WO2023160593A1 - 用于丙烯氢氧环氧化的物理混合式催化剂及制备方法和应用 - Google Patents

用于丙烯氢氧环氧化的物理混合式催化剂及制备方法和应用 Download PDF

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WO2023160593A1
WO2023160593A1 PCT/CN2023/077766 CN2023077766W WO2023160593A1 WO 2023160593 A1 WO2023160593 A1 WO 2023160593A1 CN 2023077766 W CN2023077766 W CN 2023077766W WO 2023160593 A1 WO2023160593 A1 WO 2023160593A1
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catalyst
component
gold
titanium
carrier
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French (fr)
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段学志
张志华
王千红
林斌
宋楠
杜威
王刚
周兴贵
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华东理工大学
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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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J37/04—Mixing
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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 belongs to the technical field of catalysts, and in particular relates to a physically mixed catalyst for propylene hydrogen-oxygen epoxidation and a preparation method.
  • Propylene oxide (PO) is the second largest propylene derivative after polypropylene, and is mainly used in the production of polyether polyols, propylene glycol, propylene carbonate and other chemical products.
  • the one-step epoxidation of propylene to propylene oxide (PO) in a hydrogen-oxygen mixture has the outstanding advantages of simple process, high selectivity, easy separation of products, and full utilization of reaction heat energy. It is an ideal process for PO production. In earlier studies, indicators such as the activity and stability of PO on Au/ TiO2 catalysts were poor. In order to improve the performance of PO, numerous titanium-containing materials have been used to support gold nanoparticles to catalyze the direct gas-phase epoxidation of propylene.
  • a titanium-containing carrier mainly includes TS-1, Ti-MCM-41 and so on.
  • the gold catalyst supported on titanium-containing materials is an Au-Ti bifunctional catalyst: the Au site catalyzes H2 and O2 to generate hydroperoxide species, and then epoxidizes propylene with Ti site to generate PO.
  • the catalyst requires Au to be deposited near the Ti site in order to achieve Au-Ti synergy and then obtain high PO catalytic performance. Therefore, it has higher requirements for titanium-containing supports, such as large specific surface area, excellent hydrophobicity, and four-coordinated titanium height. Dispersion, strong interaction with gold particles, etc.
  • the reaction mechanism of the hydrogenation of propane to acetone is similar to that of propylene oxide to propylene oxide, and the gold catalyst supported by the above-mentioned titanium-containing material can also be used in the reaction of hydrogenation of propane to acetone.
  • titanium-silicon molecular sieves have excellent hydrophobicity, hydrothermal stability, and high dispersion of four-coordinated titanium.
  • -B, TS-2-B The outer surface loaded gold catalyst has higher activity and better stability, but the characteristics of the small specific surface area of the carrier are not conducive to improving the dispersion and thermal stability of the gold particles, and the gold and the carrier The interaction between them is weak, so that the gold nanoparticles are easy to sinter and grow up, resulting in catalyst deactivation, which limits the development and application of high-performance and high-stability catalyst supports required by industry.
  • the present invention aims at the shortcomings of existing catalysts in the reaction of propylene oxide to propylene oxide, and provides a physical hybrid catalyst for the reaction of propylene oxide to propylene oxide and a preparation method thereof, and selects nano-gold A carrier with a higher particle sintering temperature and a stronger interfacial interaction or a larger specific surface area allows the gold particles to be better dispersed under the same loading amount to support gold, and then mixed with titanium-containing materials for propylene hydroxide Epoxidation It can also be used in the reaction of propane hydrogenation to acetone. It can not only break through the limitation that Au should be deposited near Ti on the traditional supported Au-Ti bifunctional catalyst, but also inhibit the deactivation of the catalyst. It is very important for the development of industrial The required high-performance and high-stability catalysts are of great significance.
  • the first aspect of the present invention provides a physically mixed catalyst.
  • the catalyst is obtained by physically mixing component A and component B, wherein component A is a supported gold catalyst, and component B is a titanium-containing catalyst. Material.
  • the carrier of the A-component supported gold catalyst can select gold particles to be sintered according to the volcano-shaped curve presented by the sintering initiation temperature of nano-gold ions and the interfacial interaction energy of the carrier reported in existing research.
  • Carriers with higher temperature and stronger interfacial interactions such as silica, metal oxides, binary or multi-element oxides; or carriers with larger specific surface areas that can better disperse metal particles under the same loading amount , such as molecular sieves, carbon materials, MOFs, etc., where molecular sieves do not contain Ti.
  • the carrier of the A-component supported gold catalyst is silica, metal oxide, binary or multi-component oxide, molecular sieve, carbon material, MOFs, COFs, sulfide, nitride, black phosphorus, phosphide , porous organic polymers or porous molecular solids.
  • Preferred are SiO 2 , CeO 2 , Al 2 O 3 , ZrO 2 , HZSM-5 molecular sieve, SBA-15 molecular sieve, carbon nanotubes, graphene, graphyne, activated carbon, MOFs, MOF-801, Py-PB-COF, MoS 2 or SiN etc.
  • the particle size of the gold nanoparticles supported on the carrier is less than 10 nm, preferably less than 5 nm.
  • the titanium-containing material of the B component can be conventionally used in the field, including but not limited to titanium-containing molecular sieves, TiO 2 -SiO 2 , TiO 2 or a mixture of one or more of the above materials; It is preferably an uncalcined titanium-silicon molecular sieve TS-1-B whose micropores are blocked by a template agent or an uncalcined titanium-silicon molecular sieve TS-2-B formed by stacking nanoparticles.
  • a second aspect of the present invention provides a method for preparing a physically mixed catalyst, said method comprising the steps of:
  • the present invention is further set as, the preparation of the A component supported gold catalyst in the step (1) can adopt the preparation method of the conventional supported catalyst in the art, as long as the particle size of the nano gold particles in the prepared supported gold catalyst is It is enough to reach the above range, including but not limited to the following methods:
  • the gold precursor solution and the carrier are mixed and dried to prepare the A-component loaded gold catalyst; the gold precursor solution is formed by mixing the gold precursor with the solution; the gold precursor includes chloroauric acid or its derivatives , Inorganic gold compounds and organic gold compounds. Further, when the gold precursor in the step (1) is chloroauric acid or its derivatives, component A can be prepared by urea deposition-precipitation method, sol-gel method, etc.
  • the steps include:
  • the steps include:
  • the mechanical mixing in the step (2) is one or more of mechanical stirring, ball milling, shaker mixing, and mechanical grinding.
  • the method of mechanical mixing in the step (2) is mechanical stirring
  • the two catalysts of component A and component B are placed in a mortar, and mixed with a stirring bar, which can be adjusted by controlling the stirring time and stirring rate The degree of mixing of A and B components.
  • the present invention is further set to, the mass ratio of A component and B component mechanically mixed in the step (2) is not fixed, but all need to occupy a certain proportion; the mass ratio of A component and B component is preferably 1 :1.
  • the present invention is further provided that the physically mixed catalyst obtained in the step (2) can be further subjected to high-temperature heat treatment under a certain atmosphere.
  • the heat treatment atmosphere includes one or a mixture of two or more of hydrogen, oxygen, propylene, nitrogen, carbon monoxide, argon, and air.
  • the temperature of the high temperature heat treatment is 90-500°C, preferably 150-500°C, more preferably 180-450°C, the heating rate is 0.1-5°C/min, and the heat treatment time is 1-24 hours.
  • the third aspect of the present invention provides the application of the physical mixed catalyst for the reaction of propylene oxide to propylene oxide and the reaction of propane to acetone.
  • the physical hybrid catalyst developed by the present invention has strong adaptability to gold-loaded carriers and has excellent performance in the reaction of propylene oxide hydrogenation to propylene oxide and the reaction performance of acetone hydrogenation to acetone.
  • the bifunctional catalyst Au/TS-1-B has the same catalytic activity as Au/TS-2-B, and the product selectivity is as high as more than 90%, which has great application prospects.
  • the physical hybrid catalyst developed by the present invention has a simple process. Compared with the existing supported dual-function catalysts, a carrier with a large specific surface area and a strong interaction with gold can be selected to load gold, and then be carried out with titanium-containing materials. Mixed, the gold-loaded carrier can be selected in a wide range, and is not limited by the titanium-containing carrier.
  • Fig. 1 is the catalytic activity result comparison of embodiment 1 and comparative example 1 long stability
  • Fig. 2 is the catalytic activity result comparison of embodiment 5 and comparative example 1 long stability
  • Fig. 3 is the catalytic activity result comparison of embodiment 7 and comparative example 1 long stability
  • Fig. 4 is the catalytic activity result comparison of embodiment 8 and comparative example 2 long stability
  • Fig. 5 is the HAADF-STEM figure of fresh catalyst gold nanoparticles in embodiment 1;
  • Fig. 6 is the HAADF-STEM figure of nano gold particle when catalyst reaction 80h in embodiment 1;
  • Fig. 7 is catalyst element content analysis figure among the embodiment 1;
  • FIG. 8 is an analysis diagram of catalyst element content in Comparative Example 1.
  • Au/HZSM-5 was prepared with chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/SBA-15 was prepared with chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/MOFs were prepared using chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/CNTs were prepared using chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/ CeO2 was prepared with chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/ SiO2 was prepared with chloroauric acid as precursor and mechanically stirred with TS-1-B to prepare physically mixed catalyst, The steps are as follows:
  • Au/SiN was prepared using chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/MOF-801 was prepared using chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/MOF-801 was prepared by sol-gel method using chloroauric acid as the precursor solution:
  • Au/Py-PB-COF was prepared using chloroauric acid as a precursor and mechanically stirred with TS-1-B to prepare a physically mixed catalyst. The steps are as follows:
  • Au/Py-PB-COF was prepared by sol-gel method using chloroauric acid as the precursor solution:
  • Au/MoS 2 was prepared using chloroauric acid as a precursor and mechanically stirred with TS-2-B to prepare a physically mixed catalyst. The steps are as follows:
  • the Au/TS-1-B bifunctional catalyst is prepared with chloroauric acid as a precursor, and the steps are as follows:
  • Au/TS-2-B bifunctional catalyst is prepared with chloroauric acid as a precursor, and the steps are as follows:
  • the Au/TS-1-B bifunctional catalyst is prepared with chloroauric acid as a precursor, and the steps are as follows:
  • Catalysts prepared by the above-mentioned Examples 1-15 and Comparative Examples 1-3 are used for catalytic performance evaluation in the reaction of propylene gas phase epoxidation to prepare propylene oxide, and the propylene gas phase epoxidation reaction is carried out in a fixed-bed reactor at normal pressure.
  • the catalytic results are shown in Table 1, wherein the gold loading refers to the gold loading of component A supported gold catalyst.
  • Catalysts prepared in the above-mentioned Example 1, Example 8 and Comparative Examples 1-2 are used for catalytic performance evaluation in the reaction of preparing acetone by gas-phase oxidation of propane, and the gas-phase epoxidation of propane is carried out in a fixed-bed reactor at normal pressure.
  • Catalytic result is shown in table 2, wherein,
  • the gold loading refers to the gold loading of the component A supported gold catalyst.
  • the physical mixed catalyst developed by the present invention can select a carrier with a large specific surface area and a strong interaction with gold to load gold, and then mix it with titanium-containing materials. Carrier restrictions.
  • FIG. 5 it is the HAADF-STEM figure of catalyst nano-gold particles prepared in Example 1.
  • the average particle diameter of nano-gold particles is 2.7 ⁇ 1.0nm, and the particle size distribution of nano-gold particles is narrow, and the particles are small and distributed. Uniformity and other advantages.
  • the HAADF-STEM figure of the nano-gold particles when the catalyst of Example 1 was reacted for 80 hours in the gas-phase epoxidation of propylene is shown in Figure 6, and the average particle size of the nano-gold particles was 2.9 ⁇ 1.0 nm after the reaction for 80 h, and the particle size distribution was still relatively large.
  • FIG. 7 and Figure 8 are the element content analysis diagrams of Example 1 and Comparative Example 1, respectively, and Au, Ti, Si, and O elements can be detected, indicating that the supported gold catalyst and titanium-containing material can be uniformly mixed by physical mixing.

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Abstract

本发明提供了一种用于丙烯氢氧环氧化的物理混合式催化剂及其制备方法，所述催化剂将金负载于不含钛且比表面积大、与金存在强相互作用的载体上，并与含钛材料以任意比例进行物理混合而得；这种催化剂避免了将金负载于性能优越的微孔被模板剂堵塞的未焙烧钛硅分子筛上存在的载体比表面积较小而不利于提高金颗粒的分散度及热稳定性以及金与载体之间相互作用较弱等问题，突破了传统负载型Au-Ti双功能催化剂上Au要在沉积在Ti附近的限制，对于开发工业所需高性能高稳定性催化剂具有重要的意义。

Description

用于丙烯氢氧环氧化的物理混合式催化剂及制备方法和应用 技术领域
本发明属于催化剂技术领域，具体涉及一种用于丙烯氢氧环氧化的物理混合式催化剂及制备方法。
背景技术
环氧丙烷(Propylene Oxide，简称PO)是仅次于聚丙烯的第二大丙烯衍生物，主要用于生产聚醚多元醇、丙二醇、碳酸丙烯酯等化工产品。丙烯在氢氧混合气中一步环氧化制环氧丙烷(PO)具有工艺简单、选择性高、产物易分离、反应热能充分利用的突出优势，是PO生产的理想工艺。在早期的研究中，Au/TiO2催化剂上PO的活性和稳定性等指标较差。为了提高PO的性能，众多的含钛材料被用来负载纳米金颗粒催化丙烯直接气相环氧化反应。研究发现只有锐钛矿型的TiO2能够有效催化丙烯环氧化反应，而金红石和和无定形的TiO2不能，采用Si来孤立Ti位点对于提高PO选择性具有明显的促进作用，这种含钛载体主要有TS-1、Ti-MCM-41等。
含钛材料负载的金催化剂是一种Au-Ti双功能催化剂：Au位催化H2与O2生成氢过氧化物种，之后在Ti位点与丙烯发生环氧化反应生成PO。催化剂需要Au沉积于Ti位点附近才能实现Au-Ti协同继而获得高PO催化性能，因此对含钛载体具有较高的要求，如较大的比表面积、优异的疏水性、四配位钛高度分散、与金颗粒之间具有较强的相互作用等。丙烷氢氧化制丙酮的反应机理与丙烯氢氧环氧化制环氧丙烷反应相似，上述含钛材料负载的金催化剂同样可用于丙烷氢氧化制丙酮的反应。
目前，在众多的含钛载体中，钛硅分子筛具有优异的疏水性、水热稳定性以及四配位钛高度分散等特点，虽然微孔被模板剂堵塞的未焙烧钛硅分子筛(TS-1-B、TS-2-B)外表面负载金催化剂具有较高的活性和较好的稳定性，但是载体比表面积小的特点不利于提高金颗粒的分散度及热稳定性，且金与载体之间相互作用较弱，使得纳米金颗粒容易烧结长大从而导致催化剂失活，限制了工业所需高性能高稳定性催化剂载体的开发与应用。
发明内容
本发明针对丙烯氢氧环氧化制环氧丙烷反应现有催化剂存在的不足，提供了一种用于丙烯氢氧环氧化制环氧丙烷反应物理混合式催化剂及其制备方法，选取纳米金颗粒烧结温度较高且具有较强界面相互作用的载体或者比表面积较大，使得金颗粒在相同负载量下能得到更好分散的载体来负载金，再与含钛材料混合用于丙烯氢氧环氧化 制环氧丙烷反应，同时还可用于丙烷氢氧化制丙酮反应，既能够突破传统负载型Au-Ti双功能催化剂上Au要在沉积在Ti附近的限制，又能抑制催化剂失活，对于开发工业所需高性能高稳定性催化剂具有重要的意义。
本发明的第一个方面，提供一种物理混合式催化剂，所述催化剂由A组分和B组分以物理混合的方式获得，其中A组分为负载型金催化剂，B组分为含钛材料。
本发明进一步设置为，所述A组分负载型金催化剂的载体，根据现有研究报道的纳米金离子的烧结起始温度与载体的界面作用能所呈的火山型曲线，可以选取金粒子烧结温度较高且具有较强界面相互作用的载体，例如二氧化硅、金属氧化物、双元或多元氧化物；或者选取比表面积较大在相同负载量下能够使得金属颗粒得到更好分散的载体，例如分子筛、碳材料、MOFs等，其中分子筛不含Ti元素。
具体的，所述A组分负载型金催化剂的载体为二氧化硅、金属氧化物、双元或多元氧化物、分子筛、碳材料、MOFs、COFs、硫化物、氮化物、黑磷、磷化物、多孔有机聚合物或多孔分子固体。优选为SiO2、CeO2、Al2O3、ZrO2、HZSM-5分子筛、SBA-15分子筛、碳纳米管、石墨烯、石墨炔、活性炭、MOFs、MOF-801、Py-PB-COF、MoS2或SiN等。
进一步的，所述A组分负载型金催化剂，其载体上负载的纳米金颗粒的粒径小于10nm，优选小于5nm。
本发明进一步设置为，所述B组分含钛材料可以是本领域常规使用的，包括但不限于含钛分子筛、TiO2-SiO2、TiO2或是以上一种或几种材料的混合物；优选为微孔被模板剂堵塞的未焙烧的钛硅分子筛TS-1-B或由纳米颗粒堆积而成的未焙烧的钛硅分子筛TS-2-B。
本发明的第二个方面，提供一种物理混合式催化剂的制备方法，所述方法包括如下步骤：
(1)首先制备A组分负载型金催化剂；
(2)其次将A组分和B组分含钛材料加入容器中，利用机械混合的方式来实现组分间的均匀混合，得到物理混合式催化剂。
本发明进一步设置为，所述步骤(1)中A组分负载型金催化剂的制备可采用本领域常规负载型催化剂的制备方法，只要制得的负载型金催化剂中的纳米金颗粒的粒径达到上述范围即可，包括但不限于如下方法：
将金前驱体溶液和载体混合、干燥，制备A组分负载型金催化剂；所述金前驱体溶液是将金前驱体与溶液混合而成；所述金前驱体包括氯金酸或其衍生物、无机金化合物和有机金化合物。进一步的，所述步骤(1)中的金前驱体为氯金酸或其衍生物时，可通过尿素沉积-沉淀法、溶胶-凝胶法等制备A组分。
进一步的，当所述步骤(1)通过尿素沉积-沉淀法制备A组分时的步骤包括：
(i)将pH至少为5的含有氯金酸或其衍生物的溶液与载体及尿素通过搅拌混合均匀，升温至90℃并老化6h；
(ii)采用离心的方法将固体和液体进行分离并洗涤，将得到的固体在室温下真空干燥得到A组分。
进一步的，当所述步骤(1)通过溶胶-凝胶法制备A组分时的步骤包括：
(i)将含有氯金酸或其衍生物的溶液于70℃与聚乙烯醇、乙二醇和三乙醇胺混合均匀，得到胶体溶液；
(ii)所述胶体溶液中加入载体，室温下静置，干燥，得到A组分。
本发明进一步设置为，所述步骤(2)中机械混合的方式为机械搅拌、球磨、摇床混合、机械研磨中的一种或两种以上的方式。
进一步，所述步骤(2)中机械混合的方式为机械搅拌时，将A组分和B组分两种催化剂放置于研钵中，采用搅拌棒进行混合，通过控制搅拌时间和搅拌速率可以调节A组分和B组分的混合程度。
本发明进一步设置为，所述步骤(2)中机械混合的A组分和B组分的质量比例不固定，但都需占有一定的比例；A组分和B组分的质量比优选为1:1。
本发明进一步设置为，所述步骤(2)得到的物理混合式催化剂，可进一步在一定气氛下进行高温热处理。
进一步的，所述热处理的气氛包括氢气、氧气、丙烯、氮气、一氧化碳、氩气、空气中的一种或两种以上混合物。
进一步的，所述高温热处理的温度为90-500℃，优选为150-500℃，更优选为180-450℃，升温速率为0.1-5℃/分钟，热处理时间为1-24小时。
本发明的第三个方面，提供所述物理混合式催化剂的应用，用于丙烯氢氧环氧化制环氧丙烷反应与丙烷氢氧化制丙酮反应。
本发明具有以下有益效果：
(1)本发明开发的对负载金载体适应性强且具有优异丙烯氢氧环氧化制环氧丙烷反应与丙酮氢氧化制丙酮反应性能的物理混合式催化剂，与目前催化性能优异的负载型双功能催化剂Au/TS-1-B与Au/TS-2-B的催化活性相当，产物选择性高达90％以上，具有巨大的应用前景。
(2)本发明开发的物理混合式催化剂工艺简单，相比于现有的负载型双功能催化剂，可以选择比表面积大且与金存在强相互作用的载体来负载金，再与含钛材料进行混合，负载金的载体选择范围广，不受含钛载体的限制。
附图说明
图1为实施例1与对比例1长稳定性的催化活性结果对比；
图2为实施例5与对比例1长稳定性的催化活性结果对比；
图3为实施例7与对比例1长稳定性的催化活性结果对比；
图4为实施例8与对比例2长稳定性的催化活性结果对比；
图5为实施例1中新鲜催化剂纳米金颗粒的HAADF-STEM图；
图6为实施例1中催化剂反应80h时纳米金颗粒的HAADF-STEM图；
图7为实施例1中催化剂元素含量分析图；
图8为对比例1中催化剂元素含量分析图。
具体实施方式
下面结合具体实施例对本发明的技术方案进行清楚、完整地描述。应理解，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。除非另外说明，否则所有的百分数、比率、比例、或份数按重量计。
实施例1
以氯金酸为前驱体制备Au/SiO2并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/SiO2：
将1g SiO2、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/SiO2。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例2
以氯金酸为前驱体制备Au/HZSM-5并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/HZSM-5：
将1g HZSM-5、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中 混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/HZSM-5。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例3
以氯金酸为前驱体制备Au/SBA-15并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/SBA-15：
将1g SBA-15、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/SBA-15。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例4
以氯金酸为前驱体制备Au/MOFs并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/MOFS：
将1g MOFs、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/MOFS。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例5
以氯金酸为前驱体制备Au/CNTs并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体溶液采用溶胶凝胶法制备Au/CNTs：
将1mL的氯金酸溶液(0.956mgAu/mL)加入39mL水中，在70℃恒温水浴下搅拌并缓慢加入10g聚乙烯醇，使其充分溶解，然后加入一定量的乙二醇，待搅拌溶解成均质后加入一定量的三乙醇胺并搅拌均匀，得到胶体溶液；在上述胶体溶液中加入1g碳纳米管(CNTs)，搅拌均匀在室温下静置24h，之后在110℃下干燥24h，得到负载量为0.09wt％的负载型金催化剂Au/CNTs。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例6
以氯金酸为前驱体制备Au/CeO2并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/CeO2：
将1g CeO2、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/CeO2。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例7
以氯金酸为前驱体制备Au/Al2O3并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用浸渍法制备Au/Al2O3：
将1gγ-Al2O3置于10mL玻璃烧杯中，然后用移液管称量1mL氯金酸溶液(0.956mgAu/mL)逐滴滴在γ-Al2O3上，然后用玻璃棒搅拌均匀，室温下静置12h，抽真空过滤，得到负载量为0.09wt％的负载型金催化剂Au/Al2O3。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例8
以氯金酸为前驱体制备Au/SiO2并与TS-2-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/SiO2：
将1g SiO2、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/SiO2。
(2)在室温下将上述负载型金催化剂与由纳米颗粒堆积而成的未焙烧的钛硅分子筛TS-2-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例9
以氯金酸为前驱体制备Au/SiO2并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/SiO2：
将1g SiO2、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/SiO2。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，负载型金催化剂与TS-1-B催化剂的质量比为1：2。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例10
以氯金酸为前驱体制备Au/SiO2并与TS-1-B机械搅拌制备物理混合式催化剂， 其步骤如下：
(1)以氯金酸为前驱体采用尿素沉积-沉淀法制备Au/SiO2：
将1g SiO2、39ml水、1mL氯金酸溶液(0.956mgAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，得到的固体在室温下真空干燥，得到负载量为0.09wt％的负载型金催化剂Au/SiO2。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，负载型金催化剂与TS-1-B催化剂的质量比为2：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得物理混合式催化剂。
实施例11
以氯金酸为前驱体制备Au/Al2O3并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体采用浸渍法制备Au/Al2O3：
将1gγ-Al2O3置于10mL玻璃烧杯中，然后用移液管称量1mL氯金酸溶液(0.956mgAu/mL)逐滴滴在γ-Al2O3上，然后用玻璃棒搅拌均匀，室温下静置12h，抽真空过滤，得到负载量为0.09wt％的负载型金催化剂Au/Al2O3。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，然后切换为氮气吹扫10分钟后再切换为空气，以1℃/min的速率升温至500℃处理2h，即得物理混合式催化剂。
实施例12
以氯金酸为前驱体制备Au/SiN并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体溶液采用溶胶凝胶法制备Au/SiN：
将7mL的氯金酸溶液(9.56mgAu/mL)加入10mL水中，在70℃恒温水浴下搅拌并缓慢加入10g聚乙烯醇，使其充分溶解，然后加入2mL硼氢化钠溶液(0.05mol/L)，得到胶体溶液；在上述胶体溶液中加入1g SiN，搅拌均匀在室温下静置24h，之后多次水洗，并在室温下抽真空干燥24h，得到负载量为0.50wt％的负载型金催化剂Au/SiN。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氧气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至400℃，即得物理混合式催化剂。
实施例13
以氯金酸为前驱体制备Au/MOF-801并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体溶液采用溶胶凝胶法制备Au/MOF-801：
将8mL的氯金酸溶液(9.56mgAu/mL)加入10mL水中，然后加入2mL聚乙烯吡咯烷酮，再然后加入2mL水合肼溶液(0.04mol/L)，得到胶体溶液；在上述胶体溶液中加入1g MOF-801，搅拌均匀后在室温下静置24h，之后多次水洗，并在室温下抽真空干燥24h，得到负载量为0.55wt％的负载型金催化剂Au/MOF-801。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氧气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至400℃，即得物理混合式催化剂。
实施例14
以氯金酸为前驱体制备Au/Py-PB-COF并与TS-1-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体溶液采用溶胶凝胶法制备Au/Py-PB-COF：
将8mL的氯金酸溶液(9.56mgAu/mL)加入10mL水中，然后加入2mL聚乙烯吡咯烷酮，再然后加入2mL硼氢化钠溶液(0.05mol/L)，得到胶体溶液；在上述胶体溶液中加入1g Py-PB-COF，搅拌均匀后在室温下静置24h，之后多次水洗，并在室温下抽真空干燥24h，得到负载量为0.53wt％的负载型金催化剂Au/Py-PB-COF。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氧气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至400℃，即得物理混合式催化剂。
实施例15
以氯金酸为前驱体制备Au/MoS2并与TS-2-B机械搅拌制备物理混合式催化剂，其步骤如下：
(1)以氯金酸为前驱体溶液采用溶胶凝胶法制备Au/MoS2：
将7mL的氯金酸溶液(9.56mgAu/mL)加入10mL水中，然后加入2mL聚乙烯吡咯烷酮，再然后加入2mL硼氢化钾溶液(0.05mol/L)，得到胶体溶液；在上述胶体溶液中加入1g MoS2，搅拌均匀后在室温下静置24h，之后多次水洗，并在室温下抽真空干燥24h，得到负载量为0.58wt％的负载型金催化剂Au/MoS2。
(2)在室温下将上述负载型金催化剂与未经过高温焙烧微孔被模板剂堵塞的TS-1-B进行机械搅拌，搅拌时间为15min，两种催化剂的质量比为1：1。
(3)将混合后的催化剂置于固定床反应器中，在气氛组成为氧气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至400℃，即得物理混合式催化剂。
对比例1
以氯金酸为前驱体制备Au/TS-1-B双功能催化剂，其步骤如下：
(1)将1g未经过高温焙烧微孔被模板剂堵塞的钛硅分子筛TS-1-B、39mL水、1mL氯金酸溶液(0.956gAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，将得到的固体在室温下真空干燥。
(2)将干燥后的固体置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得负载量为0.09wt％的负载型双功能催化剂。
对比例2
以氯金酸为前驱体制备Au/TS-2-B双功能催化剂，其步骤如下：
(1)将1g由纳米颗粒堆积而成的未焙烧的钛硅分子筛TS-2-B、39mL水、1mL氯金酸溶液(0.956g/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，将得到的固体在室温下真空干燥。
(2)将干燥后的固体置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，即得负载量为0.09wt％的负载型双功能催化剂。
对比例3
以氯金酸为前驱体制备Au/TS-1-B双功能催化剂，其步骤如下：
(1)将1g未经过高温焙烧微孔被模板剂堵塞的钛硅分子筛TS-1-B、39mL水、1mL氯金酸溶液(0.956gAu/mL)依次加入烧杯中混合并搅拌得到悬浊液，并向上述 悬浊液中加入0.09g的尿素；在水浴锅中将上述悬浊液升温至90℃并保持6h；采用离心的方法将固体和液体进行分离并洗涤，将得到的固体在室温下真空干燥。
(2)将干燥后的固体置于固定床反应器中，在气氛组成为氢气：氮气＝1：1.47(体积比)中从室温以1.5℃/min的速率升温至300℃，然后切换为氮气吹扫10分钟后再切换为空气，以1℃/min的速率升温至500℃处理2h，即得物理混合式催化剂。
实施例16
采用上述实施例1-15和对比例1-3制备的催化剂在丙烯气相环氧化制备环氧丙烷的反应中进行催化性能评价，丙烯气相环氧化反应在常压固定床反应器中进行，反应气氛组成为丙烯：氢气：氧气：氮气＝1：1：1：7(体积比)，空速为4000-14000mL·h- 1·gcat-1，反应温度为200℃，出口产物由气相色谱分析。催化结果如表1所示，其中，金负载量指的是组分A负载型金催化剂的金负载量。
表1
采用上述实施例1与实施例8和对比例1-2制备的催化剂在丙烷气相氧化制备丙酮的反应中进行催化性能评价，丙烷气相环氧化反应在常压固定床反应器中进行，反应气氛组成为丙烷：氢气：氧气：氮气＝1：1：1：7(体积比)，空速为4000-14000mL·h- 1·gcat-1，反应温度为200℃，出口产物由气相色谱分析。催化结果如表2所示，其中， 金负载量指的是组分A负载型金催化剂的金负载量。
表2
结合图1-4所示，分别为实施例1、5、7与对比例1和实施例8与对比例2长稳定性的催化活性结果对比，本发明的物理混合式催化剂与目前催化性能优异的Au-Ti双功能催化剂在丙烯气相环氧化反应中的催化活性相当，环氧丙烷选择性高达93％，且稳定性高。此外，比较实施例7、11与对比例1与3结果可知，选择与金存在强相互作用的氧化铝等材料作为载体时，高温焙烧处理后仍表现出较好的催化活性，明显优于高温焙烧处理的钛硅分子筛固载金催化剂。
此外，从表2可知，实施例1、8制备的物理混合式催化剂与对比例1和对比例2制备的直接负载型Au-Ti双功能催化剂在丙烷氢氧化制丙酮反应中的催化活性相当，表明这种物理混合式催化剂同样也适用于丙烷氢氧化制丙酮反应体系。
因此，本发明开发的物理混合式催化剂可以选择比表面积大且与金存在强相互作用的载体来负载金，再与含钛材料进行混合，负载型金催化剂的载体选择范围广，不受含钛载体的限制。
如图5所示，为实施例1制备得到催化剂纳米金颗粒的HAADF-STEM图，纳米金颗粒的平均粒径为2.7±1.0nm，具有纳米金颗粒粒径分布较窄，颗粒较小，分布均匀等优点。实施例1的催化剂于丙烯气相环氧化反应80h时的纳米金颗粒的HAADF-STEM图如图6所示，反应80h后纳米金颗粒的平均粒径为2.9±1.0nm，粒径分布仍较窄且反应过程中未明显长大，进而说明组分A的负载型金催化剂能够使金颗粒的团聚减弱，稳定性高。图7和图8分别为实施例1和对比例1的元素含量分析图，均能检测到Au、Ti、Si、O元素，说明通过物理混合可以将负载型金催化剂和含钛材料混合均匀。

Claims (11)

  1. 一种物理混合式催化剂，其特征在于，所述催化剂由A组分和B组分以物理混合的方式获得，其中A组分为负载型金催化剂，B组分为含钛材料。
  2. 根据权利要求1所述的催化剂，其特征在于，所述A组分负载型金催化剂的载体为二氧化硅、金属氧化物、双元或多元氧化物、分子筛、碳材料、MOFs、COFs、硫化物、氮化物、黑磷、磷化物、多孔有机聚合物或多孔分子固体。
  3. 根据权利要求2所述的催化剂，其特征在于，所述A组分负载型金催化剂的载体为SiO2、CeO2、Al2O3、ZrO2、HZSM-5分子筛、SBA-15分子筛、碳纳米管、石墨烯、石墨炔、活性炭、MOFs、MOF-801、Py-PB-COF、MoS2或SiN。
  4. 根据权利要求1所述的催化剂，其特征在于，所述A组分负载型金催化剂的载体上负载的金颗粒的粒径小于10nm。
  5. 根据权利要求4所述的催化剂，其特征在于，所述A组分负载型金催化剂的载体上负载的金颗粒的粒径小于5nm。
  6. 根据权利要求1所述的催化剂，其特征在于，所述B组分含钛材料为含钛分子筛、TiO2-SiO2、TiO2或是以上一种或几种材料的混合物。
  7. 根据权利要求6所述的催化剂，其特征在于，所述B组分含钛材料为微孔被模板剂堵塞的未焙烧钛硅分子筛TS-1-B或由纳米颗粒堆积而成的未焙烧钛硅分子筛TS-2-B。
  8. 一种物理混合式催化剂的制备方法，所述方法包括如下步骤：
    (1)首先制备A组分负载型金催化剂；
    (2)其次将A组分和B组分含钛材料利用机械混合的方式均匀混合，得到所述物理混合式催化剂。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤(2)中A组分与B组分的质量比为1:1。
  10. 根据权利要求8所述的制备方法，其特征在于，步骤(2)中机械混合的方式为机械搅拌、球磨、摇床混合、机械研磨中的一种或两种以上的方式。
  11. 权利要求1-7中任一物理混合式催化剂的应用，其特征在于，用于丙烯氢氧环氧化制环氧丙烷反应和丙烷氢氧化制丙酮反应。
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