are not limited to tetrapropylammonium hydroxide, tetrapropylammonium bromide, One or more of tetraethylammonium hydroxide, ethylenediamine, ammonia and pyridine.
S5、根据对ZSM-5沸石硅铝比的需求，以CMAl中的铝为唯一铝源，向S4得到的溶液中逐滴加入适量硅源，在室温下搅拌0.5h，再在加热至75～90℃的温度下再搅拌1h，降至室温后静置老化。ZSM-5沸石的硅铝 比不低于5；硅源包括但不限于正硅酸乙酯、单分散SiO 2、硅溶胶和白炭黑中的一种或几种。 S5. According to the requirement of the silica-aluminum ratio of ZSM-5 zeolite, using the aluminum in CMAl as the only aluminum source, add an appropriate amount of silicon source dropwise to the solution obtained in S4, stir at room temperature for 0.5h, and then heat to 75～ Stir for another 1 hour at 90°C, then stand for aging after cooling down to room temperature. The silicon-to-aluminum ratio of ZSM-5 zeolite is not less than 5; silicon sources include but are not limited to one or more of ethyl orthosilicate, monodisperse SiO 2 , silica sol and white carbon black.
S6、将S5中老化后的混合溶液转移至高压反应釜中，在120～180℃下水热反应2-4天，过滤、洗涤、干燥后得到催化剂前驱体。S6: Transfer the aged mixed solution in S5 to an autoclave, and hydrothermally react at 120-180°C for 2-4 days, filter, wash, and dry to obtain a catalyst precursor.
通常情况下，水热反应温度为，且水热反应温度越低，所需反应时间越长；在水热反应的同时可伴随搅拌。Under normal circumstances, the hydrothermal reaction temperature is, and the lower the hydrothermal reaction temperature, the longer the required reaction time; the hydrothermal reaction can be accompanied by stirring.
S7、在450～600℃下煅烧S6得到的催化剂前驱体，煅烧时间为4-6h以去除掉模板剂，煅烧气氛为空气、氮气或氩气；然后将煅烧后产物在铵盐溶液中离子交换3～5次，洗涤、过滤、干燥后再次在250-500℃下煅烧、煅烧时间4-6h、煅烧气氛为空气、氮气或氩气，煅烧后得到铝共享金属-沸石(ASMZ)双功能催化剂产品。其中，用于铵离子交换的铵盐包括但不限于氯化铵、硝酸铵和氨水中的一种或几种的混合。S7. The catalyst precursor obtained by calcining S6 at 450～600℃, the calcining time is 4-6h to remove the template, and the calcining atmosphere is air, nitrogen or argon; then the calcined product is ion exchanged in the ammonium salt solution 3 to 5 times, after washing, filtering, and drying, calcining again at 250-500℃, calcining time 4-6h, calcining atmosphere is air, nitrogen or argon, and calcined to obtain aluminum shared metal-zeolite (ASMZ) dual-function catalyst product. Among them, 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.
为了进一步使本发明共享铝的金属-沸石(ASMZ)双功能催化剂的优点和技术效果得到证实，以下结合具体实施例说明。In order to further confirm the advantages and technical effects of the aluminum-sharing metal-zeolite (ASMZ) dual-functional catalyst of the present invention, the following description is combined with specific examples.
制备例Preparation example
实施例1Example 1
本实施例提供一种具体的共享铝的金属-沸石(ASMZ)双功能催化剂，按如下步骤制备：This embodiment provides a specific aluminum-sharing metal-zeolite (ASMZ) dual-functional catalyst, which is prepared as follows:
(1)将Cu(NO 3) 2·3H 2O、Zn(NO 3) 2·6H 2O、Al(NO 3) 3·9H 2O按Cu:Zn:Al＝6:3:1的摩尔比溶于去离子水，配成1mol/L的金属盐溶液100mL，超声处理30min； (1) Put Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O, Al(NO 3 ) 3 ·9H 2 O according to the mole of Cu:Zn:Al=6:3:1 Dissolve in deionized water, make 100mL of 1mol/L metal salt solution, and ultrasonic treatment for 30min;
(2)将Na 2CO 3溶于去离子水，配成1mol/L的溶液250mL；将Na 2CO 3溶液水浴加热至55℃，在磁力搅拌下将金属盐溶液逐滴滴入，直至pH稳定在7-8。 (2) Dissolve Na 2 CO 3 in deionized water to make 250 mL of a 1mol/L solution; heat the Na 2 CO 3 solution in a water bath to 55°C, and drop the metal salt solution dropwise under magnetic stirring until the pH Stable at 7-8.
(3)待完全沉淀后，在55℃下老化过夜，过滤、洗涤后，将滤饼样品置于120℃下干燥12h制得CZAl前驱体；将滤饼样品在400℃下煅烧4h，得到样品CZAl。(3) After complete precipitation, aging at 55°C overnight. After filtering and washing, the filter cake sample is dried at 120°C for 12 hours to prepare the CZAl precursor; the filter cake sample is calcined at 400°C for 4 hours to obtain the sample CZAl.
(4)将CZAl溶于去离子水后滴加四丙基氢氧化铵，搅拌均匀后加入NaCl，将混合溶液置于室温环境下搅拌1h。(4) Dissolve CZAl in deionized water, add tetrapropylammonium hydroxide dropwise, stir evenly, add NaCl, and place the mixed solution at room temperature and stir for 1 hour.
(5)按Si:Al＝20的摩尔比向混合溶液中逐滴加入正硅酸乙酯，混合均匀后在室温条件下搅拌0.5h，随后将其置于80℃温度下油浴搅拌1h，充分搅拌后于室温条件静置老化20h。(5) Add ethyl orthosilicate dropwise to the mixed solution according to the molar ratio of Si:Al=20, mix well and stir at room temperature for 0.5h, then place it in an oil bath at 80℃ and stir for 1h. After fully stirring, stand for aging at room temperature for 20 hours.
(6)将所得溶液转移到高压反应釜中，在180℃下水热反应48h；冷却、抽滤、洗涤、干燥后，得到双功能催化剂前驱体。(6) Transfer the obtained solution to an autoclave, and hydrothermally react at 180°C for 48 hours; after cooling, suction filtration, washing, and drying, a dual-function catalyst precursor is obtained.
(7)在550℃、空气气氛中煅烧上述双功能催化剂前驱体5h以去除模板剂；在50℃下，将煅烧后产品在0.2mmol/L的氯化铵溶液中离子交换3次(固液比＜1:100)，抽滤、洗涤、干燥后在500℃、空气气氛中煅烧5h除去铵离子，获得ASMZ双功能催化剂产品。(7) Calcining the above-mentioned dual-functional catalyst precursor at 550°C in air atmosphere for 5h to remove the template; at 50°C, the calcined product is ion-exchanged 3 times in 0.2mmol/L ammonium chloride solution (solid-liquid Ratio<1:100), after suction filtration, washing, drying, calcination at 500℃, air atmosphere for 5h to remove ammonium ions to obtain ASMZ bifunctional catalyst product.
实施例2Example 2
本实施例提供一种具体的共享铝的金属-沸石(ASMZ)双功能催化剂，按如下步骤制备：This embodiment provides a specific aluminum-sharing metal-zeolite (ASMZ) dual-functional catalyst, which is prepared as follows:
(1)将Cu(NO 3) 2·3H 2O、Zn(NO 3) 2·6H 2O、Al(NO 3) 3·9H 2O按Cu:Zn:Al＝6:3:1的摩尔比溶于去离子水，配成1mol/L的金属盐溶液100mL，超声处理30min。 (1) Put Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O, Al(NO 3 ) 3 ·9H 2 O according to the mole of Cu:Zn:Al=6:3:1 It is more soluble in deionized water, made into 100mL of 1mol/L metal salt solution, and ultrasonically treated for 30min.
(2)将Na 2CO 3溶于去离子水，配成1mol/L的溶液250mL；将Na 2CO 3溶液水浴加热至55℃，在磁力搅拌下将金属盐溶液逐滴滴入，直至pH稳定在7-8。 (2) Dissolve Na 2 CO 3 in deionized water to make 250 mL of a 1mol/L solution; heat the Na 2 CO 3 solution in a water bath to 55°C, and drop the metal salt solution dropwise under magnetic stirring until the pH Stable at 7-8.
(3)待完全沉淀后，在55℃下老化过夜，过滤、洗涤后，将滤饼样品置于120℃下干燥12h制得CZAl前驱体；将滤饼样品在400℃下煅烧4h，得到样品CZAl。(3) After complete precipitation, aging at 55°C overnight. After filtering and washing, the filter cake sample is dried at 120°C for 12 hours to prepare the CZAl precursor; the filter cake sample is calcined at 400°C for 4 hours to obtain the sample CZAl.
(4)将CZAl溶于去离子水后滴加四丙基氢氧化铵，搅拌均匀后加入NaCl，将混合溶液置于室温环境下搅拌1h。(4) Dissolve CZAl in deionized water, add tetrapropylammonium hydroxide dropwise, stir evenly, add NaCl, and place the mixed solution at room temperature and stir for 1 hour.
(5)按Si:Al＝10的摩尔比向混合溶液中逐滴加入正硅酸乙酯，混合均匀后在室温条件下搅拌0.5h，随后将其置于80℃温度下油浴搅拌1h，充 分搅拌后于室温条件静置老化20h。(5) Add ethyl orthosilicate dropwise to the mixed solution according to the molar ratio of Si:Al=10, mix well and stir at room temperature for 0.5h, then place it in an oil bath at 80℃ and stir for 1h. After fully stirring, stand for aging at room temperature for 20 hours.
(6)将所得溶液转移到高压反应釜中，在180℃下水热反应48h；冷却、抽滤、洗涤、干燥后，得到双功能催化剂前驱体。(6) Transfer the obtained solution to an autoclave, and hydrothermally react at 180°C for 48 hours; after cooling, suction filtration, washing, and drying, a dual-function catalyst precursor is obtained.
(7)在550℃、空气气氛中煅烧上述双功能催化剂前驱体5h以去除模板剂；在50℃下，将煅烧后产品在0.2mmol/L的氯化铵溶液中离子交换3次(固液比＜1:100)，抽滤、洗涤、干燥后在500℃、空气气氛中煅烧5h除去铵离子，获得ASMZ双功能催化剂产品，产物中Si:Al的摩尔比约为10.0，且具备了良好的微观结构。(7) Calcining the above-mentioned dual-functional catalyst precursor at 550°C in air atmosphere for 5h to remove the template; at 50°C, the calcined product is ion-exchanged 3 times in 0.2mmol/L ammonium chloride solution (solid-liquid Ratio<1:100), after suction filtration, washing and drying, calcining at 500℃, air atmosphere for 5h to remove ammonium ions, and obtain ASMZ bifunctional catalyst product. The molar ratio of Si:Al in the product is about 10.0, and it has a good The microstructure.
催化剂的活化、表征和催化性能测试Catalyst activation, characterization and catalytic performance testing
催化剂的活化Catalyst activation
ASMZ双功能催化剂的活化在还原性气体气氛中实现。首先，将实施例1-2制备的双功能催化剂粉末在60MPa下压片(不加入粘结剂)，制成直径约为0.5mm的催化剂小球；将催化剂小球在200～350℃、氢气气氛下保温2～6h，催化剂中的CuO被还原成Cu 0；使催化剂在还原性气体气氛或惰性气体气氛中自然冷却至室温，即可获得活化后的ASMZ双功能催化剂。实验表明，活化后的催化剂在无氧条件下长期保存，即使在干燥空气中也可保存10天以上。 The activation of the ASMZ bifunctional catalyst is realized in a reducing gas atmosphere. First, the dual-functional catalyst powder prepared in Example 1-2 was tableted at 60 MPa (without adding a binder) to form catalyst pellets with a diameter of about 0.5 mm; the catalyst pellets were heated at 200-350°C under hydrogen. After holding for 2-6 hours in the atmosphere, the CuO in the catalyst is reduced to Cu 0 ; the catalyst is naturally cooled to room temperature in a reducing gas atmosphere or an inert gas atmosphere to obtain an activated ASMZ bifunctional catalyst. Experiments show that the activated catalyst can be stored for a long time under anaerobic conditions, even in dry air, it can be stored for more than 10 days.
催化剂的组成表征分析Catalyst composition characterization analysis
电感耦合等离子原子发射光谱(ICP)分析显示，实施例1制备的ASMZ双功能催化剂的整体Si元素的质量含量约为36.2％；X射线光电子能谱(XPS)分析结果显示，实施例1的ASMZ双功能催化剂的表明Si元素的质量含量约34.3％。两种方法测试数值接近，且都能表明实施例1制备的ASMZ双功能催化剂中已经出现了沸石成分。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 results showed that the ASMZ of Example 1 The dual function catalyst shows that the mass content of Si element is about 34.3%. The test values of the two methods are close, and both can indicate that the zeolite component has appeared in the ASMZ bifunctional catalyst prepared in Example 1.
通过低温氮气吸脱附测试结果显示，实施例1的ASMZ双功能催化剂的BET比表面积高达260.3m 2/g，约为传统铜锌铝催化剂的6.5倍，说明ASMZ双功能催化剂的孔结构得到了显著改善。 The results of the low-temperature nitrogen adsorption and desorption test show that the BET specific surface area of the ASMZ bifunctional catalyst of Example 1 is as high as 260.3m 2 /g, which is about 6.5 times that of the traditional copper-zinc-aluminum catalyst, indicating that the pore structure of the ASMZ bifunctional catalyst has been obtained. Significantly improved.
参见图2，X射线衍射(XRD)结果显示，实施例1的ASMZ双功 能催化剂中出现了明显的ZSM-5特征衍射峰，同时存在CuO的特征衍射峰，表明ASMZ双功能催化剂中同时存在CZAl催化剂和ZSM-5沸石的晶体结构，与预期结果一致。Referring to Figure 2, X-ray diffraction (XRD) results show that the ASMZ dual-functional catalyst of Example 1 has obvious characteristic diffraction peaks of ZSM-5 and the characteristic diffraction peaks of CuO at the same time, indicating that CZAl is also present in the ASMZ dual-functional catalyst. The crystal structure of the catalyst and ZSM-5 zeolite are consistent with the expected results.
参见图3，扫描电子显微镜(SEM)照片显示，在实施例1的ASMZ双功能催化剂中既能观察到CZAl的纳米颗粒，又能观察到立方体状的ZSM-5沸石，证明二者已经紧密结合在一起。Referring to Figure 3, the scanning electron microscope (SEM) photo shows that both CZAl nanoparticles and cubic ZSM-5 zeolite can be observed in the ASMZ bifunctional catalyst of Example 1, which proves that the two have been tightly combined. Together.
参见图4，能量色散X射线光谱(EDX)结果显示，实施例1的ASMZ双功能催化剂中铜和硅都能均匀分散，但它们趋于分散在不同区域，表明CZAl催化剂和ZSM-5沸石并未完全复合，而是相互依托生长，符合图1中所示意的目标结构。Referring to Figure 4, energy dispersive X-ray spectroscopy (EDX) results show that copper and silicon in the ASMZ bifunctional catalyst of Example 1 can be uniformly dispersed, but they tend to be dispersed in different regions, indicating that the CZAl catalyst and ZSM-5 zeolite are in parallel It is not completely recombined, but grows dependent on each other, in line with the target structure shown in Figure 1.
综上，本发明制备的一种铝共享金属-沸石(ASMZ)双功能催化剂具有良好的结构性能，满足预期设计要求。In summary, the aluminum shared metal-zeolite (ASMZ) dual-functional catalyst prepared by the present invention has good structural properties and meets the expected design requirements.
催化剂的催化性能测试Catalytic performance test of catalyst
实施例1中ASMZ双功能催化剂的催化性能测试在固定床反应器中进行。当反应温度为274℃、反应压力为3.0MPa时，使用0.55g催化剂实现的单床CO 2转化率约为21.25％，甲醇(MeOH)和二甲醚(DME)的总选择性可达85.3％左右，优于现有催化剂。在250℃、3.0MPa下连续反应10h后，其各项性能指标均没有出现明显下降(参见图5)，表明制备的ASMZ双功能催化剂具有良好的稳定性。 The catalytic performance test of the ASMZ bifunctional catalyst in Example 1 was carried out in a fixed bed reactor. When the reaction temperature is 274°C and the reaction pressure is 3.0MPa, the single-bed CO 2 conversion rate achieved by using 0.55g catalyst is about 21.25%, and the total selectivity of methanol (MeOH) and dimethyl ether (DME) can reach 85.3% Around, better than existing catalysts. After 10 hours of continuous reaction at 250°C and 3.0 MPa, the performance indicators did not decrease significantly (see Figure 5), indicating that the prepared ASMZ bifunctional catalyst has good stability.

Claims (10)

  1. 一种铝共享金属-沸石双功能催化剂，其特征在于，包含：An aluminum shared metal-zeolite dual-function catalyst, which is characterized in that it comprises:
    Cu-MO x-Al 2O 3纳米微粒和纳米ZSM-5沸石； Cu-MO x -Al 2 O 3 nano particles and nano ZSM-5 zeolite;
    M为金属元素，Cu以铜金属或铜氧化物形式存在；M is a metal element, and Cu exists in the form of copper metal or copper oxide;
    所述纳米ZSM-5沸石原位生长在所述Cu-MO x-Al 2O 3纳米微粒的表面，且所述纳米ZSM-5沸石与Cu-MO x-Al 2O 3纳米微粒共享Al原子。 The nano ZSM-5 zeolite is grown in situ on the surface of the Cu-MO x -Al 2 O 3 nanoparticles, and the nano ZSM-5 zeolite and the Cu-MO x -Al 2 O 3 nanoparticles share Al atoms .
  2. 根据权利要求1所述铝共享金属-沸石双功能催化剂，其特征在于，所述双功能催化剂的表达式为：(Cu xM yAl zO 0.5*m*y+1.5*z)·[H n(Al nSi 96-nO 192)]；其中x、y、z、n为自然数，且n＜27；其中，M＝Zn、Zr、Mn、Ce或Co，m为金属离子M的价态。 The aluminum shared metal-zeolite dual-functional catalyst according to claim 1, wherein the expression of the dual-functional catalyst is: (Cu x M y Al z O 0.5*m*y+1.5*z )·[H n (Al n Si 96-n O 192 )]; where x, y, z, n are natural numbers, and n<27; where M = Zn, Zr, Mn, Ce or Co, and m is the valence of the metal ion M state.
  3. 根据权利要求1所述铝共享金属-沸石双功能催化剂，其特征在于，The aluminum shared metal-zeolite dual-function catalyst according to claim 1, wherein:
    所述Cu-MO x-Al 2O 3纳米微粒的平均粒径不大于100nm，ZSM-5沸石的平均粒径不大于200nm，ZSM-5沸石结合在所述Cu-MO x-Al 2O 3纳米微粒表面。 The average particle size of the Cu-MO x -Al 2 O 3 nanoparticles is not greater than 100 nm, the average particle size of the ZSM-5 zeolite is not greater than 200 nm, and the ZSM-5 zeolite is bound to the Cu-MO x -Al 2 O 3 Nanoparticle surface.
  4. 一种铝共享金属-沸石(ASMZ)双功能催化剂的制备方法，其包括如下步骤：A preparation method of aluminum shared metal-zeolite (ASMZ) bifunctional catalyst, which comprises the following steps:
    S1:配制含有Cu 2+、M m+和Al 3+的混合金属盐溶液； S1: Prepare a mixed metal salt solution containing Cu 2+ , M m+ and Al 3+;
    S2:将S1得到的金属盐溶液，向被持续搅拌的沉淀剂溶液中滴入，直至溶液pH值稳定在7-8之间，得到混合溶液；S2: Drop the metal salt solution obtained by S1 into the precipitant solution that is continuously stirred until the pH value of the solution stabilizes between 7-8 to obtain a mixed solution;
    S3:使S2中的混合溶液静置老化，再将过滤、洗涤、烘干后得到的滤饼在高温下煅烧，得到加氢催化剂Cu-MO x-Al 2O 3粉末； S3: The mixed solution in S2 is allowed to stand and age, and then the filter cake obtained after filtration, washing and drying is calcined at high temperature to obtain hydrogenation catalyst Cu-MO x -Al 2 O 3 powder;
    S4:将S3得到的Cu-MO x-Al 2O 3粉末均匀分散在去离子水中，依次加入模板剂和氯化钠，室温下连续搅拌； S4: Disperse the Cu-MO x -Al 2 O 3 powder obtained from S3 uniformly in deionized water, add template and sodium chloride sequentially, and stir continuously at room temperature;
    S5:根据预设的ZSM-5沸石中硅铝比的需求，以Cu-MO x-Al 2O 3粉末中的铝为唯一铝源，向S4得到的溶液中逐滴加入适量硅源，在室温下搅拌0.5h-5h后再在加热下搅拌，经充分搅拌后，于室温下静置老化； S5: According to the requirements of the preset ratio of silicon to aluminum in the ZSM-5 zeolite, the aluminum in the Cu-MO x -Al 2 O 3 powder is used as the only aluminum source, and an appropriate amount of silicon source is added dropwise to the solution obtained by S4. Stir at room temperature for 0.5h-5h, then stir under heating, after fully stirring, stand still at room temperature for aging;
    S6:将S5中老化后的混合溶液转移至高压反应釜中，在加热条件下水热反应2-4天，冷却、过滤、洗涤、干燥后得到催化剂前驱体；S6: Transfer the aged mixed solution in S5 to an autoclave, hydrothermally react for 2-4 days under heating conditions, and obtain a catalyst precursor after cooling, filtering, washing, and drying;
    S7:高温下煅烧S6得到的催化剂前驱体以去除模板剂，然后置于铵盐溶液中离子交换3-5次，洗涤、过滤、干燥后再次煅烧，得到铝共享金属-沸石双功能催化剂。S7: The catalyst precursor obtained by calcining S6 at a high temperature to remove the template is then placed in an ammonium salt solution for ion exchange 3-5 times, washed, filtered, dried and then calcined again to obtain an aluminum shared metal-zeolite dual-functional catalyst.
  5. 根据权利要求4所述制备方法，其特征在于，步骤S2中，所述沉淀剂溶液恒温在设定温度，设定温度为45～70℃。The preparation method according to claim 4, characterized in that, in step S2, the precipitant solution is kept at a set temperature, and the set temperature is 45-70°C.
  6. 根据权利要求4所述制备方法，其特征在于，步骤S3中，老化温度为45～70℃；滤饼的煅烧温度为350～500℃，煅烧时间为4-6h，煅烧气氛为空气、氮气或氩气。The preparation method according to claim 4, wherein in step S3, the aging temperature is 45-70°C; the calcination temperature of the filter cake is 350-500°C, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or Argon.
  7. 根据权利要求4所述制备方法，其特征在于，步骤S4中，模板剂为包括但不限于四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、乙二胺、氨水和吡啶在的一种或几种。The preparation method according to claim 4, characterized in that, in step S4, the template includes but is not limited to tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia One or more of the same with pyridine.
  8. 根据权利要求4所述制备方法，其特征在于，步骤S5中，以Cu-MO x-Al 2O 3粉末中的铝为唯一铝源，加入硅源使硅铝比不低于5； The preparation method according to claim 4, characterized in that, in step S5, the aluminum in the Cu-MO x -Al 2 O 3 powder is used as the only aluminum source, and the silicon source is added so that the silicon-to-aluminum ratio is not less than 5;
    所述硅源包括但不限于正硅酸乙酯、单分散SiO 2、硅溶胶及白炭黑中的一种或几种。 The silicon source includes, but is not limited to, one or more of tetraethyl orthosilicate, monodisperse SiO 2 , silica sol, and white carbon black.
  9. 根据权利要求4所述制备方法，其特征在于，步骤S7中，The preparation method according to claim 4, wherein in step S7,
    去除模板剂的煅烧温度为450-600℃，煅烧4-6h，煅烧气氛为空气、氮气或氩气；The calcination temperature for removing the template agent is 450-600℃, calcination is 4-6h, and the calcination atmosphere is air, nitrogen or argon;
    用于铵离子交换的铵盐包括但不限于氯化铵、硝酸铵和氨水在的一种或几种；Ammonium salts used for ammonium ion exchange include but are not limited to one or more of ammonium chloride, ammonium nitrate and ammonia;
    再次煅烧温度为250-500℃，煅烧时间为4-6h，煅烧气氛为空气、氮气或氩气。The calcination temperature is 250-500°C, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
  10. 权利要求1-3任一项所述铝共享金属-沸石双功能催化剂或权利要求4-9任一项所述制备方法制备的铝共享金属-沸石双功能催化剂用于CO 2催化加氢，制备甲醇和/或二甲醚。 The aluminum shared metal-zeolite dual-functional catalyst according to any one of claims 1 to 3 or the aluminum shared metal-zeolite dual-functional catalyst prepared by the preparation method according to any one of claims 4-9 is used for CO 2 catalytic hydrogenation to prepare Methanol and/or dimethyl ether.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486350A (en) * 2024-01-02 2024-02-02 山东众思创环境工程有限公司 Treatment process of biological fermentation organic wastewater

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113797959B (en) * 2021-10-25 2022-09-06 东北大学 Zeolite molecular sieve coated metal nanoparticle catalyst and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0847644A (en) * 1994-08-04 1996-02-20 Hino Motors Ltd Catalyst for purification of exhaust gas
CN101020139A (en) * 2006-05-13 2007-08-22 厦门大学 Catalyst for preparing methanol with synthetic gas and its prepn process
CN101550352A (en) * 2008-04-03 2009-10-07 中国石油化工股份有限公司 Aromatizatian catalytic material and preparation method thereof
US20100008840A1 (en) * 2005-11-14 2010-01-14 Agency For Science, Technology And Research Highly Dispersed Metal Catalysts
CN103100434A (en) * 2011-11-11 2013-05-15 中国石油化工股份有限公司 Preparation method of catalyst carrier material containing molecular sieve and alumina
CN104646049A (en) * 2013-11-20 2015-05-27 正大能源材料(大连)有限公司 Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101934233B (en) * 2010-09-13 2011-12-07 浙江大学 Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas
CN103212418B (en) * 2013-04-25 2015-05-20 太原理工大学 Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst
CN108295892A (en) * 2018-01-30 2018-07-20 贵州大学 A kind of preparation method of γ-Al2O3@CuO-ZnO@ZSM-5 double-core shell catalysts
CN108339565A (en) * 2018-01-30 2018-07-31 贵州大学 A kind of preparation method of ZnO-Al2O3@ZSM-5 catalyst with core-casing structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0847644A (en) * 1994-08-04 1996-02-20 Hino Motors Ltd Catalyst for purification of exhaust gas
US20100008840A1 (en) * 2005-11-14 2010-01-14 Agency For Science, Technology And Research Highly Dispersed Metal Catalysts
CN101020139A (en) * 2006-05-13 2007-08-22 厦门大学 Catalyst for preparing methanol with synthetic gas and its prepn process
CN101550352A (en) * 2008-04-03 2009-10-07 中国石油化工股份有限公司 Aromatizatian catalytic material and preparation method thereof
CN103100434A (en) * 2011-11-11 2013-05-15 中国石油化工股份有限公司 Preparation method of catalyst carrier material containing molecular sieve and alumina
CN104646049A (en) * 2013-11-20 2015-05-27 正大能源材料(大连)有限公司 Preparation method of catalyst for directly synthesizing dimethyl ether from synthesis gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486350A (en) * 2024-01-02 2024-02-02 山东众思创环境工程有限公司 Treatment process of biological fermentation organic wastewater
CN117486350B (en) * 2024-01-02 2024-03-19 山东众思创环境工程有限公司 Treatment process of biological fermentation organic wastewater

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