WO2024099165A1 - 一种Ti-MWW分子筛催化剂及其制备方法和应用 - Google Patents

一种Ti-MWW分子筛催化剂及其制备方法和应用 Download PDF

Info

Publication number
WO2024099165A1
WO2024099165A1 PCT/CN2023/128161 CN2023128161W WO2024099165A1 WO 2024099165 A1 WO2024099165 A1 WO 2024099165A1 CN 2023128161 W CN2023128161 W CN 2023128161W WO 2024099165 A1 WO2024099165 A1 WO 2024099165A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
hours
molecular sieve
silicon
fluoride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/128161
Other languages
English (en)
French (fr)
Inventor
杨为民
金少青
范雪研
唐智谋
孙洪敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to KR1020257016187A priority Critical patent/KR20250102038A/ko
Priority to EP23887855.7A priority patent/EP4616944A1/en
Priority to JP2025526538A priority patent/JP2025536031A/ja
Publication of WO2024099165A1 publication Critical patent/WO2024099165A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/63—Pore volume
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the invention relates to the field of titanium silicon molecular sieve catalysts, and in particular to a Ti-MWW molecular sieve catalyst and a preparation method and application thereof.
  • Epoxides are important organic chemical raw materials, mainly including ethylene oxide, propylene oxide, 1,2-epoxypentane and 1,2-epoxyhexane.
  • epoxides are basically produced by selective oxidation of olefins.
  • EniChem has developed a method for producing propylene oxide, namely hydrogen peroxide oxidation (HPPO) (see, for example, US4410501A). It uses TS-1 titanium silicalite with MFI structure as a catalyst to generate propylene oxide by reacting propylene with hydrogen peroxide in methanol solvent. This process has the characteristics of green environmental protection and high raw material utilization, and has now been industrialized.
  • the industrial production of propylene oxide is mainly carried out in fixed bed reactors. Since the titanium silicon molecular sieve obtained by the hydrothermal method is a micron or nanometer-sized powder with no mechanical strength, if it is directly loaded into the fixed bed reactor, it will be entrained into the device pipeline by the reaction liquid during the reaction, causing pipeline blockage. In addition, it is also very difficult to separate and recover the titanium silicon molecular sieve powder from the reaction liquid after the reaction. In order to ensure the efficient and continuous fixed bed reaction, the titanium silicon molecular sieve powder needs to be made into a catalyst with good mechanical strength.
  • CN1346705A proposes to use small balls with certain mechanical strength as carriers, and to enrich titanium silicon molecular sieve on its surface by rolling ball forming, so as to improve the mechanical strength of the obtained catalyst.
  • CN112354557A discloses a method for preparing a monolithic titanium zeolite catalyst and its application, which is prepared by mixing an amorphous silicon-based binder and a polymer pore-forming agent into MWW titanium zeolite powder, adding water, stirring and kneading, mechanically forming and roasting, and then immersing in an aqueous solution of a composite cyclic nitrogen-containing organic matter, sealing and heating, filtering, drying, and roasting to obtain a monolithic propylene continuous epoxidation catalyst.
  • the Ti-MWW molecular sieve catalyst in the prior art whether or not it contains Binders all have the problems of low mechanical strength and poor catalytic performance.
  • the composition and structure of the Ti-MWW molecular sieve catalyst in the prior art can be modified to further improve its mechanical strength and catalytic performance. Therefore, there has always been a need in the art to develop a Ti-MWW molecular sieve catalyst with high mechanical strength and good catalytic performance.
  • the present invention provides a Ti-MWW molecular sieve catalyst, a preparation method and application thereof.
  • the Ti-MWW molecular sieve catalyst of the present invention comprises a titanium species in a good state, preferably having a fully crystalline structure, so as to have the characteristics of high mechanical strength and excellent catalytic performance.
  • the first aspect of the present invention provides a Ti-MWW molecular sieve catalyst, wherein the X-ray photoelectron energy spectrum of the catalyst shows peaks at 458.9 ⁇ 0.2eV and 464.8 ⁇ 0.2eV, preferably at 458.9 ⁇ 0.1eV and 464.8 ⁇ 0.1eV; preferably, the X-ray photoelectron energy spectrum of the catalyst shows peaks at 458.9 ⁇ 0.2eV, 460.3 ⁇ 0.2eV, 464.8 ⁇ 0.2eV, and 465.9 ⁇ 0.2eV, preferably at 458.9 ⁇ 0.1eV, 460.3 ⁇ 0.1eV, 464.8 ⁇ 0.1eV, and 465.9 ⁇ 0.1eV.
  • a second aspect of the present invention provides a method for preparing a Ti-MWW molecular sieve catalyst, comprising the following steps:
  • step (2) crystallizing the formed product of step (1) in the presence of an organic amine solution to obtain a catalyst precursor A;
  • the present invention also provides a Ti-MWW molecular sieve catalyst prepared by the above method.
  • the present invention provides an application of the Ti-MWW molecular sieve catalyst in olefin epoxidation reaction.
  • the present invention may include the following aspects.
  • a fully crystalline Ti-MWW molecular sieve catalyst whose UV Raman spectrum has peaks at 343 ⁇ 4cm -1 , 484 ⁇ 4cm -1 , 699 ⁇ 4cm -1 and 1097 ⁇ 4cm -1 , and 699 ⁇ 4cm -1
  • the intensity of the peak is 0.5-10 times, preferably 2-10 times, the intensity of the peak at 343 ⁇ 4 cm -1
  • the intensity of the peak at 1097 ⁇ 4 cm -1 is 0.5-10 times, preferably 2-10 times, the intensity of the peak at 343 ⁇ 4 cm -1 .
  • the molecular sieve catalyst according to Scheme 1 is characterized in that the molar ratio of silicon to titanium in the molecular sieve catalyst is 10-200, preferably 25-100; the molecular sieve catalyst also includes at least one element of boron and aluminum, preferably boron; the molar ratio of boron to silicon in the molecular sieve catalyst is 0-0.1, preferably 0-0.03, more preferably 0.005-0.03; the molar ratio of aluminum to silicon in the molecular sieve catalyst is 0-0.1, preferably 0-0.05.
  • the molecular sieve catalyst according to Scheme 1 is characterized in that the micropore volume of the molecular sieve catalyst is 0.03-0.15 cm 3 /g, preferably 0.03-0.12 cm 3 /g, more preferably 0.05-0.10 cm 3 /g; the proportion of micropore volume to total pore volume is 1%-7.5%, preferably 1-6%, more preferably 1.7%-5%.
  • the molecular sieve catalyst according to Scheme 1 is characterized in that the mechanical strength of the molecular sieve catalyst is 30-90 N/cm, preferably 40-80 N/cm.
  • a method for preparing a fully crystalline Ti-MWW molecular sieve catalyst comprising the following steps:
  • step (2) crystallizing the product obtained in step (1) in an environment containing an organic amine solution to obtain a catalyst precursor A;
  • step (3) (4) treating the catalyst precursor B in step (3) with an organic amine solution to obtain the molecular sieve catalyst.
  • the preparation method according to Scheme 6 is characterized in that the silicon source is selected from at least one of silica sol, water glass, white carbon black and tetraethyl orthosilicate; the boron source is selected from at least one of boric acid, boron trioxide and borates; the aluminum source is selected from at least one of aluminum trioxide, aluminum hydroxide, sodium aluminate, aluminum nitrate and aluminum sulfate.
  • step (1) The pore-forming agent is selected from at least one of sesbania powder, cellulose, chitosan, lignin, starch, polyethylene glycol, triblock copolymers P123 and F127; the fluoride in step (1) is selected from at least one of sodium fluoride, potassium fluoride and ammonium fluoride; the mass ratio of the raw materials in step (1), Ti-MWW molecular sieve powder, binder, pore-forming agent and fluoride is 1:0.1-1.5:0.01-0.1:0.01-0.4.
  • the preparation method according to Scheme 5 is characterized in that the process of crystallization in the environment containing organic amine solution in step (2) comprises: step (1) placing the molded object on the organic amine solution for crystallization, and the molded object is not in contact with the organic amine solution; the organic amine is at least one selected from piperidine and hexamethyleneimine; the concentration of the organic amine solution is 0.3-15 mol/L; the mass ratio of the molded object to the organic amine solution is 0.1-10:1; the crystallization conditions are: the crystallization temperature is 130-190°C, and the crystallization time is 1-9 days.
  • the preparation method according to Scheme 5 is characterized in that the process of acid solution treatment in step (3) comprises: step (2) catalyst precursor A is contacted with acid solution for reaction; the acid solution is selected from at least one of nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid or oxalic acid solution; the concentration of the acid solution is 0.3-12 mol/L; the solid-liquid mass ratio of the catalyst precursor A to the acid solution is 1:10-80; the conditions of the acid solution treatment are: the treatment temperature is 60-130°C, and the treatment time is 4-48 hours.
  • the preparation method according to Scheme 5 is characterized in that the process of treating with organic amine solution in step (4) comprises: step (3) contacting and reacting catalyst precursor B with fluoride and organic amine solution; the fluoride is selected from at least one of sodium fluoride, potassium fluoride and ammonium fluoride; the organic amine is selected from at least one of piperidine and hexamethyleneimine; the concentration of the organic amine solution is 0.3-15 mol/L; the mass ratio of the catalyst precursor B, fluoride and organic amine solution is 1:0.05-0.4:2-20; the conditions for treating with organic amine solution are: the treatment temperature is 130-190°C and the treatment time is 4-48 hours.
  • the preparation method according to Scheme 5 is characterized in that the calcination conditions in step (1) are calcination at 450-650°C in an oxygen-containing atmosphere for 4-12 hours; and the calcination conditions in step (3) are calcination at 450-650°C in an oxygen-containing atmosphere for 4-12 hours.
  • the present invention has the following advantages:
  • titanium species in good condition in the Ti-MWW molecular sieve catalyst of the present invention includes a modified non-framework hexacoordinated titanium species, or includes a framework tetracoordinated titanium species and a modified non-framework hexacoordinated titanium species. These titanium species in good condition provide the catalyst with higher catalytic performance.
  • the Ti-MWW molecular sieve catalyst preferably has a fully crystalline structure. This means that the catalyst does not contain an amorphous binder.
  • the binder does not exist in an amorphous form, but is converted into an MWW structure molecular sieve, and then becomes part of the final catalyst, thereby giving the resulting catalyst a fully crystalline structure.
  • the absence of an amorphous binder means that the shielding of the catalytic active center and the clogging of the molecular sieve pores by the amorphous binder are avoided, thereby improving the activity and stability of the catalyst;
  • the fully crystalline structure means that the mechanical strength is higher and the catalyst is not easy to pulverize and lose.
  • the catalyst is used in the olefin epoxidation reaction, and has the characteristics of high olefin conversion, high epoxide selectivity, and good catalytic stability.
  • the preferred amorphous binder includes a silicon source and a boron source, which can be efficiently converted into an MWW structure molecular sieve, thereby giving the obtained catalyst a fully crystalline structure, thereby improving the catalytic performance and mechanical strength.
  • the preparation method treats the catalyst precursor A obtained by crystallization with an acid solution and an organic amine solution, respectively, effectively converting the titanium species in the Ti-MWW molecular sieve into a titanium species in a good state, which includes a modified non-framework hexacoordinated titanium species and an optional framework tetracoordinated titanium species.
  • the preparation method of the present invention gives the obtained Ti-MWW molecular sieve catalyst excellent catalytic activity, selectivity and stability.
  • the catalyst of the present invention is used in olefin epoxidation reaction, has excellent catalytic performance, high olefin conversion rate, high epoxide selectivity, good catalytic stability, and shows good application prospects.
  • FIG1 is an X-ray photoelectron spectrum of the Ti-MWW molecular sieve catalyst prepared in Example 1;
  • FIG2 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in Example 1;
  • FIG3 is an X-ray diffraction pattern of the Ti-MWW molecular sieve catalyst prepared in Example 1;
  • FIG4 is a scanning electron microscope image of the Ti-MWW molecular sieve catalyst prepared in Example 1;
  • Figure 5 is an X-ray of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 1] Photoelectron spectrum
  • FIG6 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 1];
  • FIG7 is an X-ray diffraction pattern of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 1];
  • FIG8 is a scanning electron microscope image of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 1];
  • FIG9 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 2];
  • FIG10 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 3];
  • FIG11 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 4];
  • FIG12 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 5];
  • FIG13 is an X-ray photoelectron spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 6];
  • FIG14 is a UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 6];
  • FIG15 is an X-ray photoelectron spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 7];
  • FIG16 is the UV Raman spectrum of the Ti-MWW molecular sieve catalyst prepared in [Comparative Example 7].
  • the present invention provides a Ti-MWW molecular sieve catalyst, wherein:
  • the X-ray photoelectron energy spectrum of the catalyst shows peaks at 458.9 ⁇ 0.2eV and 464.8 ⁇ 0.2eV, and preferably shows peaks at 458.9 ⁇ 0.1eV and 464.8 ⁇ 0.1eV;
  • the X-ray photoelectron energy spectrum of the catalyst shows peaks at 458.9 ⁇ 0.2eV, 460.3 ⁇ 0.2eV, 464.8 ⁇ 0.2eV, and 465.9 ⁇ 0.2eV, and preferably shows peaks at 458.9 ⁇ 0.1eV, 460.3 ⁇ 0.1eV, 464.8 ⁇ 0.1eV, and 465.9 ⁇ 0.1eV.
  • the peaks at 460.3 ⁇ 0.2eV and 465.9 ⁇ 0.2eV are attributed to the framework tetracoordinated titanium species; the peaks at 458.9 ⁇ 0.2eV and 464.8 ⁇ 0.2eV are attributed to the modified non-framework hexacoordinated titanium species.
  • Ti-MWW molecular sieve refers to a silicon-titanium molecular sieve with a three-dimensional MWW structure.
  • Ti-MWW molecular sieves can be commercially available or prepared according to known methods in the art. Generally, Ti-MWW molecular sieves are synthesized by a hydrothermal method using boric acid as a crystallization aid (see, for example, Journal of Physical Chemistry B, 2001, 105, 2897). In this article, the Ti-MWW molecular sieve prepared by the hydrothermal method is referred to as "as-synthesized Ti-MWW molecular sieve powder".
  • Ti-MWW molecular sieve powder can be acid-treated (see, for example, Journal of Catalysis, 2001, 202, 245).
  • the acid-treated Ti-MWW molecular sieve powder is referred to as "Ti-MWW molecular sieve powder”.
  • the titanium species in the Ti-MWW molecular sieve can exist in the form of framework tetracoordinate, non-framework hexacoordinate and titanium dioxide.
  • the Ti-MWW molecular sieve raw powder prepared by the hydrothermal method contains a small amount of framework tetracoordinate titanium species and a large amount of non-framework hexacoordinate titanium species.
  • the framework tetracoordinate titanium species is the catalytic active center of olefin epoxidation, the so-called "titanium species in good condition"
  • the non-framework hexacoordinate titanium species and titanium dioxide are not the catalytic active centers of olefin epoxidation, the so-called "titanium species in bad condition”.
  • the existing technology is committed to converting non-framework hexacoordinate titanium species into framework tetracoordinate titanium species to improve the catalytic performance of the catalyst.
  • the above-mentioned acid treatment of the Ti-MWW molecular sieve raw powder is such a conversion.
  • non-framework hexacoordinated titanium species or framework tetracoordinated titanium species can be converted into modified non-framework hexacoordinated titanium species.
  • the modification of the titanium species can be reflected by the X-ray photoelectron spectrum peaks of the Ti-MWW molecular sieve. Before modification, the X-ray photoelectron spectrum of the Ti-MWW molecular sieve original powder will have peaks at 458.0 ⁇ 0.2eV and 463.8 ⁇ 0.2eV, which are attributed to the non-framework hexacoordinated titanium species.
  • the X-ray photoelectron spectrum of the Ti-MWW molecular sieve powder will have peaks at 460.3 ⁇ 0.2eV and 465.9 ⁇ 0.2eV, which are attributed to the framework tetracoordinated titanium species.
  • the X-ray photoelectron spectrum of the Ti-MWW molecular sieve powder will have peaks at 460.3 ⁇ 0.2eV and 465.9 ⁇ 0.2eV, which are attributed to the framework tetracoordinated titanium species.
  • the energy spectrum will have peaks at 458.9 ⁇ 0.2eV and 464.8 ⁇ 0.2eV, which belong to the modified non-framework hexacoordinated titanium species.
  • This modified non-framework hexacoordinated titanium species also has excellent olefin epoxidation catalytic activity, that is, it is also a titanium species in good condition, thereby giving the Ti-MWW molecular sieve catalyst of the present invention improved catalytic performance. Based on the above findings, the present invention was completed.
  • the UV Raman spectrum of the catalyst has peaks at 343 ⁇ 4cm -1 , 484 ⁇ 4cm -1 , 699 ⁇ 4cm -1 and 1097 ⁇ 4cm -1 , and the intensity of the 699 ⁇ 4cm -1 peak is 0.5-10 times, preferably 2-10 times, of the 343 ⁇ 4cm -1 peak intensity, and the intensity of the 1097 ⁇ 4cm - 1 peak is 0.5-10 times, preferably 2-10 times, of the 343 ⁇ 4cm-1 peak intensity.
  • the 343 ⁇ 4cm -1 peak is attributed to the MWW framework
  • the 484 ⁇ 4cm -1 and 1097 ⁇ 4cm -1 peaks are attributed to the framework tetracoordinated titanium species
  • the 699 ⁇ 4cm -1 peak is attributed to the non-framework hexacoordinated titanium species and/or modified non-framework hexacoordinated titanium species.
  • the catalyst has a silicon to titanium molar ratio (n Si /n Ti ) of 10-200, preferably 25-100, calculated on an atomic basis.
  • the catalyst further comprises at least one element selected from boron and aluminum, preferably boron.
  • the molar ratio of boron to silicon (n B /n Si ) is 0-0.1, preferably 0-0.03, more preferably 0.005-0.03.
  • the molar ratio of aluminum to silicon (n Al /n Si ) is 0-0.1, preferably 0-0.03.
  • the catalyst is a porous structure, which includes micropores, mesopores and macropores.
  • the pore size of the micropores is less than 2nm, such as 0.4-2nm; the pore size of the mesopores is 2-50nm; the pore size of the macropores is greater than 50nm, such as 50-500nm.
  • the micropore volume of the catalyst is 0.03-0.15cm3 /g, preferably 0.03-0.12cm3 /g, more preferably 0.05-0.10cm3 /g; the proportion of the micropore volume to the total pore volume is 1%-7.5%, preferably 1-6%, more preferably 1.7%-5%.
  • the catalyst has a full crystalline structure.
  • full crystallization refers to the absence or substantial absence of an amorphous binder in the molecular sieve catalyst.
  • substantially absent refers to the amount of an amorphous binder in the catalyst being less than 5 weight %, preferably less than 3 weight %, more preferably less than 1 weight %.
  • the binder is converted into a MWW structure molecular sieve, thereby becoming a part for the resulting catalyst.
  • the full crystalline structure can be determined by scanning electron microscopy and X-ray diffraction.
  • the mechanical strength of the catalyst is 30-90 N/cm, preferably 40-80 N/cm.
  • the present invention provides a method for preparing a Ti-MWW molecular sieve catalyst, comprising the following steps:
  • step (2) crystallizing the formed product of step (1) in the presence of an organic amine solution to obtain a catalyst precursor A;
  • the silicon-titanium molar ratio of the Ti-MWW molecular sieve powder is 5 to 120, calculated on an atomic basis.
  • the Ti-MWW molecular sieve powder can be commercially available or prepared according to the techniques disclosed in the art.
  • the binder is an amorphous binder and includes a silicon source and at least one selected from a boron source and an aluminum source.
  • the silicon source is selected from at least one of silica sol, water glass, white carbon black, and ethyl orthosilicate;
  • the boron source is selected from at least one of boric acid, boron trioxide, and borates;
  • the aluminum source is selected from at least one of aluminum trioxide, aluminum hydroxide, sodium aluminate, aluminum nitrate, and aluminum sulfate.
  • the binder can be commercially available or prepared according to the disclosed technology in the art. In one variation, the binder is prepared by mixing the components (e.g., silicon source, boron source, and aluminum source).
  • the pore-forming agent is selected from at least one of sesbania powder, cellulose, chitosan, lignin, starch, polyethylene glycol, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and polyethylene oxide-polypropylene oxide copolymer (F127).
  • the fluoride is selected from at least one of sodium fluoride, potassium fluoride and ammonium fluoride.
  • the Ti-MWW molecular sieve powder, binder, pore former and fluoride are used in a mass ratio of 1:(0.1-1.5):(0.01-0.1):(0.01-0.4).
  • step (1) before forming, the Ti-MWW molecular sieve powder, binder, pore former and fluoride are kneaded, preferably in the presence of water.
  • step (1) after kneading and forming, the product is dried. Preferably, the drying is carried out at 60-120°C for 1-24 hours.
  • the calcination is carried out at 450-650° C. in an oxygen-containing atmosphere for 4-12 hours.
  • the oxygen-containing atmosphere may be air or oxygen, preferably air.
  • step (2) the molded object in step (1) is placed above the organic amine solution, and the molded object is not in contact with the organic amine solution.
  • the organic amine is at least one selected from piperidine and hexamethyleneimine.
  • the concentration of the organic amine solution is 0.3-15 mol/L.
  • the molded object and the organic amine solution are used in a mass ratio of (0.1-10):1.
  • the crystallization is carried out in a closed environment at a temperature of 130-190° C. and under autogenous pressure for 1-9 days.
  • step (2) further comprises: washing and drying the product after crystallization.
  • the washing is water washing.
  • the drying is performed at 60-120° C. for 1-24 hours.
  • step (2) does not include calcination.
  • step (3) comprises: contacting the catalyst precursor A in step (2) with an acid solution and reacting.
  • the acid solution is selected from at least one of nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid or oxalic acid solution.
  • the concentration of the acid solution is 0.3-12 mol/L.
  • the catalyst precursor A and the acid solution are used in a mass ratio of 1:(10-80).
  • the acid solution treatment is carried out at a temperature of 60-130°C for 4-48 hours.
  • step (3) after the acid solution treatment, the product is washed and dried.
  • the washing is water washing.
  • the drying is performed at 60-120° C. for 1-24 hours.
  • the calcination in step (3) is carried out at 450-650° C. in an oxygen-containing atmosphere for 4-12 hours.
  • the oxygen-containing atmosphere may be air or oxygen, preferably air.
  • step (4) comprises: contacting the catalyst precursor B of step (3) with an organic amine solution in the presence of a fluoride and reacting.
  • the fluoride is selected from at least one of sodium fluoride, potassium fluoride and ammonium fluoride;
  • the organic amine is selected from at least one of piperidine and hexamethyleneimine.
  • the concentration of the organic amine solution is 0.3-15 mol/L.
  • the catalyst precursor B, fluoride and organic amine solution are used in a mass ratio of 1: (0.05-0.4): (2-20).
  • the organic amine solution treatment is carried out at a temperature of 130-190°C for 4-48 hours.
  • step (4) after the treatment with the organic amine solution, the product is washed and dried.
  • the washing is water washing. The drying is performed at 60-120° C. for 1-24 hours.
  • step (4) does not include calcination.
  • the present invention also provides a Ti-MWW molecular sieve catalyst prepared by the above method.
  • the Ti-MWW molecular sieve catalyst has all the characteristics of the Ti-MWW molecular sieve catalyst of the present invention as described above, which will not be described in detail here.
  • the present invention provides a Ti-MWW molecular sieve catalyst Application of catalytic agents in olefin epoxidation reactions.
  • the use comprises the steps of: mixing olefin, aqueous hydrogen peroxide solution, solvent and alkaline nitrogen-containing substance to form a feed solution, and contacting the feed solution with the catalyst to react.
  • the reaction is carried out in a fixed bed reactor.
  • the olefin is a liquefied olefin.
  • the olefin includes at least one selected from propylene, allyl chloride, butene, pentene, cyclopentene, hexene and cyclohexene.
  • the concentration of the aqueous hydrogen peroxide solution is 10-70% by mass.
  • the solvent is at least one selected from methanol, acetonitrile, propionitrile, acetone and tert-butyl alcohol.
  • the alkaline nitrogen-containing substance is at least one selected from piperidine and hexamethyleneimine.
  • the molar ratio of olefin to hydrogen peroxide is 1:0.3-1; the amount of olefin in the raw material liquid is 1-50 mass %; the amount of solvent in the raw material liquid is 30-90 mass %; the amount of alkaline nitrogen-containing substance in the raw material liquid is 1-50 ppm.
  • the reaction is carried out under the following conditions: the flow rate of the catalyst per unit mass of the raw material liquid is 3-30 mL ⁇ g cat. -1 ⁇ h -1 ; the temperature is 30-100° C., and the pressure is 0.1-4 MPa.
  • the type, state, structure, and morphology of the titanium species of the molecular sieve catalyst are determined by ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and scanning electron microscopy.
  • the silicon-titanium molar ratio, boron-silicon molar ratio, and aluminum-silicon molar ratio of the molecular sieve catalyst are determined by inductively coupled atomic emission spectroscopy.
  • the micropore volume, mesopore volume, and macropore volume of the molecular sieve catalyst are determined by nitrogen adsorption and desorption and mercury intrusion testing, respectively.
  • the mechanical strength of the molecular sieve catalyst is determined by a strength tester.
  • the UV Raman spectrum test method is: using a domestic UVRaman-100 UV Raman spectrometer for testing, with an excitation wavelength of 244nm, a laser power of 5.0mW on the sample, and a spectral resolution of 4cm -1 to obtain a UV Raman spectrum of the molecular sieve catalyst.
  • the intensity of a certain peak is obtained by subtracting the baseline background from the peak of the peak.
  • the X-ray photoelectron spectroscopy test method is: using AXIS Ultra DLD
  • the X-ray photoelectron spectrometer was used for testing, with AlK ⁇ line as the ray source (1486.6eV), the sample chamber pressure was pumped to 10 -9 Torr, and the C 1s 284.8eV spectrum peak was used for calibration. OriginPro 9 was used for peak fitting.
  • the X-ray diffraction test method is: the sample is analyzed using a Rigaku UlTima IV X-ray powder diffractometer from Japan, with CuK ⁇ rays as the radiation source. Nickel filter, 2 ⁇ scanning range 2-50°, operating voltage 40 kV, current 40 mA, scanning rate 10°/min.
  • the scanning electron microscope test method is: using a Hitachi S-4800 electron microscope for testing, with an acceleration voltage of 3 kV.
  • the inductively coupled atomic emission spectrometry testing method is: using a Varian-2000 analyzer to analyze the silicon-titanium molar ratio, boron-silicon molar ratio, and aluminum-silicon molar ratio in the sample, and dissolving the sample in a hydrofluoric acid solution before the test.
  • the nitrogen adsorption-desorption test method is: using the American Micromeritics ASAP2460 instrument to measure the nitrogen adsorption-desorption isotherm of the sample to obtain the micropore volume, wherein the measurement temperature is 77K, and before the test, the sample is vacuum pretreated at 573K for 6 hours.
  • the mercury intrusion testing method is: using a high-performance fully automatic mercury intrusion instrument AutoPore IV 9505 for testing.
  • the mechanical strength test method is: using a DL-2 particle strength tester to test. Specifically, the size of the catalyst in the force direction is first tested, and then the external force required to extrude the catalyst into powder is measured. The mechanical strength of the catalyst is obtained by dividing the external force by the size.
  • the catalytic performance of the molecular sieve catalyst is characterized by the residual hydrogen peroxide rate, the hydrogen peroxide conversion rate, the selectivity of the main product (such as epoxide) and the by-product (such as glycol and alcohol ether), the main by-product ratio and the catalyst stability time.
  • a raw liquid sample is obtained from the inlet of the reaction tube, and a reaction liquid sample is obtained from the outlet of the reaction tube.
  • the reaction liquid sample can be obtained at any stage of the reaction, for example, when the reaction liquid is just discharged from the outlet of the reaction tube, during the reaction, or at the end of the reaction.
  • the concentration of hydrogen peroxide in the raw liquid sample and the reaction liquid sample is determined by cerium sulfate titration, and the residual hydrogen peroxide rate and the hydrogen peroxide conversion rate are calculated by the following formula.
  • Hydrogen peroxide conversion rate % 1-hydrogen peroxide residual rate %.
  • the composition of the raw liquid sample and the reaction liquid sample is analyzed by gas chromatography.
  • the measurement results are used to determine the amount of olefins converted by the reaction, the amount of epoxy products generated by the reaction, and the selectivity of the main product (i.e., epoxide) and the main and by-product ratio of the main product (i.e., epoxide) to the by-product (i.e., glycol and alcohol ether) are calculated.
  • the molar amount of olefin converted in the reaction the molar amount of olefin in the raw liquid sample - the molar amount of olefin in the reaction liquid sample
  • Epoxide selectivity % molar amount of epoxide product in the reaction solution sample / molar amount of olefin converted in the reaction * 100%
  • Main product to byproduct ratio molar amount of epoxy product in the reaction solution sample / (molar amount of olefin converted in the reaction - molar amount of epoxy product in the reaction solution sample) * 100%
  • the timing is started from the start of the reaction and ends when the residual rate of hydrogen peroxide in the reaction solution sample reaches 2%, and the time between the two is the catalyst stabilization time.
  • the Ti-MWW molecular sieve powder is sample RT-03B purchased from Zhejiang Taide New Materials Co., Ltd., and its titanium species only have framework tetracoordinated titanium species.
  • the Ti-MWW molecular sieve raw powder is a sample synthesized according to the reference (Journal of Physical Chemistry B, 2001, 105, 2897), and it only contains non-framework hexacoordinated titanium species.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10 and reacted at 170° C. for 24 hours. After washing with water and drying at 100°C for 8 hours, a Ti-MWW molecular sieve catalyst was obtained, which was recorded as S1.
  • Catalyst S1 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S1 is shown in Figure 1, and peaks at 458.9, 460.3, 464.8, and 465.9 eV are observed, wherein the peaks at 460.3 and 465.9 eV are attributed to the framework tetracoordinated titanium species, and the peaks at 458.9 and 464.8 eV are attributed to the modified non-framework hexacoordinated titanium species.
  • the UV Raman spectrum of the catalyst S1 is shown in Figure 2, and peaks at 343, 484 , 699, and 1097 cm-1 are observed.
  • the peak intensity at 699 cm -1 is 5.3 times that at 343 cm -1
  • the peak intensity at 1097 cm -1 is 5.1 times that at 343 cm -1 .
  • the peak at 343 cm -1 belongs to the MWW structure
  • the peaks at 484 and 1097 cm -1 belong to the framework tetracoordinated titanium species
  • the peak at 699 cm -1 belongs to the modified non-framework hexacoordinated titanium species.
  • the X-ray diffraction pattern of the catalyst S1 is shown in Figure 3. Among them, strong diffraction peaks appear at 2 ⁇ of 3.3°, 6.6°, 7.2°, 7.9°, 9.7°, and 26.1°, and the intensity value of the diffraction peak at 2 ⁇ of 7.2° reaches 5300, indicating that S1 has an MWW structure and high crystallinity.
  • the scanning electron microscope image of the catalyst S1 is shown in Figure 4.
  • the catalyst S1 exhibits a lamellar morphology, and no nanoparticles are observed, which indicates that S1 is only a MWW structure.
  • the catalyst S1 has a silicon-titanium molar ratio of 35 and a boron-silicon molar ratio of 0.015.
  • the micropore volume of the catalyst S1 is 0.09 cm 3 /g, the proportion of the micropore volume to the total pore volume is 3.6%, and the mechanical strength is 66 N/cm.
  • (1) 90 g of Ti-MWW molecular sieve powder with a silicon-titanium molar ratio of 5 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silicon dioxide mass fraction of 40% and 15 g of boric acid), 3 g of starch and 0.9 g of potassium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • the amorphous binder includes 75 g of a silica sol with a silicon dioxide mass fraction of 40% and 15 g of boric acid
  • 3 g of starch and 0.9 g of potassium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and
  • step (3) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a solid-liquid mass ratio of 1:50, and reacted at 80° C. for 24 hours. The resulting product was washed, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S2.
  • Catalyst S2 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S2 showed peaks at 459.1, 460.1, 465.0, and 465.7 eV.
  • the UV Raman spectrum of the catalyst S2 showed peaks at 341, 487, 702 and 1094 cm -1.
  • the peak intensity at 702 cm -1 was 10 times that at 341 cm -1
  • the peak intensity at 1094 cm -1 was 10 times that at 341 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S2 are similar to FIG3 and FIG4 , respectively.
  • the catalyst S2 has a silicon-titanium molar ratio of 10 and a boron-silicon molar ratio of 0.005.
  • the micropore volume of the catalyst S2 is 0.05 cm 3 /g, the proportion of the micropore volume to the total pore volume is 1.7%, and the mechanical strength is 40 N/cm.
  • the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid
  • 9 g of cellulose and 36 g of ammonium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10 and reacted at 170° C. for 24 hours. After washing with water and drying at 100°C for 8 hours, a Ti-MWW molecular sieve catalyst was obtained, which was recorded as S3.
  • Catalyst S3 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S3 showed peaks at 458.7, 460.4, 464.6 and 466.0 eV.
  • the UV Raman spectrum of the catalyst S3 showed peaks at 345, 482, 696 and 1099 cm -1 , the peak intensity at 696 cm -1 was 0.5 times that at 345 cm -1 , and the peak intensity at 1099 cm -1 was 0.5 times that at 345 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S3 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S3 has a silicon-titanium molar ratio of 200 and a boron-silicon molar ratio of 0.03.
  • the micropore volume of the catalyst S3 is 0.07 cm 3 /g, the proportion of the micropore volume to the total pore volume is 2.3%, and the mechanical strength is 80 N/cm.
  • the amorphous binder includes 8 g of silica sol with a silica mass fraction of 25% and 1 g of sodium tetraborate
  • 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 120 g of water is added, and
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S4.
  • Catalyst S4 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S4 showed 458.7, 460.5, 464.6, 466.1eV spectral peak.
  • the UV Raman spectrum of the catalyst S4 showed peaks at 347, 480, 695 and 1101 cm -1 , the peak intensity at 695 cm -1 was 8.2 times that at 347 cm -1 , and the peak intensity at 1101 cm -1 was 7.8 times that at 347 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S4 are similar to FIG3 and FIG4 , respectively.
  • the catalyst S4 has a silicon-titanium molar ratio of 25 and a boron-silicon molar ratio of 0.003.
  • the micropore volume of the catalyst S4 is 0.06 cm 3 /g, the proportion of the micropore volume to the total pore volume is 2%, and the mechanical strength is 30 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 30 g of white carbon black, 30 g of boric acid, and 30 g of aluminum hydroxide), 3 g of sesbania powder, and 9 g of sodium fluoride were mixed under mechanical stirring, and then 120 g of water was added, and the mixture was stirred and kneaded for 4 hours to obtain a solid mixture, which was mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 650° C. for 4 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S5.
  • Catalyst S5 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S5 showed peaks at 459.0, 460.2, 464.9 and 465.8 eV.
  • the UV Raman spectrum of the catalyst S5 showed peaks at 341, 486, 701 and 1095 cm -1 .
  • the peak intensity at 701 cm -1 was 2.9 times that at 341 cm -1
  • the peak intensity at 1095 cm -1 was 2.6 times that at 341 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S5 are similar to those in FIG3 and FIG4 , respectively. like.
  • the catalyst S5 has a silicon-titanium molar ratio of 60, a boron-silicon molar ratio of 0.1, and an aluminum-silicon molar ratio of 0.1.
  • the micropore volume of the catalyst S5 is 0.1 cm 3 /g, the proportion of the micropore volume to the total pore volume is 4%, and the mechanical strength is 77 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of aluminum hydroxide), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S6.
  • Catalyst S6 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S6 showed peaks at 459.1, 460.1, 465.0, and 465.7 eV.
  • the UV Raman spectrum of the catalyst S6 showed peaks at 339, 488, 703 and 1093 cm -1 .
  • the peak intensity at 703 cm -1 was 4.9 times that at 339 cm -1
  • the peak intensity at 1093 cm -1 was 5.2 times that at 339 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S6 are similar to those in FIG3 and FIG4 , respectively.
  • the silicon-titanium molar ratio of the catalyst S6 is 37, and the aluminum-silicon molar ratio is 0.05.
  • micropore volume of the catalyst S6 is 0.12 cm 3 /g, and the micropore volume accounts for 1.3% of the total pore volume.
  • the ratio is 6% and the mechanical strength is 90N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is spheronized and granulated, dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a spherical molded product.
  • step (2) 60 g of the spherical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a spherical catalyst precursor B.
  • step (3) 40 g of the spherical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S7.
  • Catalyst S7 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S7 showed peaks at 458.9, 460.3, 464.8 and 465.9 eV.
  • the UV Raman spectrum of the catalyst S7 showed peaks at 343, 484, 699 and 1097 cm -1 .
  • the peak intensity at 699 cm -1 was 5.3 times that at 343 cm -1
  • the peak intensity at 1097 cm -1 was 5.2 times that at 343 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S7 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S7 has a silicon-titanium molar ratio of 34 and a boron-silicon molar ratio of 0.014.
  • the micropore volume of the catalyst S7 is 0.09 cm 3 /g, the proportion of the micropore volume to the total pore volume is 3.6%, and the mechanical strength is 80 N/cm.
  • 90 g of an amorphous binder (the amorphous binder comprises 75 g of silica sol with a silicon dioxide mass fraction of 40%, 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring.
  • the mixture was mixed and then 80 g of water was added, stirred and kneaded for 4 hours to obtain a solid mixture, which was mechanically extruded and dried at 100° C. for 8 hours and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S8.
  • Catalyst S8 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S8 showed peaks at 459.0, 460.2, 464.9, and 465.8 eV.
  • the UV Raman spectrum of the catalyst S8 showed peaks at 341, 486, 701 and 1095 cm -1 .
  • the peak intensity at 701 cm -1 was 4.8 times that at 341 cm -1
  • the peak intensity at 1095 cm -1 was 5.9 times that at 341 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S8 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S8 has a silicon-titanium molar ratio of 32 and a boron-silicon molar ratio of 0.017.
  • micropore volume of the catalyst S8 is 0.07 cm 3 /g, the proportion of the micropore volume to the total pore volume is 2.3%, and the mechanical strength is 56 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S9.
  • Catalyst S9 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S9 showed peaks at 458.9, 460.4, 464.8 and 466.0 eV.
  • the UV Raman spectrum of the catalyst S9 showed peaks at 345, 483, 698 and 1099 cm -1 , the peak intensity at 698 cm -1 was 5.7 times that at 345 cm -1 , and the peak intensity at 1099 cm -1 was 4.9 times that at 345 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S9 are similar to FIG3 and FIG4 , respectively.
  • the catalyst S9 has a silicon-titanium molar ratio of 34 and a boron-silicon molar ratio of 0.016.
  • micropore volume of the catalyst S9 is 0.08 cm 3 /g, the proportion of the micropore volume to the total pore volume is 3.2%, and the mechanical strength is 64 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (3) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, and reacted at 80° C. for 24 hours. After drying at 100°C for 8 hours and calcining at 550°C for 6 hours, a cylindrical catalyst precursor B was obtained.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, reacted at 170° C. for 24 hours, washed with water, and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, recorded as S10.
  • Catalyst S10 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S10 showed peaks at 459.0, 460.2, 464.9, and 465.8 eV.
  • the UV Raman spectrum of the catalyst S10 showed peaks at 341, 486, 701 and 1095 cm - 1 , the peak intensity at 701 cm -1 was 4.5 times that at 341 cm -1 , and the peak intensity at 1095 cm -1 was 4.9 times that at 341 cm -1 .
  • the X-ray diffraction pattern and the scanning electron microscope image of the catalyst S10 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S10 has a silicon-titanium molar ratio of 42 and a boron-silicon molar ratio of 0.02.
  • the micropore volume of the catalyst S10 is 0.06 cm 3 /g, the proportion of the micropore volume to the total pore volume is 2%, and the mechanical strength is 45 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, reacted at 170° C. for 24 hours, washed with water, and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, recorded as S11.
  • Catalyst S11 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S11 showed peaks at 458.9, 460.4, 464.8 and 466.0 eV.
  • the UV Raman spectrum of the catalyst S11 showed peaks at 345, 482, 698 and 1099 cm -1 , the peak intensity at 698 cm -1 was 6 times that at 345 cm -1 , and the peak intensity at 1099 cm -1 was 5 times that at 345 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S11 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S11 has a silicon-titanium molar ratio of 30 and a boron-silicon molar ratio of 0.01.
  • micropore volume of the catalyst S11 is 0.07 cm 3 /g, the proportion of the micropore volume to the total pore volume is 2.3%, and the mechanical strength is 69 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 12 mol/L hydrochloric acid solution in a mass ratio of 1:10, reacted at 130° C. for 4 hours, washed with water, dried at 100° C. for 8 hours and calcined at 450° C. for 12 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S12.
  • Catalyst S12 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S12 showed peaks at 458.9, 460.5, 464.8 and 466.1 eV.
  • the UV Raman spectrum of the catalyst S12 showed peaks at 344, 481, 698, and 1100 cm - 1.
  • the peak intensity at 698 cm -1 was 3.3 times that at 344 cm -1
  • the peak intensity at 1100 cm -1 was 2.4 times that at 344 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S12 are similar to those in FIG3 and FIG4 , respectively.
  • the silicon-titanium molar ratio of the catalyst S12 is 57, and the boron-silicon molar ratio is 0.004.
  • the micropore volume of the catalyst S12 is 0.1 cm 3 /g, the proportion of the micropore volume to the total pore volume is 4%, and the mechanical strength is 48 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 0.3 mol/L oxalic acid solution at a mass ratio of 1:80, reacted at 60°C for 48 hours, washed with water, dried at 100°C for 8 hours and calcined at 650°C for 4 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S13.
  • Catalyst S13 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S13 showed peaks at 459.1, 460.1, 465.0 and 465.7 eV.
  • the UV Raman spectrum of the catalyst S13 showed peaks at 341, 488, 702, and 1093 cm - 1.
  • the peak intensity at 702 cm -1 was 5.9 times that at 341 cm -1
  • the peak intensity at 1093 cm -1 was 5.7 times that at 341 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S13 are similar to those in FIG3 and FIG4 , respectively. like.
  • the catalyst S13 has a silicon-titanium molar ratio of 27 and a boron-silicon molar ratio of 0.08.
  • the catalyst S13 has a micropore volume of 0.05 cm 3 /g, a proportion of the micropore volume to the total pore volume of 1.7%, and a mechanical strength of 60 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L hexamethyleneimine solution in a mass ratio of 1:0.2:20, and reacted at 170°C for 48 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S14.
  • Catalyst S14 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S14 showed peaks at 458.9, 460.3, 464.8 and 465.9 eV.
  • the UV Raman spectrum of the catalyst S14 showed peaks at 342, 484 , 700 and 1097 cm -1.
  • the intensity of the peak at 700 cm -1 was 5 times that of the peak at 342 cm -1
  • the intensity of the peak at 1097 cm -1 was 4.8 times that of the peak at 342 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S14 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S14 has a silicon-titanium molar ratio of 39 and a boron-silicon molar ratio of 0.018.
  • micropore volume of the catalyst S14 is 0.08 cm 3 /g, the proportion of the micropore volume to the total pore volume is 3.2%, and the mechanical strength is 62 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with potassium fluoride and 15 mol/L piperidine solution in a mass ratio of 1:0.4:2, and reacted at 190°C for 4 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S15.
  • Catalyst S15 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S15 showed peaks at 459.0, 460.2, 464.9 and 465.8 eV.
  • the UV Raman spectrum of the catalyst S15 showed peaks at 342, 485, 701 and 1095 cm - 1 , the peak intensity at 701 cm -1 was 6.8 times that at 342 cm -1 , and the peak intensity at 1095 cm -1 was 3.2 times that at 342 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S15 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S15 has a silicon-titanium molar ratio of 37 and a boron-silicon molar ratio of 0.025.
  • the micropore volume of the catalyst S15 is 0.15 cm 3 /g, the proportion of the micropore volume to the total pore volume is 7.5%, and the mechanical strength is 64 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of silica sol with a silicon dioxide mass fraction of 40%, 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride were mixed under mechanical stirring, and then 80 g of water was added, stirred and kneaded for 4 hours to obtain a solid mixture, and mechanically After extrusion molding, the product was dried at 100°C for 8 hours and then calcined at 550°C for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with sodium fluoride and 0.3 mol/L piperidine solution in a mass ratio of 1:0.05:20, and reacted at 130° C. for 48 hours. The mixture was washed with water and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as S16.
  • Catalyst S16 was tested as described above.
  • the X-ray photoelectron spectrum of the catalyst S16 showed peaks at 458.9, 460.3, 464.8 and 465.9 eV.
  • the UV Raman spectrum of the catalyst S16 showed peaks at 344, 482, 698 and 1098 cm - 1 , the peak intensity at 698 cm -1 was 3.3 times that at 344 cm -1 , and the peak intensity at 1098 cm -1 was 6.9 times that at 344 cm -1 .
  • the X-ray diffraction pattern and scanning electron microscope image of the catalyst S16 are similar to those in FIG3 and FIG4 , respectively.
  • the catalyst S16 has a silicon-titanium molar ratio of 36 and a boron-silicon molar ratio of 0.01.
  • the micropore volume of the catalyst S16 is 0.03 cm 3 /g, the proportion of the micropore volume to the total pore volume is 1%, and the mechanical strength is 57 N/cm.
  • Liquid phase continuous epoxidation of propylene was carried out in the presence of the Ti-MWW molecular sieve catalysts prepared in Examples 1, 2, 3, 6, 11, 12, 15 and 16 to evaluate their catalytic performance.
  • An aqueous solution with a mass fraction of hydrogen peroxide of 30% was selected to prepare an aqueous solution of hydrogen peroxide containing a piperidine concentration of 15 ppm, and it was mixed with the solvent
  • the two raw material liquids were fed by plunger pumps respectively, and the two raw material liquids were premixed before entering the reaction tube.
  • the mixed raw material liquid samples entering the reaction tube were collected and tested as described above.
  • the mass fraction of propylene was 18.7%
  • the mass fraction of acetonitrile was 61.0%
  • the molar ratio of propylene to hydrogen peroxide was 1:0.4
  • the flow rate of the total raw material unit mass catalyst was 6mL ⁇ g cat. -1 ⁇ h -1 .
  • the reaction liquid samples flowing out of the reaction tube were collected and tested as described above. The results are shown in Table 1.
  • the two raw material liquids were fed separately by plunger pumps, and the two raw material liquids were premixed before entering the reaction tube.
  • the mixed raw material liquid samples entering the reaction tube were collected and tested as described above.
  • the mass fraction of allyl chloride was 27.7%
  • the mass fraction of acetonitrile was 54.2%
  • the molar ratio of allyl chloride to hydrogen peroxide was 1:0.4
  • the flow rate of the total raw material unit mass catalyst was 4mL ⁇ g cat. -1 ⁇ h -1 .
  • the reaction liquid samples flowing out of the reaction tube were collected and tested as described above. The results are shown in Table 2 below:
  • 90 g of an amorphous binder (the amorphous binder comprises 75 g of silica sol with a silicon dioxide mass fraction of 40%, 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring.
  • the mixture was mixed and then 80 g of water was added, stirred and kneaded for 4 hours to obtain a solid mixture, which was mechanically extruded and dried at 100° C. for 8 hours and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (1) 60 g of the cylindrical molded product of step (1) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80° C. for 24 hours, washed with water, dried at 100° C. for 8 hours and calcined at 550° C. for 6 hours to obtain a cylindrical catalyst precursor.
  • step (3) 40 g of the cylindrical catalyst precursor of step (2) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, reacted at 170° C. for 24 hours, washed with water, and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, recorded as D1.
  • Catalyst D1 was tested as described above.
  • the UV Raman spectrum of D1 is shown in Figure 6. Only the 491 and 1080 cm -1 peaks are observed, and no peaks belonging to the MWW structure are observed. The 491 and 1080 cm-1 peaks belong to the tetracoordinated titanium species. Such a result is mainly attributed to the presence of amorphous binders in the catalyst, which are not converted into components of the molecular sieve. The presence of amorphous binders obscures the molecular sieve, so that the MWW structure of the molecular sieve cannot be detected by UV Raman.
  • the X-ray diffraction pattern of D1 is shown in Figure 7.
  • Diffraction peaks appear at 2 ⁇ of 3.3°, 6.6°, 7.2°, 7.9°, 9.7°, and 26.1°.
  • the intensity of the diffraction peak at 2 ⁇ of 7.2° is about 2500, which is significantly weaker than that of S1, indicating that the main body of D1 is still MWW structure, but the crystallinity is low.
  • there are strong broad diffraction peaks in the 17.5-30° region which further indicates that D1 still has amorphous species.
  • the molar ratio of silicon to titanium in D1 is 30, and the molar ratio of boron to silicon is 0.06.
  • micropore volume of D1 is 0.04 cm 3 /g, the proportion of micropore volume to total pore volume is 1.4%, and the mechanical strength is 29 N/cm.
  • 90 g of an amorphous binder (the amorphous binder comprises 75 g of silica sol with a silicon dioxide mass fraction of 40%, 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring.
  • the mixture was mixed and then 80 g of water was added, stirred and kneaded for 4 hours to obtain a solid mixture, which was mechanically extruded and dried at 100° C. for 8 hours and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (3) 40 g of the cylindrical catalyst precursor of step (2) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, reacted at 170° C. for 24 hours, washed with water, and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, recorded as D2.
  • Catalyst D2 was tested as described above.
  • the silicon-titanium molar ratio of D2 is 31, and the boron-silicon molar ratio is 0.05.
  • micropore volume of D2 is 0.08 cm 3 /g, the proportion of micropore volume to total pore volume is 3.2%, and the mechanical strength is 68 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (3) 60 g of the cylindrical catalyst precursor of step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80° C. for 24 hours, washed with water, dried at 100° C. for 8 hours and calcined at 550° C. for 6 hours to obtain a Ti-MWW molecular sieve catalyst. Make D3.
  • Catalyst D3 was tested as described above.
  • the UV Raman spectrum of D3 is shown in Figure 10. Peaks at 343, 490, and 1092 cm -1 are observed, and the intensity of the 1092 cm -1 peak is 10.2 times that of the 343 cm -1 peak. This indicates the presence of a large number of framework tetracoordinated titanium species.
  • the silicon-titanium molar ratio of D3 is 36, and the boron-silicon molar ratio is 0.017.
  • micropore volume of D3 is 0.16 cm 3 /g, the proportion of micropore volume to total pore volume is 7.8%, and the mechanical strength is 58 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid) and 3 g of sesbania powder are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with ammonium fluoride and 3 mol/L piperidine solution in a mass ratio of 1:0.1:10, and reacted at 170°C for 24 hours. The mixture was washed with water and dried at 100°C for 8 hours to obtain a Ti-MWW molecular sieve catalyst, which was recorded as D4.
  • Catalyst D4 was tested as described above.
  • the X-ray photoelectron spectrum of D4 showed peaks at 459.7 and 465.4 eV, which were attributed to the tetracoordinated titanium species.
  • the UV Raman spectrum of D4 is shown in Figure 11. Peaks at 340, 488, and 1087 cm -1 are observed. The intensity of the 1087 cm -1 peak is 10.9 times that of the 340 cm -1 peak. This indicates that there is a large Amount of tetracoordinated titanium species.
  • the silicon-titanium molar ratio of D4 is 33, and the boron-silicon molar ratio is 0.012.
  • micropore volume of D4 is 0.05 cm 3 /g, the proportion of micropore volume to total pore volume is 1.7%, and the mechanical strength is 36 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product.
  • step (2) 60 g of the cylindrical catalyst precursor A described in step (2) was mixed with 2 mol/L nitric acid solution at a mass ratio of 1:50, reacted at 80°C for 24 hours, washed with water, dried at 100°C for 8 hours and calcined at 550°C for 6 hours to obtain a cylindrical catalyst precursor B.
  • step (3) 40 g of the cylindrical catalyst precursor B described in step (3) was mixed with 3 mol/L piperidine solution in a mass ratio of 1:10, reacted at 170° C. for 24 hours, washed with water, and dried at 100° C. for 8 hours to obtain a Ti-MWW molecular sieve catalyst, recorded as D5.
  • Catalyst D5 was tested as described above.
  • the X-ray photoelectron spectrum of D5 observed peaks at 460.6 and 466.2 eV, which were attributed to the tetracoordinated titanium species.
  • the UV Raman spectrum of D5 is shown in Figure 12. Peaks at 342, 490, and 1102 cm -1 are observed, and the intensity of the 1102 cm -1 peak is 10.3 times that of the 342 cm -1 peak. This indicates the presence of a large number of framework tetracoordinated titanium species.
  • the silicon-titanium molar ratio of D5 is 36, and the boron-silicon molar ratio is 0.017.
  • micropore volume of D5 is 0.04 cm 3 /g, the proportion of micropore volume to total pore volume is 1.3%, and the mechanical strength is 74 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture, which is mechanically extruded and dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product, which is recorded as D6.
  • Catalyst D6 was tested as described above.
  • the X-ray photoelectron spectrum of D6 is shown in Figure 13, where peaks at 460.2 and 465.8 eV are observed, which are attributed to the tetracoordinated titanium species.
  • the UV Raman spectrum of D6 is shown in Figure 14, where peaks at 343, 492, and 1094 cm -1 are observed, and the intensity of the 1094 cm -1 peak is 9.7 times that of the 343 cm -1 peak, indicating the presence of a large number of framework tetracoordinated titanium species.
  • the X-ray photoelectron spectrum and UV Raman spectrum of the Ti-MWW molecular sieve powder are similar to Figure 13 and Figure 14, respectively, indicating that mechanical extrusion molding does not affect the state of the titanium species of the catalyst D6.
  • the silicon-titanium molar ratio of D6 is 38, and the boron-silicon molar ratio is 0.11.
  • micropore volume of D6 is 0.13 cm 3 /g, the proportion of micropore volume to total pore volume is 5.4%, and the mechanical strength is 28 N/cm.
  • 90 g of an amorphous binder (the amorphous binder includes 75 g of a silica sol with a silica mass fraction of 40% and 15 g of boric acid), 3 g of sesbania powder and 9 g of sodium fluoride are mixed under mechanical stirring, and then 80 g of water is added, and the mixture is stirred and kneaded for 4 hours to obtain a solid mixture.
  • the mixture is dried at 100° C. for 8 hours, and then calcined at 550° C. for 6 hours to obtain a cylindrical molded product, which is recorded as D7.
  • Catalyst D7 was tested as described above.
  • the silicon-titanium molar ratio of D7 is 37, and the boron-silicon molar ratio is 0.12.
  • micropore volume of D7 is 0.12 cm 3 /g, the proportion of micropore volume to total pore volume is 5.3%, and the mechanical strength is 26 N/cm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

一种Ti-MWW分子筛催化剂及其制备方法和应用。所述Ti-MWW分子筛催化剂的X射线光电子能谱图在458.9±0.2eV、464.8±0.2eV处出现谱峰，优选在458.9±0.2eV、460.3±0.2eV、464.8±0.2eV、465.9±0.2eV处出现谱峰。所述Ti-MWW分子筛催化剂用于烯烃环氧化反应中，具有烯烃转化率高、环氧化物选择性高、催化稳定性好的特点。

Description

一种Ti-MWW分子筛催化剂及其制备方法和应用 技术领域
本发明涉及钛硅分子筛催化剂领域，具体涉及一种Ti-MWW分子筛催化剂及其制备方法和应用。
背景技术
环氧化物是重要的有机化工原料，主要包括环氧乙烷、环氧丙烷、1,2-环氧戊烷及1,2-环氧己烷等。目前，环氧化物基本都由烯烃选择氧化生产得到。EniChem公司开发了一种生产环氧丙烷的方法，即过氧化氢氧化法(HPPO)(参见例如US4410501A)。它采用MFI结构的TS-1钛硅分子筛作为催化剂，通过丙烯与过氧化氢在甲醇溶剂中反应生成环氧丙烷。该过程具有绿色环保、原料利用率高等特点，目前已经实现工业化。然而，由于TS-1分子筛尺寸约0.5nm的十圆环孔道不利于大分子扩散，其在用于分子尺寸稍大的环己烯环氧化上就面临着较大的挑战。为此，吴鹏教授等人开发了新一代钛硅分子筛Ti-MWW(Journal of Catalysis,2001,202,245)。与TS-1分子筛相比，Ti-MWW分子筛不仅烯烃转化率更高，环氧化物的选择性也更好。
目前，环氧丙烷的工业生产主要在固定床反应器中进行。由于水热法制得的钛硅分子筛为微米或纳米尺寸的粉体，没有机械强度，若将其直接装填在固定床反应器中，将在反应过程中被反应液夹带进入装置管路，造成管路堵塞。另外，反应结束后从反应液中分离回收钛硅分子筛粉体也非常困难。为了保证固定床反应高效连续进行，需要将钛硅分子筛粉体制成具有良好机械强度的催化剂。
CN1346705A提出采用具有一定机械强度的小球为载体，通过滚球成型的方式使得钛硅分子筛在其表面富集，以提高所得催化剂的机械强度。CN112354557A公开了一种整体式钛沸石催化剂制备方法及其应用，通过将无定形硅基粘结剂和高分子造孔剂混入MWW钛沸石粉体，加水搅拌捏合，机械成型焙烧之后，再浸入复合环状含氮有机物的水溶液中密封加热，经过过滤、干燥、焙烧之后，得到整体式丙烯连续环氧化催化剂。
总的来说，现有技术中的Ti-MWW分子筛催化剂，不管是否含有 粘结剂，都存在机械强度低、催化性能差的问题。理论上而言，可以对现有技术中的Ti-MWW分子筛催化剂的组成和结构进行改造，从而进一步提高其机械强度和催化性能。因此，本领域中一直需要开发机械强度高、催化性能好的Ti-MWW分子筛催化剂。
发明内容
为了解决现有技术中存在的问题，即Ti-MWW分子筛催化剂机械强度低、催化性能差，本发明提供一种Ti-MWW分子筛催化剂，其制备方法和应用。本发明的Ti-MWW分子筛催化剂包含状态好的钛物种，优选具有全结晶结构，从而具有机械强度高和催化性能优异的特点。
为实现上述目的，本发明第一方面提供一种Ti-MWW分子筛催化剂，其中，催化剂的X射线光电子能谱图在458.9±0.2eV、464.8±0.2eV处出现谱峰，优选在458.9±0.1eV、464.8±0.1eV处出现谱峰；优选，催化剂的X射线光电子能谱图在458.9±0.2eV、460.3±0.2eV、464.8±0.2eV、465.9±0.2eV处出现峰，优选在458.9±0.1eV、460.3±0.1eV、464.8±0.1eV、465.9±0.1eV处出现峰。
本发明第二方面提供一种制备Ti-MWW分子筛催化剂的方法，包括如下步骤：
(1)将Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物成型，焙烧得到成型物；
(2)将步骤(1)成型物在含有机胺溶液存在下晶化，得到催化剂前驱体A；
(3)将步骤(2)催化剂前驱体A进行酸溶液处理，焙烧得到催化剂前驱体B；
(4)将步骤(3)催化剂前驱体B进行有机胺溶液处理，制得所述催化剂。
与此同时，本发明还提供了由上述方法制备的Ti-MWW分子筛催化剂。
此外，本发明提供了一种上述Ti-MWW分子筛催化剂在烯烃环氧化反应中的应用。
例如，本发明可以包括以下方案。
1、一种全结晶Ti-MWW分子筛催化剂，其紫外拉曼谱图在343±4cm-1、484±4cm-1、699±4cm-1和1097±4cm-1处出现谱峰，699±4cm-1 谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍，1097±4cm-1谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍。
2、根据方案1所述分子筛催化剂，其特征在于，所述分子筛催化剂中硅钛摩尔比为10-200，优选为25-100；所述分子筛催化剂还包括硼元素、铝元素中至少一种元素，优选包括硼元素；所述分子筛催化剂中，硼硅摩尔比为0-0.1，优选为0-0.03，更优选为0.005-0.03；所述分子筛催化剂中，铝硅摩尔比为0-0.1，优选为0-0.05。
3、根据方案1所述分子筛催化剂，其特征在于，所述分子筛催化剂的微孔体积为0.03-0.15cm3/g，优选为0.03-0.12cm3/g，更优选为0.05-0.10cm3/g；微孔体积占总孔体积的比例为1％-7.5％，优选为1-6％，更优选为1.7％-5％。
4、根据方案1所述分子筛催化剂，其特征在于，所述分子筛催化剂的机械强度为30-90N/cm，优选为40-80N/cm。
5、一种全结晶Ti-MWW分子筛催化剂的制备方法，包括如下步骤：
(1)将Ti-MWW分子筛粉体、粘结剂、造孔剂、氟化物捏合成型，焙烧得到成型物；
(2)将步骤(1)成型物在含有机胺溶液环境下晶化，得到催化剂前驱体A；
(3)将步骤(2)催化剂前驱体A进行酸溶液处理，焙烧得到催化剂前驱体B；
(4)将步骤(3)催化剂前驱体B进行有机胺溶液处理，制得所述分子筛催化剂。
6、根据方案5所述制备方法，其特征在于，步骤(1)中所述粘结剂为包括硅源以及选自硼源、铝源中的至少一种；所述粘结剂组成中，以氧化物计，摩尔比SiO2：B2O3：Al2O3＝1：x：y，其中x＝0-0.5，y＝0-0.5，x+y＝0.02-1。
7、根据方案6所述制备方法，其特征在于，所述硅源选自硅溶胶、水玻璃、白炭黑和正硅酸乙酯中的至少一种；所述硼源选自硼酸、三氧化二硼和硼酸盐中的至少一种；所述铝源选自三氧化二铝、氢氧化铝、偏铝酸钠、硝酸铝和硫酸铝中的至少一种。
8、根据方案5-7任一所述制备方法，其特征在于，步骤(1)中所 述造孔剂选自田菁粉、纤维素、壳聚糖、木质素、淀粉、聚乙二醇、三嵌段共聚物P123和F127中的至少一种；步骤(1)中所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种；步骤(1)中的原料，Ti-MWW分子筛粉体、粘结剂、造孔剂、氟化物的质量比为1：0.1-1.5：0.01-0.1：0.01-0.4。
9、根据方案5所述制备方法，其特征在于，步骤(2)中所述含有机胺溶液环境下晶化的过程包括：步骤(1)成型物置于有机胺溶液上方进行晶化，成型物与有机胺溶液不接触；所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种；所述有机胺溶液的浓度为0.3-15mol/L；所述成型物与有机胺溶液的质量比为0.1-10：1；所述晶化的条件为：晶化温度为130-190℃，晶化时间为1-9天。
10、根据方案5所述制备方法，其特征在于，步骤(3)中所述酸溶液处理的过程包括：步骤(2)催化剂前驱体A与酸溶液接触反应；所述酸溶液选自硝酸、盐酸、硫酸、甲酸、乙酸或草酸溶液中的至少一种；所述酸溶液的浓度为0.3-12mol/L；所述催化剂前驱体A与酸溶液的固液质量比为1：10-80；所述酸溶液处理的条件为：处理温度为60-130℃，处理时间为4-48小时。
11、根据方案5所述制备方法，其特征在于，步骤(4)中所述有机胺溶液处理的过程包括：步骤(3)催化剂前驱体B与氟化物、有机胺溶液接触反应；所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种；所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种；所述有机胺溶液的浓度为0.3-15mol/L；所述催化剂前驱体B、氟化物、有机胺溶液的质量比为1：0.05-0.4：2-20；所述有机胺溶液处理的条件为：处理温度为130-190℃，处理时间为4-48小时。
12、根据方案5所述制备方法，其特征在于，步骤(1)中所述焙烧条件为450-650℃含氧气氛焙烧4-12小时；步骤(3)中所述焙烧条件为450-650℃含氧气氛焙烧4-12小时。
13、方案5-12任一项制备方法制备得到的分子筛催化剂。
14、方案1-4任一项所述分子筛催化剂或方案13所述的分子筛催化剂在烯烃环氧化反应中的应用。
与现有技术相比，本发明具有如下优点：
1、本发明的Ti-MWW分子筛催化剂中存在大量状态好的钛物种， 其包括改性的非骨架六配位钛物种，或包括骨架四配位钛物种与改性的非骨架六配位钛物种。这些状态好的钛物种为所述催化剂提供更高的催化性能。而且，所述Ti-MWW分子筛催化剂优选具有全结晶结构。这意味着，催化剂不含无定形粘结剂。换言之，粘合剂不是以无定形形式存在，而是被转化为MWW结构分子筛，进而成为最终的催化剂的一部分，从而赋予所得催化剂全结晶结构。一方面，不存在无定形粘结剂意味着，避免了无定形粘合剂对催化活性中心的遮蔽和对分子筛孔道的堵塞，从而提高了催化剂的活性和稳定性；另一方面，全结晶结构意味着机械强度更高，催化剂不易粉化流失。所述催化剂用于烯烃环氧化反应中，具有烯烃转化率高、环氧化物选择性高、催化稳定性好的特点。
2、本发明的制备方法中，优选的无定形粘结剂中包括硅源和硼源，其可以高效地被转化为MWW结构分子筛，从而赋予所得催化剂全结晶结构，由此提高催化性能和机械强度。另外，所述制备方法对晶化得到的催化剂前驱体A分别进行酸溶液处理和有机胺溶液处理，有效地将Ti-MWW分子筛中的钛物种转化为状态好的钛物种，其包括改性的非骨架六配位钛物种和任选的骨架四配位钛物种。本发明的制备方法赋予所得的Ti-MWW分子筛催化剂优异的催化活性、选择性和稳定性。
3、本发明催化剂用于烯烃环氧化反应中，具有优异的催化性能，烯烃转化率高、环氧化物选择性高、催化稳定性好，展现出良好的应用前景。
附图说明
图1为【实施例1】制备得到的Ti-MWW分子筛催化剂的X射线光电子能谱图；
图2为【实施例1】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图3为【实施例1】制备得到的Ti-MWW分子筛催化剂的X射线衍射图；
图4为【实施例1】制备得到的Ti-MWW分子筛催化剂的扫描电镜图；
图5为【对比例1】制备得到的Ti-MWW分子筛催化剂的X射线 光电子能谱图；
图6为【对比例1】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图7为【对比例1】制备得到的Ti-MWW分子筛催化剂的X射线衍射图；
图8为【对比例1】制备得到的Ti-MWW分子筛催化剂的扫描电镜图；
图9为【对比例2】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图10为【对比例3】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图11为【对比例4】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图12为【对比例5】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图13为【对比例6】制备得到的Ti-MWW分子筛催化剂的X射线光电子能谱图；
图14为【对比例6】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图；
图15为【对比例7】制备得到的Ti-MWW分子筛催化剂的X射线光电子能谱图；
图16为【对比例7】制备得到的Ti-MWW分子筛催化剂的紫外拉曼谱图。
具体实施方式
在本发明中，除非另有其他明确说明，否则百分比、百分含量均以质量计。除非另有其他明确说明，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的步骤或组成部分，而并未排除其他步骤或其他组成部分。
除了在实施例外，在本文中，参数的所有数值都应理解为在所有情况下均由术语“约”修饰，无论“约”是否实际上出现在该数值之前。
在一个方案中，本发明提供一种Ti-MWW分子筛催化剂，其中， 催化剂的X射线光电子能谱图在458.9±0.2eV、464.8±0.2eV处出现谱峰，优选在458.9±0.1eV、464.8±0.1eV处出现谱峰；优选地，催化剂的X射线光电子能谱图在458.9±0.2eV、460.3±0.2eV、464.8±0.2eV、465.9±0.2eV处出现谱峰，优选在458.9±0.1eV、460.3±0.1eV、464.8±0.1eV、465.9±0.1eV处出现谱峰。在460.3±0.2eV、465.9±0.2eV处出现的谱峰归属于骨架四配位钛物种；在458.9±0.2eV、464.8±0.2eV处出现的谱峰归属于改性的非骨架六配位钛物种。
在本文中，“Ti-MWW分子筛”指的是具有三维MWW结构的硅钛分子筛。Ti-MWW分子筛可以商购获得或根据本领域中的已知方法制备。通常，Ti-MWW分子筛通过以硼酸为晶化助剂的水热法合成得到(参见，例如Journal of Physical Chemistry B,2001,105,2897)。在本文中将由水热法制备的Ti-MWW分子筛称为“Ti-MWW分子筛原粉(as-synthesized Ti-MWW molecular sieve powder)”。本领域中已经提出对Ti-MWW分子筛原粉进行改造以提高其催化性能的方法。例如，可以对Ti-MWW分子筛原粉进行酸处理(参见，例如Journal of Catalysis,2001,202,245)。在本文中将进行了酸处理的Ti-MWW分子筛原粉称为“Ti-MWW分子筛粉体”。
Ti-MWW分子筛中的钛物种可以以骨架四配位、非骨架六配位及二氧化钛的形式存在。水热法制得的Ti-MWW分子筛原粉含有少量骨架四配位钛物种和大量的非骨架六配位钛物种。通常认为，骨架四配位钛物种是烯烃环氧化的催化活性中心，即所谓的“状态好的钛物种”；而非骨架六配位钛物种以及二氧化钛并非烯烃环氧化的催化活性中心，即所谓的“状态不好的钛物种”。现有技术致力于将非骨架六配位钛物种转化为骨架四配位钛物种，以提高催化剂的催化性能。上述对Ti-MWW分子筛原粉进行酸处理就是这样的转化。
发明人意外发现，非骨架六配位钛物种或骨架四配位钛物种可以转化为改性的非骨架六配位钛物种。钛物种的改性可以通过Ti-MWW分子筛的X射线光电子能谱峰体现。在改性前，Ti-MWW分子筛原粉的X射线光电子能谱图会在458.0±0.2eV、463.8±0.2eV处出现谱峰，其归属于非骨架六配位钛物种。或者，Ti-MWW分子筛粉体的X射线光电子能谱图会在460.3±0.2eV、465.9±0.2eV处出现谱峰，其归属于骨架四配位钛物种。改性后，Ti-MWW分子筛粉体的X射线光电子 能谱图会在458.9±0.2eV、464.8±0.2eV处出现谱峰，其归属于改性的非骨架六配位钛物种。这种改性的非骨架六配位钛物种也具有优异的烯烃环氧化催化活性，即也是一种状态好的钛物种，从而为本发明的Ti-MWW分子筛催化剂赋予改善的催化性能。基于上述发现完成了本发明。
优选，所述催化剂的紫外拉曼谱图在343±4cm-1、484±4cm-1、699±4cm-1和1097±4cm-1处出现谱峰，并且699±4cm-1谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍，1097±4cm-1谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍。通常，343±4cm-1谱峰归属于MWW骨架，484±4cm-1、1097±4cm-1谱峰归属于骨架四配位钛物种，699±4cm-1谱峰归属于非骨架六配位钛物种和/或改性的非骨架六配位钛物种。
优选，以原子计，所述催化剂的硅钛摩尔比(nSi/nTi)为10-200，优选为25-100。
优选，所述催化剂还包括硼和铝中的至少一种元素，优选包括硼元素。以原子计，硼硅摩尔比(nB/nSi)为0-0.1，优选为0-0.03，更优选为0.005-0.03。以原子计，铝硅摩尔比(nAl/nSi)为0-0.1，优选为0-0.03。
优选，所述催化剂为多孔结构，其包含微孔、介孔和大孔。其中，微孔的孔径为小于2nm，例如0.4-2nm；介孔的孔径为2-50nm；大孔的孔径为大于50nm，例如50-500nm。在一个变型中，所述催化剂的微孔体积为0.03-0.15cm3/g，优选为0.03-0.12cm3/g，更优选为0.05-0.10cm3/g；微孔体积占总孔体积的比例为1％-7.5％，优选为1-6％，更优选为1.7％-5％。
优选，所述催化剂具有全结晶结构。本文中，所述“全结晶”指的是分子筛催化剂中不存在或基本上不存在无定形粘合剂。“基本上不存在”指的是无定形粘合剂在催化剂中的量为小于5重量％，优选小于3重量％，更优选小于1重量％。粘合剂被转化为MWW结构分子筛，从而成为所得催化剂的一部分。全结晶结构可以通过扫描电镜和X射线衍射进行确定。
优选，所述催化剂的机械强度为30-90N/cm，优选为40-80N/cm。
在另一个实施方案中，本发明提供一种Ti-MWW分子筛催化剂的制备方法，包括如下步骤：
(1)将Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物成型，焙烧得到成型物；
(2)将步骤(1)成型物在含有机胺溶液存在下晶化，得到催化剂前驱体A；
(3)将步骤(2)催化剂前驱体A进行酸溶液处理，焙烧得到催化剂前驱体B；
(4)将步骤(3)催化剂前驱体B进行有机胺溶液处理，制得所述催化剂。
优选，以原子计，所述Ti-MWW分子筛粉体的硅钛摩尔比为5-120。所述Ti-MWW分子筛粉体可以商购获得，或根据本领域公开技术来制备。
优选，所述粘结剂为无定形粘结剂，并且包括硅源以及选自硼源、铝源中的至少一种。优选地，所述无定形粘结剂包括硅源和硼源。更优选，以氧化物计，硅源：硼源：铝源的摩尔比为1：x：y，其中x＝0-0.5，y＝0-0.5，x+y＝0.02-1。优选，所述硅源选自硅溶胶、水玻璃、白炭黑和正硅酸乙酯中的至少一种；所述硼源选自硼酸、三氧化二硼和硼酸盐中的至少一种；所述铝源选自三氧化二铝、氢氧化铝、偏铝酸钠、硝酸铝和硫酸铝中的至少一种。所述粘合剂可以商购获得，或根据本领域公开技术来制备。在一个变型中，所述粘结剂通过混合各组分(例如硅源、硼源和铝源)来制备。
优选，所述造孔剂选自田菁粉、纤维素、壳聚糖、木质素、淀粉、聚乙二醇、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)和聚环氧乙烷-聚环氧丙烷共聚物(F127)中的至少一种。
优选，所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种。
优选，步骤(1)中，Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物以质量比为1：(0.1-1.5)：(0.01-0.1)：(0.01-0.4)使用。
优选，步骤(1)中，在成型前，将Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物捏合，优选在水存在下进行捏合。任选，步骤(1)中，在捏合和成型后，对产物进行干燥。优选，所述干燥在60-120℃下进行1-24小时
优选，步骤(1)中，所述焙烧在450-650℃下在含氧气氛中焙烧4-12小时。所述含氧气氛可以是空气，氧气，优选是空气。
优选，步骤(2)中，步骤(1)成型物被置于有机胺溶液上方，并且成型物与有机胺溶液不接触。
优选，步骤(2)中，所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种。在一个变型中，所述有机胺溶液的浓度为0.3-15mol/L。优选，所述成型物与有机胺溶液以质量比为(0.1-10)：1使用。在一个变型中，所述晶化在密闭环境中，在130-190℃温度下，在自生压力下，进行1-9天。
优选，步骤(2)中还包括：在晶化后对产物进行洗涤和干燥。优选，所述洗涤为水洗。优选，所述干燥在60-120℃下进行1-24小时。
优选，步骤(2)中不包括焙烧。
优选，步骤(3)包括：使步骤(2)催化剂前驱体A与酸溶液接触并进行反应。所述酸溶液选自硝酸、盐酸、硫酸、甲酸、乙酸或草酸溶液中的至少一种。所述酸溶液的浓度为0.3-12mol/L。所述催化剂前驱体A与酸溶液以质量比为1：(10-80)使用。所述酸溶液处理在温度为60-130℃下进行4-48小时。
任选，在步骤(3)中，在酸溶液处理后，对产物进行洗涤和干燥。优选，所述洗涤为水洗。优选，所述干燥在60-120℃下进行1-24小时。
优选，步骤(3)中所述焙烧在450-650℃下在含氧气氛中进行4-12小时。所述含氧气氛可以是空气，氧气，优选是空气。
优选，步骤(4)包括：在氟化物存在下使步骤(3)催化剂前驱体B与有机胺溶液接触并进行反应。所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种；所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种。所述有机胺溶液的浓度为0.3-15mol/L。所述催化剂前驱体B、氟化物和有机胺溶液以质量比为1：(0.05-0.4)：(2-20)使用。所述有机胺溶液处理在温度为130-190℃下进行4-48小时。
任选，步骤(4)中，在有机胺溶液处理后，对产物进行洗涤和干燥。优选，所述洗涤为水洗。所述干燥在60-120℃下进行1-24小时。
优选，步骤(4)中不包括焙烧。
在另一个实施方案中，本发明还提供了由上述方法制备的Ti-MWW分子筛催化剂。所述Ti-MWW分子筛催化剂具有如前所述的本发明Ti-MWW分子筛催化剂的所有特征，在此不再赘述。
在另一个实施方案中，本发明提供了一种上述Ti-MWW分子筛催 化剂在烯烃环氧化反应中的应用。
优选，所述应用包括以下步骤：混合烯烃、过氧化氢水溶液、溶剂和碱性含氮物质，以形成原料液，和使原料液与所述催化剂接触并进行反应。在一个变型中，所述反应在固定床反应器中进行。
优选，所述烯烃为液化烯烃。所述烯烃包括选自丙烯、氯丙烯、丁烯、戊烯、环戊烯、己烯和环己烯中的至少一种。所述过氧化氢水溶液的浓度为10-70质量％。所述溶剂为选自甲醇、乙腈、丙腈、丙酮和叔丁醇中的至少一种。所述碱性含氮物质为哌啶、六亚甲基亚胺中的至少一种。
优选，所述原料液中，烯烃与过氧化氢的摩尔比为1：0.3-1；烯烃占原料液的量为1-50质量％；溶剂占原料液的量为30-90质量％；所述碱性含氮物质占原料液的量为1-50ppm。
优选，所述反应在以下条件下进行：所述原料液的单位质量催化剂的流量为3-30mL·gcat. -1·h-1；温度为30-100℃，压力为0.1-4MPa。
实施例
通过以下实施例使本发明的特点和优点显而易见。实施例旨在描述而非以任何方式限制本发明。
测试方法：
在本发明中，例如在以下的实施例和比较例中，分子筛催化剂的钛物种的种类、状态、结构、形貌分别通过紫外拉曼光谱、X射线光电子能谱、X射线衍射、扫描电镜确定。分子筛催化剂的硅钛摩尔比、硼硅摩尔比、铝硅摩尔比通过电感耦合原子发射光谱确定。分子筛催化剂的微孔体积、介孔与大孔体积分别通过氮气吸脱附、压汞法测试确定。并且根据测试结果如下计算微孔体积占总孔体积的比例，即微孔体积占总孔体积的比例＝微孔体积除于微孔体积加介孔与大孔体积的和。分子筛催化剂的机械强度通过强度测试仪确定。
在本发明中，紫外拉曼光谱测试方法是：采用国产的UVRaman-100紫外拉曼光谱仪进行测试，激发波长为244nm，照到样品上的激光功率为5.0mW，光谱分辨率为4cm-1，获得分子筛催化剂紫外拉曼光谱图。其中，某个谱峰的强度由该谱峰的峰值减去基线背景得到。
在本发明中，X射线光电子能谱测试方法是：采用AXIS Ultra DLD  X射线光电子能谱仪进行测试，AlKα线为射线源(1486.6eV)，样品腔压力抽至10-9Torr，以C 1s 284.8eV谱峰进行校准。采用OriginPro 9进行分峰拟合。
在本发明中，X射线衍射测试方法是：采用日本理学Rigaku UlTima IV型X-射线粉末衍射仪分析样品，CuKα线为射线源镍滤光片，2θ扫描范围2-50°，操作电压40kV，电流40mA，扫描速率10°/min。
在本发明中，扫描电镜测试方法是：采用日立S-4800电子显微镜进行测试，加速电压3kV。
在本发明中，电感耦合原子发射光谱测试方法是：采用Varian-2000分析仪分析样品中的硅钛摩尔比、硼硅摩尔比、铝硅摩尔比，测试前将样品利用氢氟酸溶液溶解。
在本发明中，氮气吸脱附测试方法是：采用美国麦克ASAP2460仪器测定样品的氮气吸附-脱附等温线，以据此得出微孔体积。其中，测定温度77K，并且在测试前，将样品在573K真空预处理6小时。
在本发明中，压汞法测试方法是：采用高性能全自动压汞仪AutoPore IV 9505进行测试。
在本发明中，机械强度测试方法是：采用DL-2型颗粒强度测试仪进行测试。具体地说，先测试施力方向上催化剂的尺寸，再测定将催化剂挤压成粉末所需施加的外力。用所述外力除以所述尺寸，即得到催化剂的机械强度。
在本发明中，例如在以下的实施例和比较例中，分子筛催化剂的催化性能通过过氧化氢残留率、过氧化氢转化率、主产物(例如环氧化物)及副产物(例如二醇与醇醚)的选择性、主副产物比和催化剂稳定时间来表征。
在本发明中，从反应管入口获得原料液样品，从反应管出口获得反应液样品。可以在反应的任何阶段，例如，在反应管出口刚排出反应液时、在反应过程中或反应结束时获得反应液样品。采用硫酸铈滴定法确定原料液样品、反应液样品中过氧化氢的浓度，并通过下式计算过氧化氢残留率和过氧化氢转化率。
过氧化氢转化率％＝1-过氧化氢残留率％。
在本发明中，使用气相色谱分析原料液样品、反应液样品的组成。利用测量结果来确定反应转化的烯烃的量、反应生成的环氧产物的量，并计算主产物(即环氧化物)的选择性以及主产物(即环氧化物)与副产物(即二醇与醇醚)的主副产物比。
反应中转化的烯烃的摩尔量＝原料液样品中的烯烃的摩尔量-反应液样品中的烯烃的摩尔量
环氧化物选择性％＝反应液样品的环氧产物的摩尔量/反应中转化的烯烃的摩尔量*100％
主副产物比＝反应液样品的环氧产物的摩尔量/(反应中转化的烯烃的摩尔量-反应液样品的环氧产物的摩尔量)*100％
在本发明中，从反应开始计时，当反应液样品中过氧化氢的残留率达到2％时计时结束，两者之间的时间为催化剂稳定时间。
在实施例和对比例中，Ti-MWW分子筛粉体为购自浙江泰德新材料有限公司的样品RT-03B，其钛物种只有骨架四配位钛物种。Ti-MWW分子筛原粉为参照文献(Journal of Physical Chemistry B,2001,105,2897)合成的样品，其只含有非骨架六配位钛物种。
【实施例1】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小 时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S1。
如上所述，对催化剂S1进行测试。
所述催化剂S1的X射线光电子能谱图如图1所示，观察到458.9、460.3、464.8、465.9eV谱峰。其中，460.3、465.9eV谱峰归属于骨架四配位钛物种，458.9、464.8eV谱峰归属于改性的非骨架六配位钛物种。
所述催化剂S1的紫外拉曼谱图如图2所示，观察到343、484、699、1097cm-1谱峰，699cm-1谱峰强度是343cm-1谱峰强度的5.3倍，1097cm-1谱峰强度是343cm-1谱峰强度的5.1倍。其中，343cm-1谱峰归属于MWW结构，484、1097cm-1谱峰归属于骨架四配位钛物种，699cm-1谱峰归属于改性非骨架六配位钛物种。
所述催化剂S1的X射线衍射图如图3所示。其中，在2θ为3.3°、6.6°、7.2°、7.9°、9.7°、26.1°处出现强衍射峰，其中2θ为7.2°处的衍射峰的强度值达5300，表明S1具有MWW结构、结晶度高。
所述催化剂S1的扫描电镜图如图4所示。其中，所述催化剂S1呈现片层形貌，没有观察到纳米小颗粒。这表明S1仅为MWW结构。
所述催化剂S1的硅钛摩尔比为35，硼硅摩尔比为0.015。
所述催化剂S1的微孔体积为0.09cm3/g，微孔体积占总孔体积的比例为3.6％，机械强度为66N/cm。
【实施例2】
(1)将90克硅钛摩尔比为5的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克淀粉和0.9克氟化钾在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按固液质量比为1：50混合，于80℃进行反应24小时，经水 洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S2。
如上所述，对催化剂S2进行测试。
所述催化剂S2的X射线光电子能谱图观察到459.1、460.1、465.0、465.7eV谱峰。
所述催化剂S2的紫外拉曼谱图观察到341、487、702、1094cm-1谱峰，702cm-1谱峰强度是341cm-1谱峰强度的10倍，1094cm-1谱峰强度是341cm-1谱峰强度的10倍。
所述催化剂S2的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S2的硅钛摩尔比为10，硼硅摩尔比为0.005。
所述催化剂S2的微孔体积为0.05cm3/g，微孔体积占总孔体积的比例为1.7％，机械强度为40N/cm。
【实施例3】
(1)将90克硅钛摩尔比为120的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、9克纤维素和36克氟化铵在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小 时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S3。
如上所述，对催化剂S3进行测试。
所述催化剂S3的X射线光电子能谱图观察到458.7、460.4、464.6、466.0eV谱峰。
所述催化剂S3的紫外拉曼谱图观察到345、482、696、1099cm-1谱峰，696cm-1谱峰强度是345cm-1谱峰强度的0.5倍，1099cm-1谱峰强度是345cm-1谱峰强度的0.5倍。
所述催化剂S3的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S3的硅钛摩尔比为200，硼硅摩尔比0.03。
所述催化剂S3的微孔体积为0.07cm3/g，微孔体积占总孔体积的比例为2.3％，机械强度为80N/cm。
【实施例4】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、9克无定形粘结剂(所述无定形粘结剂包括8克二氧化硅质量分数为25％的硅溶胶、1克四硼酸钠)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入120克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后450℃焙烧12小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S4。
如上所述，对催化剂S4进行测试。
所述催化剂S4的X射线光电子能谱图观察到458.7、460.5、464.6、 466.1eV谱峰。
所述催化剂S4的紫外拉曼谱图观察到347、480、695、1101cm-1谱峰，695cm-1谱峰强度是347cm-1谱峰强度的8.2倍，1101cm-1谱峰强度是347cm-1谱峰强度的7.8倍。
所述催化剂S4的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S4的硅钛摩尔比为25，硼硅摩尔比为0.003。
所述催化剂S4的微孔体积为0.06cm3/g，微孔体积占总孔体积的比例为2％，机械强度为30N/cm。
【实施例5】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括30克白炭黑、30克硼酸、30克氢氧化铝)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入120克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后650℃焙烧4小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S5。
如上所述，对催化剂S5进行测试。
所述催化剂S5的X射线光电子能谱图观察到459.0、460.2、464.9、465.8eV谱峰。
所述催化剂S5的紫外拉曼谱图观察到341、486、701、1095cm-1谱峰，701cm-1谱峰强度是341cm-1谱峰强度的2.9倍，1095cm-1谱峰强度是341cm-1谱峰强度的2.6倍。
所述催化剂S5的X射线衍射图、扫描电镜图分别与图3、图4类 似。
所述催化剂S5的硅钛摩尔比为60，硼硅摩尔比为0.1，铝硅摩尔比为0.1。
所述催化剂S5的微孔体积为0.1cm3/g，微孔体积占总孔体积的比例为4％，机械强度为77N/cm。
【实施例6】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克氢氧化铝)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S6。
如上所述，对催化剂S6进行测试。
所述催化剂S6的X射线光电子能谱图观察到459.1、460.1、465.0、465.7eV谱峰。
所述催化剂S6的紫外拉曼谱图观察到339、488、703、1093cm-1谱峰，703cm-1谱峰强度是339cm-1谱峰强度的4.9倍，1093cm-1谱峰强度是339cm-1谱峰强度的5.2倍。
所述催化剂S6的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S6的硅钛摩尔比为37，铝硅摩尔比为0.05。
所述催化剂S6的微孔体积为0.12cm3/g，微孔体积占总孔体积的 比例为6％，机械强度为90N/cm。
【实施例7】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行滚圆造粒成型后，100℃干燥8小时，然后550℃焙烧6小时，得到球状成型物。
(2)将90克步骤(1)所述球状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到球状催化剂前驱体A。
(3)将60克步骤(2)所述球状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到球状催化剂前驱体B。
(4)将40克步骤(3)所述球状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S7。
如上所述，对催化剂S7进行测试。
所述催化剂S7的X射线光电子能谱图观察到458.9、460.3、464.8、465.9eV谱峰。
所述催化剂S7的紫外拉曼谱图观察到343、484、699、1097cm-1谱峰，699cm-1谱峰强度是343cm-1谱峰强度的5.3倍，1097cm-1谱峰强度是343cm-1谱峰强度的5.2倍。
所述催化剂S7的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S7的硅钛摩尔比为34，硼硅摩尔比为0.014。
所述催化剂S7的微孔体积为0.09cm3/g，微孔体积占总孔体积的比例为3.6％，机械强度为80N/cm。
【实施例8】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混 合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于900克浓度为0.3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S8。
如上所述，对催化剂S8进行测试。
所述催化剂S8的X射线光电子能谱图观察到459.0、460.2、464.9、465.8eV谱峰。
所述催化剂S8的紫外拉曼谱图观察到341、486、701、1095cm-1谱峰，701cm-1谱峰强度是341cm-1谱峰强度的4.8倍，1095cm-1谱峰强度是341cm-1谱峰强度的5.9倍。
所述催化剂S8的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S8的硅钛摩尔比为32，硼硅摩尔比为0.017。
所述催化剂S8的微孔体积为0.07cm3/g，微孔体积占总孔体积的比例为2.3％，机械强度为56N/cm。
【实施例9】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于9克浓度为15 mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S9。
如上所述，对催化剂S9进行测试。
所述催化剂S9的X射线光电子能谱图观察到458.9、460.4、464.8、466.0eV谱峰。
所述催化剂S9的紫外拉曼谱图观察到345、483、698、1099cm-1谱峰，698cm-1谱峰强度是345cm-1谱峰强度的5.7倍，1099cm-1谱峰强度是345cm-1谱峰强度的4.9倍。
所述催化剂S9的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S9的硅钛摩尔比为34，硼硅摩尔比为0.016。
所述催化剂S9的微孔体积为0.08cm3/g，微孔体积占总孔体积的比例为3.2％，机械强度为64N/cm。
【实施例10】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的六亚甲基亚胺溶液上方，二者不接触，于密闭环境，130℃晶化9天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、 100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S10。
如上所述，对催化剂S10进行测试。
所述催化剂S10的X射线光电子能谱图观察到459.0、460.2、464.9、465.8eV谱峰。
所述催化剂S10的紫外拉曼谱图观察到341、486、701、1095cm- 1谱峰，701cm-1谱峰强度是341cm-1谱峰强度的4.5倍，1095cm-1谱峰强度是341cm-1谱峰强度的4.9倍。
所述催化剂S10的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S10的硅钛摩尔比为42，硼硅摩尔比为0.02。
所述催化剂S10的微孔体积为0.06cm3/g，微孔体积占总孔体积的比例为2％，机械强度为45N/cm。
【实施例11】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的六亚甲基亚胺溶液上方，二者不接触，于密闭环境，190℃晶化1天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作 S11。
如上所述，对催化剂S11进行测试。
所述催化剂S11的X射线光电子能谱图观察到458.9、460.4、464.8、466.0eV谱峰。
所述催化剂S11的紫外拉曼谱图观察到345、482、698、1099cm- 1谱峰，698cm-1谱峰强度是345cm-1谱峰强度的6倍，1099cm-1谱峰强度是345cm-1谱峰强度的5倍。
所述催化剂S11的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S11的硅钛摩尔比为30，硼硅摩尔比为0.01。
所述催化剂S11的微孔体积为0.07cm3/g，微孔体积占总孔体积的比例为2.3％，机械强度为69N/cm。
【实施例12】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与12mol/L盐酸溶液按质量比为1：10混合，于130℃进行反应4小时，经水洗、100℃干燥8小时和450℃焙烧12小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S12。
如上所述，对催化剂S12进行测试。
所述催化剂S12的X射线光电子能谱图观察到458.9、460.5、464.8、466.1eV谱峰。
所述催化剂S12的紫外拉曼谱图观察到344、481、698、1100cm- 1谱峰，698cm-1谱峰强度是344cm-1谱峰强度的3.3倍，1100cm-1谱峰强度是344cm-1谱峰强度的2.4倍。
所述催化剂S12的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S12的硅钛摩尔比为57，硼硅摩尔比为0.004。
所述催化剂S12的微孔体积为0.1cm3/g，微孔体积占总孔体积的比例为4％，机械强度为48N/cm。
【实施例13】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与0.3mol/L草酸溶液按质量比为1：80混合，于60℃进行反应48小时，经水洗、100℃干燥8小时和650℃焙烧4小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S13。
如上所述，对催化剂S13进行测试。
所述催化剂S13的X射线光电子能谱图观察到459.1、460.1、465.0、465.7eV谱峰。
所述催化剂S13的紫外拉曼谱图观察到341、488、702、1093cm- 1谱峰，702cm-1谱峰强度是341cm-1谱峰强度的5.9倍，1093cm-1谱峰强度是341cm-1谱峰强度的5.7倍。
所述催化剂S13的X射线衍射图、扫描电镜图分别与图3、图4类 似。
所述催化剂S13的硅钛摩尔比为27，硼硅摩尔比为0.08。
所述催化剂S13的微孔体积为0.05cm3/g，微孔体积占总孔体积的比例为1.7％，机械强度为60N/cm。
【实施例14】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的六亚甲基亚胺溶液按质量比1：0.2：20混合，于170℃进行反应48小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S14。
如上所述，对催化剂S14进行测试。
所述催化剂S14的X射线光电子能谱图观察到458.9、460.3、464.8、465.9eV谱峰。
所述催化剂S14的紫外拉曼谱图观察到342、484、700、1097cm- 1谱峰，700cm-1谱峰强度是342cm-1谱峰强度的5倍，1097cm-1谱峰强度是342cm-1谱峰强度的4.8倍。
所述催化剂S14的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S14的硅钛摩尔比为39，硼硅摩尔比为0.018。
所述催化剂S14的微孔体积为0.08cm3/g，微孔体积占总孔体积的比例为3.2％，机械强度为62N/cm。
【实施例15】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化钾、15mol/L的哌啶溶液按质量比1：0.4：2混合，于190℃进行反应4小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S15。
如上所述，对催化剂S15进行测试。
所述催化剂S15的X射线光电子能谱图观察到459.0、460.2、464.9、465.8eV谱峰。
所述催化剂S15的紫外拉曼谱图观察到342、485、701、1095cm- 1谱峰，701cm-1谱峰强度是342cm-1谱峰强度的6.8倍，1095cm-1谱峰强度是342cm-1谱峰强度的3.2倍。
所述催化剂S15的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S15的硅钛摩尔比为37，硼硅摩尔比为0.025。
所述催化剂S15的微孔体积为0.15cm3/g，微孔体积占总孔体积的比例为7.5％，机械强度为64N/cm。
【实施例16】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械 挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化钠、0.3mol/L的哌啶溶液按质量比1：0.05：20混合，于130℃进行反应48小时，经水洗、100℃干燥8小时，制得Ti-MWW分子筛催化剂，记作S16。
如上所述，对催化剂S16进行测试。
所述催化剂S16的X射线光电子能谱图观察到458.9、460.3、464.8、465.9eV谱峰。
所述催化剂S16的紫外拉曼谱图观察到344、482、698、1098cm- 1谱峰，698cm-1谱峰强度是344cm-1谱峰强度的3.3倍，1098cm-1谱峰强度是344cm-1谱峰强度的6.9倍。
所述催化剂S16的X射线衍射图、扫描电镜图分别与图3、图4类似。
所述催化剂S16的硅钛摩尔比为36，硼硅摩尔比为0.01。
所述催化剂S16的微孔体积为0.03cm3/g，微孔体积占总孔体积的比例为1％，机械强度为57N/cm。
【工作实施例17-24】
在实施例1、2、3、6、11、12、15、16制备的Ti-MWW分子筛催化剂存在下分别进行丙烯液相连续环氧化反应，以评价其催化性能。
将2克上述Ti-MWW分子筛催化剂破碎成20-40目的颗粒，并填充在不锈钢反应管中，其中反应管两端用玻璃珠填充。反应在以下条件下进行：反应温度为40℃，反应压力为2.0MPa，采用下进料上出料的模式。使用氮气平衡丙烯压力至2.5MPa以保证丙烯完全液化。丙烯的原料液单独进料，记为原料液A。选用过氧化氢质量分数为30％的水溶液，配制含哌啶浓度为15ppm的过氧化氢水溶液，并将其与溶剂 乙腈混合，记为原料液B。两股原料液分别采用柱塞泵进料，并且两股原料液在进入反应管之前先预混。收集进入反应管的混合的原料液样品，对其进行如上所述的测试。在混合的原料进料流中，丙烯的质量分数为18.7％，乙腈的质量分数为61.0％，丙烯与过氧化氢摩尔比为1：0.4，总原料单位质量催化剂的流量为6mL·gcat. -1·h-1。收集流出反应管的反应液样品，对其进行如上所述的测试。其结果如表1所示。
表1各实施例催化剂在丙烯液相连续环氧化反应中的催化性能

注：a.在反应管出口刚排出反应液时获取反应液样品来计算过氧化氢转化率与残留
率。
【工作实施例25-28】
在实施例1、6、11、16制备的Ti-MWW分子筛催化剂存在下分别 进行氯丙烯液相连续环氧化反应，以评价其催化性能。
将2克Ti-MWW分子筛催化剂破碎成20-40目的颗粒，并填充在不锈钢反应管中，其中反应管两端用玻璃珠填充。反应在以下条件下进行：反应温度为60℃，反应压力为0.6MPa，采用下进料上出料的模式。氯丙烯的原料液单独进料，记为原料液A。选用过氧化氢质量分数为30％的水溶液，配制含六亚甲基亚胺浓度为50ppm的过氧化氢水溶液，并将其与溶剂乙腈混合，记为原料液B。两股原料液分别采用柱塞泵进料，并且两股原料液在进入反应管之前先预混。收集进入反应管的混合的原料液样品，对其进行如上所述的测试。在混合的原料进料流中，氯丙烯的质量分数为27.7％，乙腈的质量分数为54.2％，氯丙烯与过氧化氢摩尔比为1：0.4，总原料单位质量催化剂的流量为4mL·gcat. -1·h-1。收集流出反应管的反应液样品，对其进行如上所述的测试。其结果如下表2所示：
表2各实施例催化剂在氯丙烯液相连续环氧化反应中的催化性能

注：a.在反应管出口刚排出反应液时获取反应液样品来计算过氧化氢转化率与残留
率。
【对比例1】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混 合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将60克步骤(1)所述圆柱状成型物与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体。
(3)将40克步骤(2)所述圆柱状催化剂前驱体与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，得到Ti-MWW分子筛催化剂，记作D1。
如上所述，对催化剂D1进行测试。
D1的X射线光电子能谱图如图5所示，观察到459.5、465.1eV谱峰，归属于四配位钛物种。
D1的紫外拉曼谱图如图6所示，只观察到491、1080cm-1谱峰，没有观察到归属于MWW结构的谱峰。491、1080cm-1谱峰归属于四配位钛物种。这样的结果主要归结于催化剂中仍然存在无定形粘结剂，其没有转化为分子筛的组分。无定形粘结剂的存在遮蔽了分子筛，从而无法通过紫外拉曼检测到分子筛的MWW结构。
D1的X射线衍射图如图7所示，在2θ为3.3°、6.6°、7.2°、7.9°、9.7°、26.1°处出现衍射峰，其中2θ为7.2°处的衍射峰的强度值为2500左右，强度明显弱于S1，表明D1的主体仍为MWW结构，但结晶度低。另外，在17.5-30°区域还有较强的宽衍射峰，进一步表明D1还存在无定形物种。
扫描电镜图如图8所示，在催化剂中除了观察到片层形貌外，还观察到纳米小颗粒。这再次表明D1存在无定形物种。与图7显示的结果相一致。
D1的硅钛摩尔比为30，硼硅摩尔比为0.06。
D1的微孔体积为0.04cm3/g，微孔体积占总孔体积的比例为1.4％，机械强度为29N/cm。
【对比例2】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混 合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体。
(3)将40克步骤(2)所述圆柱状催化剂前驱体与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，得到Ti-MWW分子筛催化剂，记作D2。
如上所述，对催化剂D2进行测试。
D2的X射线光电子能谱图观察到460.0、465.6eV谱峰，归属于骨架四配位钛物种。
D2的紫外拉曼谱图如图9所示，观察到342、491、1090cm-1谱峰，1090cm-1谱峰强度是342cm-1谱峰强度的11.2倍。这表明存在大量骨架四配位钛物种。
D2的X射线衍射图、扫描电镜图分别与图3、图4类似。
D2的硅钛摩尔比为31，硼硅摩尔比为0.05。
D2的微孔体积为0.08cm3/g，微孔体积占总孔体积的比例为3.2％，机械强度为68N/cm。
【对比例3】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体。
(3)将60克步骤(2)所述圆柱状催化剂前驱体与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到Ti-MWW分子筛催化剂，记 作D3。
如上所述，对催化剂D3进行测试。
D3的X射线光电子能谱图观察到460.0、465.6eV谱峰，归属于骨架四配位钛物种。
D3的紫外拉曼谱图如图10所示。观察到343、490、1092cm-1谱峰，1092cm-1谱峰强度是343cm-1谱峰强度的10.2倍。这表明存在大量骨架四配位钛物种。
D3的X射线衍射图、扫描电镜图分别与图3、图4类似。
D3的硅钛摩尔比为36，硼硅摩尔比为0.017。
D3的微孔体积为0.16cm3/g，微孔体积占总孔体积的比例为7.8％，机械强度为58N/cm。
【对比例4】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)和3克田菁粉在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与氟化铵、3mol/L的哌啶溶液按质量比1：0.1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，得到Ti-MWW分子筛催化剂，记作D4。
如上所述，对催化剂D4进行测试。
D4的X射线光电子能谱图观察到459.7、465.4eV谱峰，归属于四配位钛物种。
D4的紫外拉曼谱图如图11所示，观察到340、488、1087cm-1谱峰，1087cm-1谱峰强度是340cm-1谱峰强度的10.9倍。这表明存在大 量四配位钛物种。
D4的X射线衍射图、扫描电镜图分别与图7、图8类似。
D4的硅钛摩尔比为33，硼硅摩尔比为0.012。
D4的微孔体积为0.05cm3/g，微孔体积占总孔体积的比例为1.7％，机械强度为36N/cm。
【对比例5】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物。
(2)将90克步骤(1)所述圆柱状成型物放置于60克浓度为3mol/L的哌啶溶液上方，二者不接触，于密闭环境，170℃晶化2天，经水洗、100℃干燥8小时，得到圆柱状催化剂前驱体A。
(3)将60克步骤(2)所述圆柱状催化剂前驱体A与2mol/L硝酸溶液按质量比为1：50混合，于80℃进行反应24小时，经水洗、100℃干燥8小时和550℃焙烧6小时，得到圆柱状催化剂前驱体B。
(4)将40克步骤(3)所述圆柱状催化剂前驱体B与3mol/L的哌啶溶液按质量比1：10混合，于170℃进行反应24小时，经水洗、100℃干燥8小时，得到Ti-MWW分子筛催化剂，记作D5。
如上所述，对催化剂D5进行测试。
D5的X射线光电子能谱图观察到460.6、466.2eV谱峰，归属于四配位钛物种。
D5的紫外拉曼谱图如图12所示，观察到342、490、1102cm-1谱峰，1102cm-1谱峰强度是342cm-1谱峰强度的10.3倍。这表明存在大量骨架四配位钛物种。
D5的X射线衍射图、扫描电镜图分别与图3、图4类似。
D5的硅钛摩尔比为36，硼硅摩尔比为0.017。
D5的微孔体积为0.04cm3/g，微孔体积占总孔体积的比例为1.3％，机械强度为74N/cm。
【对比例6】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛粉体、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物，记作D6。
如上所述，对催化剂D6进行测试。
D6的X射线光电子能谱图如图13所示，观察到460.2、465.8eV谱峰，归属于四配位钛物种。
D6的紫外拉曼谱图如图14所示，观察到343、492、1094cm-1谱峰，1094cm-1谱峰强度是343cm-1谱峰强度的9.7倍。这表明存在大量骨架四配位钛物种。
Ti-MWW分子筛粉体的X射线光电子能谱图、紫外拉曼谱图分别与图13、图14类似，表明机械挤压成型不影响催化剂D6钛物种的状态。
D6的X射线衍射图、扫描电镜图分别与图7、图8类似。
D6的硅钛摩尔比为38，硼硅摩尔比为0.11。
D6的微孔体积为0.13cm3/g，微孔体积占总孔体积的比例为5.4％，机械强度为28N/cm。
【对比例7】
(1)将90克硅钛摩尔比为20的Ti-MWW分子筛原粉、90克无定形粘结剂(所述无定形粘结剂包括75克二氧化硅质量分数为40％的硅溶胶、15克硼酸)、3克田菁粉和9克氟化钠在机械搅拌的条件下混合，然后加入80克水，搅拌捏合4小时，得到固体混合物，进行机械挤压成型后，100℃干燥8小时，然后550℃焙烧6小时，得到圆柱状成型物，记作D7。
如上所述，对催化剂D7进行测试。
D7的X射线光电子能谱图如图15所示，只观察到458.0、463.8eV谱峰，归属于非骨架六配位钛物种。
D7的紫外拉曼谱图如图16所示，只观察到440、700cm-1谱峰，归属于非骨架六配位钛物种。
Ti-MWW分子筛原粉的X射线光电子能谱图、紫外拉曼谱图分别 与图15、图16类似，表明机械挤压成型不影响催化剂D7钛物种的状态。
D7的X射线衍射图、扫描电镜图分别与图7、图8类似。
D7的硅钛摩尔比为37，硼硅摩尔比为0.12。
D7的微孔体积为0.12cm3/g，微孔体积占总孔体积的比例为5.3％，机械强度为26N/cm。
【对比工作例8-11】
用对比例1-7得到的Ti-MWW分子筛催化剂D1-D7分别重复工作实施例17-24，以评价其催化性能。结果如下表3所示：
表3各对比例催化剂在丙烯液相连续环氧化反应中的催化性能

注：a.在反应管出口刚排出反应液时获取反应液样品来计算过氧化氢转化率与残留
率。
以上详细描述了本发明的具体实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单 变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (15)

  1. 一种Ti-MWW分子筛催化剂，其中，催化剂的X射线光电子能谱图在458.9±0.2eV、464.8±0.2eV处出现谱峰，优选在458.9±0.1eV、464.8±0.1eV处出现谱峰；
    优选地，在458.9±0.2eV、460.3±0.2eV、464.8±0.2eV、465.9±0.2eV处出现谱峰，优选在458.9±0.1eV、460.3±0.1eV、464.8±0.1eV、465.9±0.1eV处出现谱峰。
  2. 根据权利要求1所述的催化剂，其特征在于，其紫外拉曼谱图在343±4cm-1、484±4cm-1、699±4cm-1和1097±4cm-1处出现谱峰；
    优选地，699±4cm-1谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍，并且1097±4cm-1谱峰的强度是343±4cm-1谱峰强度的0.5-10倍，优选为2-10倍。
  3. 根据权利要求1所述的催化剂，其特征在于，所述催化剂的硅钛摩尔比为10-200，优选为25-100；所述催化剂还包括硼和铝中的至少一种元素，优选包括硼元素；硼硅摩尔比为0-0.1，优选为0-0.03，更优选为0.005-0.03；铝硅摩尔比为0-0.1，优选为0-0.05。
  4. 根据权利要求1所述的催化剂，其特征在于，所述催化剂的微孔体积为0.03-0.15cm3/g，优选为0.03-0.12cm3/g，更优选为0.05-0.10cm3/g；微孔体积占总孔体积的比例为1％-7.5％，优选为1-6％，更优选为1.7％-5％。
  5. 根据权利要求1所述的催化剂，其特征在于，所述催化剂具有全结晶结构，优选所述催化剂的机械强度为30-90N/cm，优选为40-80N/cm。
  6. 一种制备Ti-MWW分子筛催化剂的方法，包括如下步骤：
    (1)将Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物成型，焙烧得到成型物；
    (2)将步骤(1)成型物在含有机胺溶液存在下晶化，得到催化剂前驱体A；
    (3)将步骤(2)催化剂前驱体A进行酸溶液处理，焙烧得到催化剂前驱体B；
    (4)将步骤(3)催化剂前驱体B进行有机胺溶液处理，制得所 述催化剂。
  7. 根据权利要求6所述的方法，其特征在于，所述粘结剂包括硅源以及选自硼源、铝源中的至少一种；以氧化物计，硅源：硼源：铝源的摩尔比为1：x：y，其中x＝0-0.5，y＝0-0.5，x+y＝0.02-1。
  8. 根据权利要求7所述的方法，其特征在于，所述硅源选自硅溶胶、水玻璃、白炭黑和正硅酸乙酯中的至少一种；所述硼源选自硼酸、三氧化二硼和硼酸盐中的至少一种；所述铝源选自三氧化二铝、氢氧化铝、偏铝酸钠、硝酸铝和硫酸铝中的至少一种。
  9. 根据权利要求6-8任一所述的方法，其特征在于，所述造孔剂选自田菁粉、纤维素、壳聚糖、木质素、淀粉、聚乙二醇、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)和聚环氧乙烷-聚环氧丙烷共聚物(F127)中的至少一种；所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种；Ti-MWW分子筛粉体、粘结剂、造孔剂和氟化物以质量比为1：(0.1-1.5)：(0.01-0.1)：(0.01-0.4)使用。
  10. 根据权利要求6所述的方法，其特征在于，步骤(2)包括：步骤(1)成型物被置于有机胺溶液上方，并且成型物与有机胺溶液不接触；所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种；所述有机胺溶液的浓度为0.3-15mol/L；所述成型物与有机胺溶液的质量比为0.1-10：1；所述晶化在温度为130-190℃下进行1-9天。
  11. 根据权利要求6所述的方法，其特征在于，步骤(3)包括：使步骤(2)催化剂前驱体A与酸溶液接触并进行反应；所述酸溶液选自硝酸、盐酸、硫酸、甲酸、乙酸或草酸溶液中的至少一种；所述酸溶液的浓度为0.3-12mol/L；所述催化剂前驱体A与酸溶液的质量比为1：10-80；所述酸溶液处理在温度为60-130℃下进行4-48小时。
  12. 根据权利要求6所述的方法，其特征在于，步骤(4)包括：在氟化物存在下使步骤(3)催化剂前驱体B与有机胺溶液接触并进行反应；所述氟化物选自氟化钠、氟化钾和氟化铵中的至少一种；所述有机胺为选自哌啶、六亚甲基亚胺中的至少一种；所述有机胺溶液的浓度为0.3-15mol/L；所述催化剂前驱体B、氟化物和有机胺溶液的质量比为1：0.05-0.4：2-20；所述有机胺溶液处理在温度为130-190℃下进行4-48小时。
  13. 根据权利要求6所述的方法，其特征在于，步骤(1)中所述 焙烧在450-650℃在含氧气氛中进行4-12小时；步骤(3)中所述焙烧在450-650℃在含氧气氛中进行4-12小时。
  14. 权利要求5-13任一项的方法制备得到的催化剂。
  15. 权利要求1-5任一项所述的催化剂或权利要求14所述的催化剂在烯烃环氧化反应中的应用。
PCT/CN2023/128161 2022-11-10 2023-10-31 一种Ti-MWW分子筛催化剂及其制备方法和应用 Ceased WO2024099165A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020257016187A KR20250102038A (ko) 2022-11-10 2023-10-31 Ti-MWW 분자체 촉매 및 그 제조방법과 응용
EP23887855.7A EP4616944A1 (en) 2022-11-10 2023-10-31 Ti-mww molecular sieve catalyst, preparation method therefor, and use thereof
JP2025526538A JP2025536031A (ja) 2022-11-10 2023-10-31 Ｔｉ－ＭＷＷ分子ふるい触媒、その調製方法およびその使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211408458.1 2022-11-10
CN202211408458.1A CN118022824A (zh) 2022-11-10 2022-11-10 一种全结晶Ti-MWW分子筛催化剂及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2024099165A1 true WO2024099165A1 (zh) 2024-05-16

Family

ID=90993898

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/128161 Ceased WO2024099165A1 (zh) 2022-11-10 2023-10-31 一种Ti-MWW分子筛催化剂及其制备方法和应用

Country Status (5)

Country Link
EP (1) EP4616944A1 (zh)
JP (1) JP2025536031A (zh)
KR (1) KR20250102038A (zh)
CN (1) CN118022824A (zh)
WO (1) WO2024099165A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120268451A (zh) * 2025-06-09 2025-07-08 浙江泰德新材料有限公司 一种Ti-MWW分子筛催化剂、制备方法及其在双氧水直接与烯烃环氧化制备环氧化合物中的应用
CN121082313A (zh) * 2025-11-05 2025-12-09 江西师范大学 CuOX/Ti-MWW复合催化剂及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410501A (en) 1979-12-21 1983-10-18 Snamprogetti S.P.A. Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides
CN1346705A (zh) 2001-09-13 2002-05-01 大连理工大学 一种复合催化剂的制备及其应用
CN1686795A (zh) * 2005-04-18 2005-10-26 华东师范大学 一种 Ti－MWW 分子筛的合成方法
CN106967011A (zh) * 2016-01-14 2017-07-21 中国石油化工股份有限公司 一种烯烃氧化的方法
CN109678171A (zh) * 2017-10-19 2019-04-26 中国石油化工股份有限公司 高外表面积、高骨架钛含量Ti-MWW分子筛及其制备方法与催化应用
CN113880111A (zh) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Ti-MWW分子筛及其制备方法与应用
US20220008904A1 (en) * 2019-06-14 2022-01-13 Dalian University Of Technology Alkali metal ion modified titanium silicalite zeolite ts-1 for gas phase epoxidation of propylene and hydrogen peroxide and preparation method thereof
US20220008903A1 (en) * 2019-06-14 2022-01-13 Dalian University Of Technology Alkali metal ion modified titanium silicalite zeolite for gas phase epoxidation of propylene and hydrogen peroxide and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090216033A1 (en) * 2008-02-27 2009-08-27 Lekhac Bi Epoxidation catalyst
CN102441430B (zh) * 2010-10-11 2013-06-12 中国石油化工股份有限公司 一种催化剂及其制备方法和环氧化烯烃的方法
CN109081359B (zh) * 2017-06-13 2020-10-23 中国石油化工股份有限公司 分子筛scm-15、其合成方法及其用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410501A (en) 1979-12-21 1983-10-18 Snamprogetti S.P.A. Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides
CN1346705A (zh) 2001-09-13 2002-05-01 大连理工大学 一种复合催化剂的制备及其应用
CN1686795A (zh) * 2005-04-18 2005-10-26 华东师范大学 一种 Ti－MWW 分子筛的合成方法
CN106967011A (zh) * 2016-01-14 2017-07-21 中国石油化工股份有限公司 一种烯烃氧化的方法
CN109678171A (zh) * 2017-10-19 2019-04-26 中国石油化工股份有限公司 高外表面积、高骨架钛含量Ti-MWW分子筛及其制备方法与催化应用
US20220008904A1 (en) * 2019-06-14 2022-01-13 Dalian University Of Technology Alkali metal ion modified titanium silicalite zeolite ts-1 for gas phase epoxidation of propylene and hydrogen peroxide and preparation method thereof
US20220008903A1 (en) * 2019-06-14 2022-01-13 Dalian University Of Technology Alkali metal ion modified titanium silicalite zeolite for gas phase epoxidation of propylene and hydrogen peroxide and preparation method thereof
CN113880111A (zh) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Ti-MWW分子筛及其制备方法与应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF CATALYSIS, vol. 202, 2001, pages 245
JOURNAL OF PHYSICAL CHEMISTRY B, vol. 105, 2001, pages 2897
See also references of EP4616944A1

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120268451A (zh) * 2025-06-09 2025-07-08 浙江泰德新材料有限公司 一种Ti-MWW分子筛催化剂、制备方法及其在双氧水直接与烯烃环氧化制备环氧化合物中的应用
CN121082313A (zh) * 2025-11-05 2025-12-09 江西师范大学 CuOX/Ti-MWW复合催化剂及其制备方法和应用

Also Published As

Publication number Publication date
EP4616944A1 (en) 2025-09-17
CN118022824A (zh) 2024-05-14
KR20250102038A (ko) 2025-07-04
JP2025536031A (ja) 2025-10-30

Similar Documents

Publication Publication Date Title
CN113058643B (zh) 一种改性ts-1分子筛复合催化剂及其制备方法和应用
TWI640362B (zh) Molecular sieve, manufacturing method thereof and use thereof
EP4616944A1 (en) Ti-mww molecular sieve catalyst, preparation method therefor, and use thereof
CN104069886B (zh) 一种用于水相糠醛加氢制环戊酮的催化剂的制备方法及其应用
CN102190316A (zh) 介孔丝光沸石的合成方法
CN104891520A (zh) 一种固相合成多级孔分子筛的方法
CN110316740A (zh) 一种空心核壳结构钛硅分子筛催化剂及其制备方法
CN111253217B (zh) 一种环己烯水合制备环己醇的方法
CN117504816B (zh) 一种含氧化物深度净化用高效分子筛吸附剂及其制备和应用
Zhang et al. The synthesis of pure and uniform nanosized TS-1 crystals with a high titanium content and a high space–time yield
CN108821304A (zh) 高活性多级孔钛硅分子筛及其制备方法和应用
US12129185B2 (en) Alpha-phase nickel hydroxide and preparation method and use thereof
CN106607079A (zh) 甲醇制芳烃的催化剂及其用途
CN116177561B (zh) 一种具有中空多级孔的zsm-5纳米晶材料及其制备方法和应用
CN109251193B (zh) 制备碳酸丙烯酯的方法
CN114225961B (zh) 一种用于合成环氧丙烷的催化剂及其制备方法和应用
CN115957808A (zh) 全结晶mww结构钛硅分子筛催化剂及其制备方法与应用
CN112206811B (zh) 一种甲醇转化制丙烯催化剂及其制备方法和应用
Umegaki et al. Immobilized molybdic acid on porous silica-alumina hollow sphere particles for acid-promoted hydrolytic hydrogen evolution from ammonia borane
CN118812372A (zh) 聚阳离子结构导向剂和纳米片状Beta分子筛及其制备和应用
CN111732110A (zh) 一种NaY沸石及其制备方法
Ma et al. One-pot synthesis of hierarchical mesoporous ZSM-5 from the assembly of nanocrystals using urea as additive
CN106964393B (zh) 丙烯制造用催化剂、该催化剂的制造方法和丙烯的制造方法
CN116273158B (zh) 钛硅分子筛及其制备方法和应用
CN115990509B (zh) 一种苯与甲醇烷基化催化剂及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23887855

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2501002876

Country of ref document: TH

ENP Entry into the national phase

Ref document number: 2025526538

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025526538

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20257016187

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 11202502904X

Country of ref document: SG

WWP Wipo information: published in national office

Ref document number: 11202502904X

Country of ref document: SG

WWE Wipo information: entry into national phase

Ref document number: 202547054332

Country of ref document: IN

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112025008515

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2023887855

Country of ref document: EP

Ref document number: 2025114959

Country of ref document: RU

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 202547054332

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2023887855

Country of ref document: EP

Effective date: 20250610

WWP Wipo information: published in national office

Ref document number: 1020257016187

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2025114959

Country of ref document: RU

WWP Wipo information: published in national office

Ref document number: 2023887855

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 112025008515

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20250429