WO2022142710A1 - 球形钛硅分子筛催化剂及其制备方法 - Google Patents

球形钛硅分子筛催化剂及其制备方法 Download PDF

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WO2022142710A1
WO2022142710A1 PCT/CN2021/128086 CN2021128086W WO2022142710A1 WO 2022142710 A1 WO2022142710 A1 WO 2022142710A1 CN 2021128086 W CN2021128086 W CN 2021128086W WO 2022142710 A1 WO2022142710 A1 WO 2022142710A1
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molecular sieve
titanium
silicon molecular
original powder
sieve catalyst
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PCT/CN2021/128086
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English (en)
French (fr)
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熊德胜
庄岩
罗从光
崔曜
褚小东
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上海华谊新材料有限公司
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Priority to EP21913454.1A priority Critical patent/EP4272868A1/en
Priority to US18/270,427 priority patent/US20240100512A1/en
Publication of WO2022142710A1 publication Critical patent/WO2022142710A1/zh

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    • B01J35/51—
    • 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
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J2229/60—Synthesis on support
    • B01J2229/62—Synthesis on support in or on other molecular sieves
    • B01J35/30—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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 a spherical titanium-silicon molecular sieve catalyst, its preparation method and its application in preparing hydroquinone by hydroxylation of phenol.
  • Hydroquinone and catechol are two important chemical raw materials and chemical intermediates, which have a wide range of uses.
  • Catechol can be used as rubber hardener, electroplating additive, skin antiseptic bactericide, hair dye, photographic developer, color photo antioxidant, fur dyeing developer, paint and varnish anti-peeling agent.
  • Hydroquinone is mainly used in developers, anthraquinone dyes, azo dyes, synthetic ammonia cosolvents, rubber antioxidants, polymerization inhibitors, stabilizers for coatings and flavors, and antioxidants.
  • the industrial production of hydroquinone includes cumene process, phenol hydroxylation process and aniline process.
  • the phenol hydroxylation process uses phenol as raw material, hydrogen peroxide as oxidant, and obtains hydroquinone and phthalate through hydroxylation reaction. Phenol, the by-product is water, so this is a green process route.
  • the catalysts used in the phenol hydroxylation process include homogeneous iron catalysts, perchloric acid catalysts and solid titanium-silicon molecular sieve catalysts.
  • Example 1 of US4701428 it first obtains titanium-silicon molecular sieve raw powder by centrifugation, prepares an aqueous solution of tetraethylorthosilicate and tetrapropylammonium hydroxide, and then mixes the two and sprays them to form , to obtain microspherical titanium-silicon molecular sieve catalyst.
  • spray-drying molding can advantageously produce microspherical titanium-silicon molecular sieve catalyst
  • the performance of micro-spherical titanium-silicon molecular sieve prepared by spray-forming is worse than that of the original titanium-silicon molecular sieve powder before molding.
  • the strength of the spherical titanium-silicon molecular sieve with silica as the binder is still not very good.
  • the spherical particles will be broken and a large number of fine particles will be generated. During the separation process, these particles will penetrate the filter screen. loss, resulting in increased catalyst consumption.
  • CN103212435A proposes a preparation method of spherical titanium-silicon molecular sieve.
  • the amorphous silica binder on the surface of the catalyst of spray-forming microsphere titanium-silicon molecular sieve is transformed into a crystalline form of dioxide.
  • Silicon improves the catalytic oxidation activity of the microsphere titanium silicon molecular sieve, and also ensures the mechanical strength of the microsphere titanium silicon molecular sieve.
  • the preparation process of this method is complicated, and the mechanical strength of the titanium-silicon molecular sieve after forming is still not very high.
  • CN111115653A discloses a modification method of spray-forming microspherical titanium-silicon molecular sieve, which includes a molecular sieve forming step and a catalyst modification step.
  • the molecular sieve forming step includes:
  • the titanium source was added dropwise to tert-butanol, stirred for 30 min, and then added to the above-mentioned mother liquor A, and aged at 50° C. for 24 hours under stirring to obtain mother liquor B;
  • the mother liquor B is formed by spray drying to obtain the molded molecular sieve.
  • the inlet temperature of the spray drying process is 180-200°C, and the outlet temperature is 100-105°C.
  • This molecular sieve forming method is complicated in process, resulting in high cost.
  • the catalyst prepared by this method has a catalytic activity similar to that of the original titanium-silicon molecular sieve powder, and the microspherical titanium-silicon molecular sieve has good mechanical strength and can be used for a long time. Structural stability can be maintained during the catalytic reaction.
  • one aspect of the present invention relates to a kind of microsphere titanium silicon molecular sieve catalyst, and it has the following composition:
  • M is a metal element selected from alkaline earth metals, transition metals, or a combination of two or more thereof;
  • the titanium-silicon molecular sieve original powder has the following composition:
  • Another aspect of the present invention relates to a preparation method of a microsphere titanium-silicon molecular sieve catalyst, wherein the microsphere titanium-silicon molecular sieve catalyst has the following composition:
  • M is selected from alkaline earth metals, transition metal elements, or a combination of two or more thereof;
  • the method includes:
  • the titanium-silicon molecular sieve original powder has the following composition:
  • Fig. 1 is the SEM electron microscope picture of the microsphere titanium silicon molecular sieve of an example of the present invention.
  • microsphere titanium-silicon molecular sieve catalyst of the present invention has the following composition:
  • x 0.0005-0.04, preferably 0.001-0.035, more preferably 0.002-0.030, more preferably 0.003-0.025, preferably 0.004-0.020, preferably 0.005-0.01.
  • y 0.005-0.2, preferably 0.008-0.15, more preferably 0.012-0.010, preferably 0.015-0.08, preferably 0.03-0.05.
  • M is selected from alkaline earth metals, transition metal elements, or a combination of two or more thereof.
  • M is selected from calcium, magnesium, zinc, nickel, aluminum, iron, copper, cobalt, or a combination of two or more thereof.
  • the average particle size (ie D50 particle size) of the microsphere titanium-silicon molecular sieve catalyst is 10-50 microns, preferably 13-47 microns, more preferably 16-44 microns, preferably 20-40 microns, preferably 25-35 microns.
  • the preparation method of the microsphere titanium-silicon molecular sieve catalyst of the present invention comprises the following steps:
  • the titanium-silicon molecular sieve original powder has the following composition:
  • x 0.0005-0.04, preferably 0.001-0.035, more preferably 0.002-0.030, more preferably 0.003-0.025, preferably 0.004-0.020, preferably 0.005-0.01.
  • the method for providing the titanium-silicon molecular sieve raw powder is not particularly limited, and can be a conventional method known in the art.
  • the titanium-silicon molecular sieve raw powder can be provided by the method disclosed in US4410501.
  • the method for providing titanium-silicon molecular sieve raw powder comprises the following steps:
  • the molar ratio of silica sol and organic template agent is 1:0.02-0.2, preferably 1:0.04-0.18, more preferably 1:0.06-0.16, and preferably It is 1:0.08-0.14, preferably 1:0.1-0.12.
  • the molar ratio of silica sol and phosphate is 1:0.01-0.5, preferably 1:0.04-0.45, more preferably 1:0.08-0.4, preferably 1 : 0.1-0.35, preferably 1: 0.15-0.3.
  • the organic templating agent suitable for the method of the present invention is not particularly limited, and can be conventional organic templating agents known in the art.
  • the organic template agent is selected from alkyl ammonium halides, for example: R 10-20 (R 1-4 ) 3 ammonium halides, such as cetyltrimethylammonium bromide, cetyltrimethylammonium bromide, Alkyl Triethyl Ammonium Bromide, Cetyl Diethyl Methyl Ammonium Bromide, Cetyl Trimethyl Ammonium Chloride, Cetyl Triethyl Ammonium Chloride, Cetyl Diethyl Ammonium methylammonium chloride, or a mixture thereof.
  • the phosphates used in the present invention are selected from alkaline earth metal phosphates, transition metal phosphates, or a combination of two or more thereof.
  • the phosphate is selected from zinc phosphate, aluminum dihydrogen phosphate, aluminum hydrogen phosphate, aluminum phosphate, magnesium phosphate, calcium phosphate, nickel phosphate, iron phosphate, copper phosphate, cobalt phosphate or two thereof or a combination of more, preferably selected from zinc phosphate, aluminum dihydrogen phosphate, magnesium phosphate, calcium phosphate or a combination of two or more thereof.
  • the method for mixing the silica sol, the organic template and the phosphate in proportion is not particularly limited, and may be a conventional mixing method known in the art.
  • the method of the present invention comprises the steps of mixing the above-mentioned binder with the original powder of titanium-silicon molecular sieve.
  • the ratio of the binder to the original powder of titanium-silicon molecular sieve during mixing is 1: 2-20, preferably 1:4-18, more preferably 1:6-16, preferably 1:8-14, preferably 1:10-12.
  • the method of mixing the binder and the original powder of titanium silicon molecular sieve is not particularly limited, as long as the two can be uniformly mixed.
  • the spray drying method suitable for the present invention is not particularly limited, and can be a conventional method known in the art, for example, the spray drying molding method disclosed in CN111115653A can be used.
  • the inlet temperature of the sprayer is 180-200°C and the outlet temperature is 100-105°C during spray drying.
  • the method of the present invention includes a firing step.
  • a suitable firing method is not particularly limited, and may be a conventional method known in the art.
  • the firing is carried out in air, and the firing temperature is 350-600°C, preferably 380-560°C, more preferably 400-530°C.
  • the preparation method of the microspherical titanium-silicon molecular sieve catalyst of the present invention comprises:
  • the preparation method of the spherical titanium-silicon molecular sieve catalyst of the present invention comprises the steps of uniformly mixing organic template agent, phosphate, binder silica sol and titanium-silicon molecular sieve original powder, and then spray-forming and roasting to obtain microspherical titanium-silicon molecular sieve.
  • the catalyst has catalytic activity similar to that of the original titanium-silicon molecular sieve powder, and the microsphere titanium-silicon molecular sieve has good mechanical strength and can maintain structural stability during a long-term catalytic reaction.
  • the spherical titanium-silicon molecular sieve catalyst of the invention can be used for the hydroxylation of phenol to produce quinone.
  • the catalyzed reaction of the hydroxylation of phenol to produce diphenol comprises the following steps:
  • the reaction of phenol and hydrogen peroxide is carried out in the reaction kettle, the reaction pressure is normal pressure, the reaction temperature is 30 ⁇ 90°C, the phenol concentration is 5 ⁇ 50%, and the phenol and H 2 O 2 molar ratio is 10 ⁇ 1, after the reaction is completed, it is filtered through a filter cloth The reaction solution and the spherical titanium-silicon molecular sieve are separated, and the filtered spherical molecular sieve is returned to the reactor for the next reaction.
  • the spherical titanium-silicon molecular sieve catalyst prepared by the method of the invention has catalytic activity similar to that of the original titanium-silicon molecular sieve powder, and the spherical titanium-silicon molecular sieve has good mechanical strength and can maintain structural stability during long-term catalytic reaction.
  • TS-1 titanium-silicon molecular sieve was synthesized, and the molar ratio of TiO 2 : SiO 2 : TPAOH: H 2 O during synthesis was 0.03:1:0.20:20, and the slurry was separated by high-speed centrifugation after crystallization, Then, the solid is redispersed into water, washed with water for several times, and then dried to obtain the original powder of titanium silicon molecular sieve TS-1 containing a template agent, and the particle size of the original powder is 200-300 nm.
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace the roasting atmosphere is air, and the roasting temperature is 500° C., and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • Fig. 1 The SEM electron microscope image of the prepared microsphere titanium-silicon molecular sieve is shown in Fig. 1 .
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 550 DEG C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 550°C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 580 DEG C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace the roasting atmosphere is air, and the roasting temperature is 500° C., and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace the roasting atmosphere is air, and the roasting temperature is 500° C., and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 500 DEG C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1. Then, the original catalyst powder was calcined at 550° C. in an air atmosphere to obtain an unshaped TS-1 titanium-silicon molecular sieve.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 500°C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 500 DEG C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the original powder of titanium-silicon molecular sieve was synthesized by the same method as in Example 1.
  • the spherical titanium-silicon molecular sieve catalyst was synthesized according to the following method:
  • roasting the spherical titanium-silicon molecular sieve intermediate in a muffle furnace, the roasting atmosphere is air, and the roasting temperature is 500 DEG C, and the spherical titanium-silicon molecular sieve catalyst is obtained after roasting.
  • the performance of the catalysts of Examples 1 to 7 and Comparative Examples 1 to 4 in the reaction of catalyzing the hydroxylation of phenol to produce quinone was tested.
  • the reaction was carried out in a three-necked round-bottomed flask with a reflux condenser, mechanically stirred, and heated in a constant temperature water bath.
  • the reaction pressure was normal pressure
  • the reaction temperature was 70°C
  • the phenol concentration was 50%
  • the mass ratio of catalyst and phenol was 1:20
  • the molar ratio of phenol and H 2 O 2 was 3: 1
  • the hydrogen peroxide was slowly added dropwise through a peristaltic pump, and the reaction time was 6 Hour.
  • reaction solution is centrifuged using a filter cloth with an average pore size of 1 micron, and a small amount of titanium-silicon molecular sieve fine particles will be lost through the filter cloth during filtration.
  • the filtered solid was returned to the flask for the next reaction.
  • the catalyst was taken out, dried and calcined to obtain a white catalyst, which was weighed and compared with the weight of the catalyst initially put in to calculate the retention rate of the catalyst:
  • the conversion rate of phenol is close to the limited utilization rate of hydrogen peroxide, and the loss of the catalyst is still very small after 10 cycles of use, indicating that the spherical titanium-silicon molecular sieve of the present invention has good mechanical strength and can be used in a long-term catalytic reaction process. Maintain structural stability.

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  • Organic Chemistry (AREA)
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Abstract

公开了球形钛硅分子筛催化剂及其制备方法，所述微球钛硅分子筛催化剂具有如下组成：xTiO 2·(1-x)SiO 2/yMPO 4，其中，x＝0.0005-0.04,y＝0.005-0.20；M是选自碱土金属、过渡金属或其两种或更多种组合的金属元素；它是用如下方法制得的：(i)提供具有如下组成的钛硅分子筛原粉：xTiO 2·(1-x)SiO 2，其中，x＝0.0005-0.04,y＝0.005-0.20；(ii)将硅溶胶、有机模板剂和磷酸盐按照比例混合，得到粘合剂；(iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂。

Description

球形钛硅分子筛催化剂及其制备方法 技术领域
本发明涉及一种球形钛硅分子筛催化剂、其制备方法以及其在苯酚羟基化制对苯二酚中的应用。
背景技术
对苯二酚和邻苯二酚是两种重要的化工原料和化工中间体，具有广泛的用途。邻苯二酚可用作橡胶硬化剂、电镀添加剂、皮肤防腐杀菌剂、染发剂、照相显影剂、彩照抗氧化剂、毛皮染色显色剂、油漆和清漆抗起皮剂。对苯二酚主要用于显影剂、蒽醌染料、偶氮染料、合成氨助溶剂、橡胶防老剂、阻聚剂、涂料和香精的稳定剂、抗氧剂。
目前工业上生产苯二酚的技术包括异丙苯工艺、苯酚羟基化工艺和苯胺工艺，其中苯酚羟基化工艺以苯酚为原料，双氧水为氧化剂，通过羟基化反应得到对苯二酚和邻苯二酚，副产物是水，所以这是一条绿色的工艺路线。苯酚羟基化工艺使用的催化剂包括均相铁催化剂、高氯酸催化剂和固体钛硅分子筛催化剂。上世纪八十年代初，意大利Taramasso在USP4410501中，公开了一种被称为钛硅分子筛(TS-1)的新型催化氧化材料，它用于苯酚羟基化工艺时，具有很好的催化活性和选择性。
但由于钛硅分子筛原始晶粒微小(100～500nm)，在工业运行过程中不利于催化剂与产物的分离和回收，故需要将钛硅分子筛催化剂进一步成型成为微球钛硅分子筛催化剂。常规成型方法有挤条成型和喷雾成型，挤条成型催化剂适用于固定床反应器，喷雾成型适用于淤浆床工艺。喷雾成型作为制备微球钛硅分子筛催化剂主要方法，专利US5500199、EP00265018、US4701428均对喷雾干燥成型过程进行了描述。
例如，如US4701428的实施例1所述，它首先通过离心分离获得钛硅分子筛原粉，将四乙基原硅酸酯与氢氧化四丙基铵配制成水溶液，随后将两种混合后喷雾成型，得到微球状钛硅分子筛催化剂。
尽管喷雾干燥成型能够有利地制得微球状钛硅分子筛催化剂，但是发现通过 喷雾成型制备的微球钛硅分子筛的性能比成型前的钛硅分子筛原粉要差。而且二氧化硅做粘结剂的球形钛硅分子筛的强度仍然不是很好，在长时间的运转过程中，球形颗粒会发生破碎，产生大量细微的颗粒，在分离过程中这些颗粒会透过滤网损失掉，造成催化剂消耗变大。
为解决上述问题，CN103212435A提出了一种球形钛硅分子筛的制备方法，通过添加二次晶化过程，定向转化喷雾成型微球钛硅分子筛催化剂表面无定形二氧化硅粘结剂为晶型二氧化硅，提高了微球钛硅分子筛的催化氧化活性，也保证了微球钛硅分子筛的机械强度。但是该方法制备过程复杂，而且成型后钛硅分子筛的机械强度仍然不是很高。
CN111115653A公开了一种喷雾成型微球状钛硅分子筛的改性方法，包括分子筛成型步骤和催化剂改性步骤。所述分子筛成型步骤包括：
(1)喷雾母液准备：将硅溶胶和造孔剂加入到分子筛母液中，得到母液A，通过浓硝酸调节母液A的pH为9-10；所述分子筛母液中含有钛硅分子筛；
将钛源滴加至叔丁醇中，搅拌30min，随后加入到上述母液A中，搅拌状态下，于50℃老化24小时，得到母液B；
(2)分子筛成型：将所述母液B采用喷雾干燥成型得到成型的分子筛，所述喷雾干燥过程的入口温度为180-200℃，出口温度100-105℃。
这种分子筛成型方法过程复杂，导致成本偏高。
因此，仍需要提供一种球形钛硅分子筛催化剂的制备方法，用这种方法制得的催化剂具有与钛硅分子筛原粉类似的催化活性，而且微球钛硅分子筛机械强度好，在长时间的催化反应过程中能够保持结构稳定性。还需要提供用上述方法制得的球形钛硅分子筛催化剂。
发明内容
因此，本发明的一个方面涉及一种微球钛硅分子筛催化剂，它具有如下组成：
xTiO 2·(1-x)SiO 2/yMPO 4
其中，x＝0.0005-0.04,y＝0.005-0.2
M是选自碱土金属、过渡金属或其两种或更多种组合的金属元素；
它是用如下方法制得的：
(i)提供钛硅分子筛原粉，所述钛硅分子筛原粉具有如下组成：
xTiO 2·(1-x)SiO 2
其中，x＝0.0005-0.04；
(ii)将硅溶胶、有机模板剂和磷酸盐按照摩尔比SiO 2:有机模板剂:磷酸盐为1:0.02-0.2:0.01-0.5的比例混合，得到粘合剂；所述磷酸盐选自碱土金属磷酸盐、过渡金属磷酸盐或其两种或多种的组合；
(iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂，所述粘合剂与钛硅分子筛原粉相混合时，粘合剂中的二氧化硅与钛硅分子筛原粉的重量比为1：2-20。
本发明的另一个方面涉及一种微球钛硅分子筛催化剂的制备方法，所述微球钛硅分子筛催化剂具有如下组成：
xTiO 2·(1-x)SiO 2/yMPO 4
其中，x＝0.0005-0.04,y＝0.005-0.2；
M选自碱土金属、过渡金属元素或其两种或更多种的组合；
所述方法包括：
(i)提供钛硅分子筛原粉，所述钛硅分子筛原粉具有如下组成：
xTiO 2·(1-x)SiO 2
其中，x＝0.0005-0.04；
(ii)将硅溶胶、有机模板剂和磷酸盐按照摩尔比SiO 2:有机模板剂:磷酸盐为1:0.02-0.2:0.01-0.5的比例混合，得到粘合剂；所述磷酸盐选自碱土金属磷酸盐、过渡金属磷酸盐或其两种或更多种的组合；
(iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂，所述粘合剂与钛硅分子筛原粉相混合时，粘合剂中的二氧化硅与钛硅分子筛原粉的重量比为1：2-20。
附图说明
下面结合附图进一步说明本发明，附图中：
图1是本发明一个实例的微球钛硅分子筛的SEM电镜图。
具体实施方式
本发明微球钛硅分子筛催化剂具有如下组成：
xTiO 2·(1-x)SiO 2/yMPO 4
其中，x＝0.0005-0.04,较好为0.001-0.035，更好为0.002-0.030，更好为 0.003-0.025，宜为0.004-0.020，优选0.005-0.01。
y＝0.005-0.2，较好为0.008-0.15，更好为0.012-0.010，宜为0.015-0.08，优选0.03-0.05。
M选自碱土金属、过渡金属元素或其两种或更多种的组合。
在本发明的一个实例中，M选自钙、镁、锌、镍、铝、铁、铜、钴、或其两种或更多种的组合。
在本发明的一个实例中，所述微球钛硅分子筛催化剂的平均粒径(即D50粒径)为10-50微米，较好为13-47微米，更好为16-44微米，宜为20-40微米，优选25-35微米。
本发明微球钛硅分子筛催化剂的制备方法包括如下步骤：
(i)提供钛硅分子筛原粉，所述钛硅分子筛原粉具有如下组成：
xTiO 2·(1-x)SiO 2
其中，x＝0.0005-0.04,较好为0.001-0.035，更好为0.002-0.030，更好为0.003-0.025，宜为0.004-0.020，优选0.005-0.01。
用于提供钛硅分子筛原粉的方法无特别的限制，可以是本领域已知的常规方法，例如，可采用US4410501公开的方法提供所述钛硅分子筛原粉。
在本发明的一个实例中，所述提供钛硅分子筛原粉的方法包括如下步骤：
在一个装有搅拌器并处于无二氧化碳环境中反应容器中加入四乙基原硅酸酯和钛酸四乙酯，随后逐渐加入氢氧化四乙基铵溶液，搅拌，并加热至80-90℃以加速水解并蒸发形成的乙醇；接着加水并将反应物转入带有搅拌器的钛反应釜中，加热至170-180℃，并在该温度下搅拌9-12天，洗涤后得到晶体状产物，最后将该产物在500-600℃的温度下烧制5-7小时，得到钛硅分子筛原粉。
(ii)将硅溶胶、有机模板剂和磷酸盐按照摩尔比SiO 2:有机模板剂:磷酸盐为1:0.02-0.2:0.01-0.5的比例混合，得到粘合剂；所述磷酸盐选自碱土金属磷酸盐、过渡金属的磷酸盐或其两种或更多种的组合；
本发明粘合剂中，硅溶胶和有机模板剂的摩尔比(SiO 2:有机模板剂)为1:0.02-0.2，较好为1:0.04-0.18，更好为1:0.06-0.16，宜为1:0.08-0.14，优选1:0.1-0.12。
本发明粘合剂中，硅溶胶和磷酸盐的摩尔比(SiO 2:磷酸盐)为1:0.01-0.5，较好为1:0.04-0.45，更好为1:0.08-0.4，宜为1:0.1-0.35，优选1:0.15-0.3。
适用于本发明方法的有机模板剂无特别的限制，可以是本领域已知的常规有 机模板剂。在本发明的一个实例中，所述有机模板剂选自烷基卤化铵，例如：R 10-20(R 1-4) 3卤化铵，如十六烷基三甲基溴化铵、十六烷基三乙基溴化铵、十六烷基二乙基甲基溴化铵、十六烷基三甲基氯化铵、十六烷基三乙基氯化铵、十六烷基二乙基甲基氯化铵、或其混合物。
本发明使用的磷酸盐选自碱土金属磷酸盐、过渡金属的磷酸盐或其两种或更多种的组合。在本发明的一个实例中，所述磷酸盐选自磷酸锌、磷酸二氢铝、磷酸氢铝、磷酸铝、磷酸镁、磷酸钙、磷酸镍、磷酸铁、磷酸铜、磷酸钴或其两种或更多种的组合，较好选自磷酸锌、磷酸二氢铝、磷酸镁、磷酸钙或其两种或更多种的组合。
将硅溶胶、有机模板剂和磷酸盐按比例混合的方法无特别的限制，可以是本领域已知的常规混合方法。
(iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂，所述粘合剂与钛硅分子筛原粉相混合时，粘合剂中的二氧化硅与钛硅分子筛原粉的重量比为1：2-20。
本发明方法包括将上述粘合剂与钛硅分子筛原粉相混合的步骤，按所述粘合剂中二氧化硅的重量计，混合时粘合剂与钛硅分子筛原粉的比例为1：2-20，较好为1：4-18，更好为1：6-16，宜为1：8-14，优选1：10-12。
将所述粘合剂与钛硅分子筛原粉相混合的方法无特别的限制，只要能将两者均匀混合即可。
适合于本发明的喷雾干燥方法无特别的限制，可以是本领域已知的常规方法，例如，可采用CN111115653A公开的喷雾干燥成型方法。在本发明的一个实例中，喷雾干燥时喷雾器入口温度为180-200℃，出口温度100-105℃。
在喷雾干燥成型后，本发明方法包括烧制步骤。适合的烧制方法无特别的限制，可以是本领域已知的常规方法。在本发明的一个实例中，所述烧制是在空气中进行的，烧制温度为350-600℃，较好为380-560℃，更好为400-530℃。
在本发明的一个较好的实例中，本发明微球状钛硅分子筛催化剂的制备方法包括：
(i)按照美国专利US4410501公开的方法合成TS-1钛硅分子筛：以预定的TiO 2:SiO 2:TPAOH:H 2O的摩尔比将浆料混合并晶化，晶化之后将浆液通过高速离心实现分离，然后将固体重新分散入水中，通过多次水洗进行洗涤，然后烘干得 到含有模板剂的钛硅分子筛TS-1原粉，原粉的粒径尺寸为200～300nm；
(ii)按预定的比例将硅溶胶、十六烷基三甲基溴化铵、磷酸盐混合均匀，形成含有模板剂和磷酸盐的粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，搅拌；
(iii)将前述的混合溶液通过喷雾干燥成型，得到球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在焙烧炉(例如马弗炉)中焙烧，得到球形钛硅分子筛催化剂。
本发明球形钛硅分子筛催化剂的制备方法包括将有机模板剂、磷酸盐与粘结剂硅溶胶、钛硅分子筛原粉混合均匀后，再经过喷雾成型和焙烧，得到微球钛硅分子筛。催化剂具有与钛硅分子筛原粉类似的催化活性，而且微球钛硅分子筛机械强度好，在长时间的催化反应过程中能够保持结构稳定性。
本发明球形钛硅分子筛催化剂可用于苯酚羟基化制苯二酚。在本发明的一个实例中，所述苯酚羟基化制苯二酚的催化反应包括以下步骤：
苯酚和双氧水反应在反应釜中进行，反应压力为常压，反应温度30～90℃，苯酚浓度5～50％，苯酚和H 2O 2摩尔比为10～1，反应完成之后通过滤布过滤分离反应液和球形钛硅分子筛，过滤后的球形分子筛返回反应釜进行下一次反应。
本发明方法制备的球形钛硅分子筛催化剂具有与钛硅分子筛原粉类似的催化活性，而且球形钛硅分子筛机械强度好，在长时间的催化反应过程中能够保持结构稳定性。
下面结合实施例更详细地说明本发明。
实施例1
钛硅分子筛原粉的制备：
按照专利US4410501报道的方法合成TS-1钛硅分子筛，合成时TiO 2:SiO 2:TPAOH:H 2O的摩尔比为0.03:1:0.20:20，晶化之后将浆液通过高速离心实现分离，然后将固体重新分散入水中，通过多次水洗进行洗涤，然后烘干得到含有模板剂的钛硅分子筛TS-1原粉，原粉的粒径尺寸为200～300nm。
球形钛硅分子筛催化剂的制备：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵：磷酸锌摩 尔比为1∶0.1：0.1混合均匀，形成含有模板剂和磷酸盐的粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶10，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为35微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
制得的微球钛硅分子筛的SEM电镜图如图1所示。
实施例2
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵：磷酸二氢铝摩尔比为1∶0.1：0.1混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶10，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为48微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为550℃，焙烧后得到球形钛硅分子筛催化剂。
实施例3
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基氯化铵：磷酸二氢铝摩尔比为1∶0.15：0.1混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶10，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为47微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度 为550℃，焙烧后得到球形钛硅分子筛催化剂。
实施例4
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基氯化铵：磷酸镁摩尔比为1∶0.15：0.18混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶5，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为32微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为580℃，焙烧后得到球形钛硅分子筛催化剂。
实施例5
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵：磷酸钙摩尔比为1∶0.15：0.05混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶10，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为42微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
实施例6
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵：磷酸二氢铝摩尔比为1∶0.15：0.04混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅 分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶15，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为28微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
实施例7
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵：磷酸二氢铝摩尔比为1∶0.15：0.4混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶15，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为55微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
对比例1
按照实施例1相同的方法合成钛硅分子筛原粉。然后在550℃、空气气氛下焙烧催化剂原粉，得到未成型的TS-1钛硅分子筛。
对比例2
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶钛硅分子筛原粉重量比为1:10添加钛硅分子筛，混合均匀；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为37微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度 为500℃，焙烧后得到球形钛硅分子筛催化剂。
对比例3
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶磷酸二氢铝摩尔比为1∶0.4混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶15，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为52微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
对比例4
按照实施例1相同的方法合成钛硅分子筛原粉。
按照下面的方法合成球形钛硅分子筛催化剂：
(1)按照硅溶胶(30％浓度)中的SiO 2∶十六烷基三甲基溴化铵摩尔比为1∶0.15，混合均匀，形成粘结剂溶液，然后将含有模板剂的钛硅分子筛原粉加入到混合溶液中，添加的比例为SiO 2与原粉的重量比为1∶15，在30℃强烈搅拌2小时；
(2)将前述的混合溶液通过喷雾干燥成型，得到D 50为28微米的球形钛硅分子筛催化剂中间体；
(3)将球形钛硅分子筛中间体在马弗炉中焙烧，焙烧气氛为空气，焙烧温度为500℃，焙烧后得到球形钛硅分子筛催化剂。
实施例8
测试实施例1～7和对比实施例1～4的催化剂在催化苯酚羟基化制苯二酚反应中的性能。反应在一个带有回流冷凝管的三口圆底烧瓶中进行，机械搅拌，恒温水浴加热。反应压力为常压，反应温度70℃，苯酚浓度50％，催化剂和苯酚的质量比1:20，苯酚和H 2O 2摩尔比为3:1，双氧水通过蠕动泵缓慢滴加，反应时间6小时。反应完成之后使用平均孔径为1微米的滤布离心分离反应液，过滤时会有 微量的钛硅分子筛细颗粒透过滤布损失掉。将过滤后的固体返回到烧瓶中，进行下一次反应。
通过液相色谱分析反应液中的苯酚、邻苯二酚和对苯二酚的含量。
苯酚转化率计算公式如下：
Figure PCTCN2021128086-appb-000001
双氧水有效利用率计算公式如下：
Figure PCTCN2021128086-appb-000002
循环使用10次之后，将催化剂取出，干燥、焙烧，得到白色的催化剂，称重，并与最初投入的催化剂的重量进行对比，计算催化剂的保留率：
Figure PCTCN2021128086-appb-000003
反应结果如下表：
  苯酚转化率 H 2O 2有效利用率 催化剂保留率
实施例1 26.5％ 80.3％ 88.2％
实施例2 27.2％ 82.4％ 97.5％
实施例3 26.1％ 79.1％ 96.5％
实施例4 23.2％ 70.3％ 96.6％
实施例5 22.8％ 69.1％ 92.3％
实施例6 28.1％ 85.2％ 94.5％
实施例7 26.1％ 79.1％ 98.8％
对比例1 28.2％ 85.5％ 完全透过滤布
对比例2 21.3％ 64.5％ 76.8％
对比例3 20.3％ 61.5％ 98.1％
对比例4 26.8％ 81.2％ 65.3％
从表中评价结果可知，相对于钛硅分子筛TS-1原粉来说，采用常规技术喷雾成型得到的微球钛硅分子筛催化剂的催化活性有明显的降低，而且反应10次之后，催化剂破损严重，催化剂细粉透过了滤布，造成催化剂的损耗很大；而本发明得到的球形钛硅分子筛催化剂的催化活性明显高于常规技术制备的催化剂，达到了钛硅分子筛TS-1原粉的水平，苯酚的转化率和双氧水有限利用率接近，而且催化剂经过10次循环使用之后，催化剂的损耗仍然很小，说明本发明的球形钛硅分子筛机械强度好，在长时间的催化反应过程中能够保持结构稳定性。

Claims (11)

  1. 一种微球钛硅分子筛催化剂，它具有如下组成：
    xTiO 2·(1-x)SiO 2/yMPO 4
    其中，x＝0.0005-0.04,y＝0.005-0.2；
    M是选自碱土金属、过渡金属或其两种或更多种组合的金属元素；
    它是用如下方法制得的：
    (i)提供钛硅分子筛原粉，所述钛硅分子筛原粉具有如下组成：
    xTiO 2·(1-x)SiO 2
    其中，x＝0.0005-0.04；
    (ii)将硅溶胶、有机模板剂和磷酸盐按照摩尔比SiO 2:有机模板剂:磷酸盐为1:0.02-0.2:0.01-0.5的比例混合，得到粘合剂；所述磷酸盐选自碱土金属磷酸盐、过渡金属磷酸盐或其两种或多种的组合；
    (iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂，所述粘合剂与钛硅分子筛原粉相混合时，粘合剂中的二氧化硅与钛硅分子筛原粉的重量比为1：2-20。
  2. 如权利要求1所述的微球钛硅分子筛催化剂，其特征在于
    x＝0.001-0.035，更好为0.002-0.030，更好为0.003-0.025，宜为0.004-0.020，优选0.005-0.01；
    y＝0.008-0.15，更好为0.012-0.010，宜为0.015-0.08，优选0.03-0.05。
  3. 如权利要求1所述的微球钛硅分子筛催化剂，其特征在于M选自钙、镁、锌、镍、铝、铁、铜、钴、或其两种或更多种的组合。
  4. 如权利要求1-3中任一项所述的微球钛硅分子筛催化剂，其特征在于，按硅溶胶中的SiO 2计，
    硅溶胶和有机模板剂的摩尔比为1:0.04-0.18，更好为1:0.06-0.16，宜为1:0.08-0.14，优选1:0.1-0.12；
    硅溶胶和磷酸盐的摩尔比为1:0.04-0.45，更好为1:0.08-0.4，宜为1:0.1-0.35，优选1:0.15-0.3。
  5. 如权利要求1-3中任一项所述的微球钛硅分子筛催化剂，其特征在于，所述有机模板剂选自十六烷基三甲基溴化铵、十六烷基三乙基溴化铵、十六烷基二乙基甲基溴化铵、十六烷基三甲基氯化铵、十六烷基三乙基氯化铵、十六烷基二乙基甲基氯化铵、或其混合物。
  6. 如权利要求1-3中任一项所述的微球钛硅分子筛催化剂，其特征在于，按所述粘合剂中二氧化硅的重量计，混合时粘合剂与钛硅分子筛原粉的比例为1：4-18，更好为1：6-16，宜为1：8-14，优选1：10-12。
  7. 一种微球钛硅分子筛催化剂的制备方法，所述微球钛硅分子筛催化剂具有如下组成：
    xTiO 2·(1-x)SiO 2/yMPO 4
    其中，x＝0.0005-0.04,y＝0.005-0.2；
    M选自碱土金属、过渡金属元素或其两种或更多种的组合；
    所述方法包括：
    (i)提供钛硅分子筛原粉，所述钛硅分子筛原粉具有如下组成：
    xTiO 2·(1-x)SiO 2
    其中，x＝0.0005-0.04；
    (ii)将硅溶胶、有机模板剂和磷酸盐按照摩尔比SiO 2:有机模板剂:磷酸盐为1:0.02-0.2:0.01-0.5的比例混合，得到粘合剂；所述磷酸盐选自碱土金属磷酸盐、过渡金属磷酸盐或其两种或更多种的组合；
    (iii)将所述粘合剂与钛硅分子筛原粉相混合、喷雾干燥成型并烧制得到钛硅分子筛催化剂，所述粘合剂与钛硅分子筛原粉相混合时，粘合剂中的二氧化硅与钛硅分子筛原粉的重量比为1：2-20。
  8. 如权利要求7所述的方法，其特征在于
    x＝0.001-0.035，更好为0.002-0.030，更好为0.003-0.025，宜为0.004-0.020，优选0.005-0.01；
    y＝0.008-0.15，更好为0.012-0.010，宜为0.015-0.08，优选0.03-0.05。
  9. 如权利要求7所述的方法，其特征在于M选自钙、镁、锌、镍、铝、铁、铜、钴、或其两种或更多种的组合；所述有机模板剂选自十六烷基三甲基溴化铵、十六烷基三乙基溴化铵、十六烷基二乙基甲基溴化铵、十六烷基三甲基氯化铵、十六烷基三乙基氯化铵、十六烷基二乙基甲基氯化铵、或其混合物。
  10. 如权利要求7-9中任一项所述的方法，其特征在于，按硅溶胶中的SiO 2计，
    硅溶胶和有机模板剂的摩尔比为1:0.04-0.18，更好为1:0.06-0.16，宜为1:0.08-0.14，优选1:0.1-0.12；
    硅溶胶和磷酸盐的摩尔比为1:0.04-0.45，更好为1:0.08-0.4，宜为1:0.1-0.35，优选1:0.15-0.3。
  11. 如权利要求7-9中任一项所述的方法，其特征在于，按所述粘合剂中二氧化硅的重量计，混合时粘合剂与钛硅分子筛原粉的比例为1：4-18，更好为1：6-16，宜为1：8-14，优选1：10-12。
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