CN106311324A - Method for preparing molecular sieve based catalyst - Google Patents

Method for preparing molecular sieve based catalyst Download PDF

Info

Publication number
CN106311324A
CN106311324A CN201610689607.4A CN201610689607A CN106311324A CN 106311324 A CN106311324 A CN 106311324A CN 201610689607 A CN201610689607 A CN 201610689607A CN 106311324 A CN106311324 A CN 106311324A
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
crystallization
sieve catalyst
temperature
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.)
Pending
Application number
CN201610689607.4A
Other languages
Chinese (zh)
Inventor
苏建丽
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.)
Qingdao Wenchuang Technology Co Ltd
Original Assignee
Qingdao Wenchuang Technology Co Ltd
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 Qingdao Wenchuang Technology Co Ltd filed Critical Qingdao Wenchuang Technology Co Ltd
Priority to CN201610689607.4A priority Critical patent/CN106311324A/en
Publication of CN106311324A publication Critical patent/CN106311324A/en
Pending 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for preparing a molecular sieve based catalyst. The method comprises the following steps: mixing and hydrolyzing a silicon source, a template agent, a mineralizer, water and ethanol at normal temperature; slowly adding a mixture of a titanium source and the residual silicon source into the hydrolyzed silicon hydroxide solution under rapid stirring, and forming gel; transferring the gel into a crystallization kettle for crystallization; washing, filtering and roasting a crystallized molecular sieve so as to remove the template agent, wherein the calcination temperature is 500-600 DEG C, and the calcination time is 4-6 hours to obtain the composite porous molecular sieve based catalyst. The catalyst is simple in preparation process and high in production efficiency; and moreover, because the molecular sieve structure contains organic functional groups and composite pores with hydrophobic property and carbon deposition resistance, the catalyst is excellent in hydrophobic property and mass transfer performance and high in activity, selectivity and stability, and can be used in the process of producing corresponding epoxides through olefin epoxidation by taking H2O2, ethylbenzene hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide and the like as oxidizing agents.

Description

A kind of preparation method of molecular sieve catalyst
Technical field
The invention belongs to chemical technology field, relate to the preparation method of a kind of molecular sieve catalyst, specifically, particularly to logical Cross hydrothermal crystallizing method by four-coordination active titanium species and the Si-(CH containing organo-functional group2)n1-Si、Si-O-Si(R4)n2With Ti-O-Si(R4)n2Assemble in situ is in the molecular sieve catalyst with composite pore structural.
Background technology
The hydroxylating etc. of selective oxidation, the ammoxidation of ketone/aldehyde and the aromatic hydrocarbons of hydro carbons is respectively provided with by titanium porous molecular sieve materials Good catalysis activity, can be as the catalyst of alkene epoxidation He other multiple reaction, before having wide commercial Application Scape.
Through retrieval, patent US4410501 makes public for the first time the synthetic method of TS-1 molecular sieve.The method is with tetrapropyl hydrogen-oxygen Changing the aqueous solution of ammonium, organic titanate and organosilicon acid esters is that titanium silicon mixed colloidal solution prepared by raw material, then brilliant by hydro-thermal It is combined to HTS.Owing to TS-1 molecular sieve is incorporated into molecule sieve skeleton the transition metal titanium atom with feature of appraising at the current rate Frame, defines the oxidation reduction catalyst with selectional feature, has good catalytic oxidation performance.This molecular sieve is from 1983 Since year synthesis first, with H2O2Ammoxidation (EP 0267362), alkene epoxidation (EP for the ketone of oxidant 1100119), the field such as hydroxylating (US 4396783) of aromatic hydrocarbons has shown good commercial Application potentiality.
For the epoxidation reaction of olefin and its derivatives, owing to TS-1 is the micro-pore zeolite with MFI structure, aperture It is about 0.55nm, is limited to the use of with H2O2Prepare for oxidizer catalytic epoxidation propylene in the technique of expoxy propane.When with bigger chi Very little organic peroxide, if hydrogen peroxide ethylbenzene and cumyl hydroperoxide are oxidizing propylene and bigger alkene Time, TS-1 is almost without catalysis activity.And with H2O2For oxidant, TS-1 molecular sieve is the Selective Oxidation of catalyst In, it is desirable to catalyst has certain hydrophobicity, it is simple to make the organic reactant with hydrophobic property adsorb at catalyst surface On react, and generate heavier component be difficult to adhere on a catalyst and affect activity and the stability of catalyst.Logical HTS prepared in the case of Chang has certain hydrophobicity, but this hydrophobicity is relatively weak, does not have generation The molten carbon ability of heavier component, catalyst easily inactivates, poor stability.
When patent US 4367342 and US3923843 discloses with the amorphous silica of titaniferous for catalyst, peroxide Changing hydrogen ethylbenzene can be expoxy propane by epoxidation of propylene.But the amorphous silica carrier specific surface area owing to being used is little, Ti content is low, and catalyst surface hydrophobicity is poor, and product expoxy propane easily at its surface ring opening hydrolysis and gathers further Symphysis becomes the polymer of larger molecular weight to be attached to catalyst surface, affects the catalyst selectivity to expoxy propane, goes forward side by side One step causes catalysqt deactivation.Therefore, such catalyst cannot be competent at macrocyclic efficient propylene catalytic epoxidation system.
Patent CN1500004A and CN 1248579A disclose with cumyl hydroperoxide or hydrogen peroxide ethylbenzene for oxidation Agent, Selective Oxidation of Propylene can be become expoxy propane by Ti-MCM41 mesoporous molecular sieve catalyst.But for improving Ti-MCM41 catalysis The hydrophobicity of agent, after molecular sieve catalyst end of synthesis, needs to use sillylation reagent to carry out catalyst additionally Silylanizing process so that the production process of catalyst is loaded down with trivial details, inefficiency, manufacturing cost is high.
Through retrieval, it was found that Nature magazine (1994,368,321) describes another and has meso-hole structure spy The titanium-containing molecular sieve catalyst (Ti-HMS) levied.Compared with Ti-MCM41, Ti-HMS has superior technique economy.But Ti- HMS catalysis material is due to catalyst active center's skewness, and surface hydrophobic is poor, with organic peroxide as oxidant When carrying out alkene epoxidation, product yield is low, poor catalyst stability, and deactivation rate is fast.
Therefore, for molecular sieve catalyst, in particular for the molecular sieve catalyst of epoxidation reaction of olefines, except titanium Outside the existence form of species, its pore passage structure and surface hydrophobic are also the key factors affecting its catalytic performance.Pore passage structure Determine applicable raw material and product molecule size, and surface hydrophobic determines the selectivity of product.Therefore, fabricated in situ There is composite pore structural and the good novel molecular sieve catalyst of surface hydrophobic is the developing direction of olefin epoxidation catalysts.
Summary of the invention
It is big that the technical problem to be solved in the present invention is to provide a kind of aperture, and has the selectivity of excellence and dividing of stability The preparation method of sub-sieve catalyst.
For solving above-mentioned technical problem, the technical scheme is that described synthetic method comprises the steps: that (1) will Silicon source Si (OR1)4、(R2O)3Si-(CH2)n1-Si(OR3)3(R4)n2Si(OR5)4-n2The 1/4 of total amount～4/5 and whole template Agent [(CH3)3CH3(CH2)n3N+]X-, mineralizer [(CH3C n4H 2n4)4NH4]+OH-And the mixture of water and ethanol enters at normal temperatures Row mixed hydrolysis；(2) after hydrolysis terminates, by titanium source Ti (OR6)4It is slowly added under fast stirring with the mixture in excess silicon source In silicon hydroxide solution after hydrolysis, carry out plastic, gelling temperature-5～60 DEG C；(3) transfer to crystallizing kettle enters by colloid Row crystallization, crystallization temperature 100～160 DEG C, crystallization time 1～72 hours；(4) carry out the molecular sieve after crystallization washing, filtering And roasting is to remove template, sintering temperature 500～600 DEG C, roasting 4～6 hours, obtain composite holes molecular sieve catalyst.
Further, the 1/3～3/4 of Zhan Gui source, the silicon source total amount added in described step (1)；In described step (2) Gelling temperature is 10～30 DEG C；Crystallization temperature in described step (3) is 120 DEG C, and crystallization time is 12～40 hours；Described step Suddenly the sintering temperature in (4) is 550 DEG C.
It is an advantage of the current invention that:
(1) molecular sieve catalyst of the present invention, the quaternary ammonium salt using relatively macromole size is template so that it is at organic hydroxide Under the mineralization of ammonium, fabricated in situ contains the composite holes catalysis material of mesopore-macropore structure, makes it possible to be applicable to different points The olefin hydrocarbon molecules of sub-size and corresponding epoxidation product, and solve mass transfer problem；Secondly, with the silicon source containing organo-functional group Part substituted for silicon acid esters, makes the HTS of synthesis not only have Si-O-Si key, a Si-O-Ti key, but also have hydrophobic and Molten carbon functional Si-(CH2)n1-Si、Si-O-Si(R4)n2With Ti-O-Si (R4)n2Functional group, so that catalyst has excellence Selectivity and stability；
(2) synthetic method of the molecular sieve catalyst of the present invention, uses and is loaded into active titanium species and the one of organo-functional group in situ Step synthetic method, significantly reduces production cost and the production cycle of molecular sieve catalyst, makes industrialized production be more feasible And economy.
Detailed description of the invention
The following examples can make professional and technical personnel that the present invention is more fully understood, but the most therefore by this Bright it is limited among described scope of embodiments.
Embodiment 1
Under the gentle agitation of room, add the silicon source tetraethyl orthosilicate of total amount 70%, two (triethoxysilyl) methane by accounting for plan Template cetyl trimethylammonium bromide, mineralizer tetraethyl hydroxide is joined with the mixed solution of trimethyoxysilane The mixed solution of ammonium and water is hydrolyzed, forms colourless transparent solution I；By residue 30% silicon source tetraethyl orthosilicate, two Shape is fully mixed with titanium source butyl titanate again after (triethoxysilyl) methane and trimethyoxysilane mixing Become mixed solution II；Under-5 DEG C and quick stirring, solution II is slowly added in solution I, forms light yellow transparent solution, And continue to stir 1 hour, it is designated as solution III；Solution III is transferred to carry out in stainless steel autoclave Crystallizing treatment, crystallization temperature 140 DEG C, crystallization time 72 hours.The pH value carry out the molecular sieve after crystallization filtering, washing to filtrate is 7～8, then exists Dry 12 hours for 110 DEG C, 550 DEG C of roastings 5 hours, obtain the composite holes molecular sieve catalyst of very hydrophobic.
During above-mentioned system with molecular sieve for preparing is standby, the component relationship of the amount of each material is [(CH3)3CH3 (CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2-Si(OC2H5)3: CH3Si(OCH3)3 :Ti(OC4H9)4:H2O =0.3:0.4:1:0.3:0.1:0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrum spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, Absworption peak is not had at other wavelength.Its infrared (FT-IR) spectrum spectrogram is at 960cm-1There is an obvious absworption peak at place. 95% embodiment 2
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, reduce the addition of butyl titanate.The amount of each material Component relationship is [(CH3)3CH3(CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2-Si (OC2H5)3: CH3Si(OCH3)3 :Ti(OC4H9)4:H2O=0.3:0.4:1:0.3:0.1:0.03:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrum spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, Absworption peak is not had at other wavelength.Its infrared (FT-IR) spectrum spectrogram is at 960cm-1There is an obvious absworption peak at place. The aperture size in the hole of more than 95% is more than 2nm.
Embodiment 3
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, reduce (C2H5O)3Si-CH2-Si(OC2H5)3Addition. The component relationship of the amount of each material is [(CH3)3CH3(CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4: (C2H5O)3Si-CH2-Si(OC2H5)3: CH3Si(OCH3)3 :Ti(OC4H9)4:H2O =0.3:0.4:1:0.2: 0.1:0.04: 10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, at it Absworption peak is not had at its wavelength.Its infrared spectrum spectrogram (FT-IR) is at 960cm-1There is an obvious absworption peak at place.95% with On the aperture size in hole more than 2nm.
Embodiment 4
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, adjust template and the addition of mineralizer.Each material The component relationship of amount is [(CH3)3CH3(CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si- CH2-Si(OC2H5)3: CH3Si(OCH3)3 :Ti(OC4H9)4:H2O=0.4:0.3:1:0.3:0.1:0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, at it Absworption peak is not had at its wavelength.Its infrared spectrum spectrogram (FT-IR) is at 960cm-1There is an obvious absworption peak at place.95% with On the aperture size in hole more than 2nm.
Embodiment 5
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, by (C2H5O)3Si-CH2-Si(OC2H5)3Replace with (C2H5O)3Si-CH2CH2-Si(OC2H5)3, the component relationship of the amount of each material is: [(CH3)3CH3 (CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2CH2-Si(OC2H5)3: CH3Si(OCH3)3 :Ti(OC4H9)4: H2O=0.3:0.4:1:0.3:0.1:0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, at it Absworption peak is not had at its wavelength.Its infrared spectrum spectrogram (FT-IR) is at 960cm-1There is an obvious absworption peak at place.95% with On the aperture size in hole more than 2nm.
Embodiment 6
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, by CH3Si(OCH3)3Replace with (CH3)2Si(OCH3)2, respectively The component relationship of the amount of material is: [(CH3)3CH3 (CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4: (C2H5O)3Si-CH2-Si(OC2H5)3: (CH3)2Si(OCH3)2 :Ti(OC4H9)4:H2O =0.3:0.4:1:0.3: 0.1: 0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrum spectrogram of this molecular sieve catalyst has stronger absworption peak at about 215 nm, Absworption peak is not had at other wavelength.Its infrared (FT-IR) spectrum spectrogram is at 960cm-1There is an obvious absworption peak at place. The aperture size in the hole of more than 95% is more than 2nm.
Embodiment 7～9
Molecular sieve catalyst prepared by embodiment 1～3 is carried out performance evaluation: at a band mechanical agitation and external jacket electric furnace Carrying out in the 1L stainless steel autoclave of heating, the outer set electric furnace automatic temp controller that adds of reaction temperature is adjusted.Dense with weight Degree be the ethylbenzene solution of the hydrogen peroxide ethylbenzene (EBHP) of 30% be oxidant, the addition of 30wt%EBHP oxidation solution is 400g, The addition of propylene is 185g, and the addition of molecular sieve catalyst is 8 g, reaction temperature 95 DEG C, reaction pressure 3.6MPa, reaction Time 3h.The catalytic performance test of molecular sieve catalyst the results are shown in Table 1.
In table 1, the result of embodiment 7～9 corresponds respectively to the molecular sieve catalyst as prepared by embodiment 1～3.
Embodiment 10～12
Molecular sieve catalyst prepared by embodiment 4～6 is carried out performance evaluation: at a band mechanical agitation and external jacket electric furnace Carrying out in the 1L stainless steel autoclave of heating, the outer set electric furnace automatic temp controller that adds of reaction temperature is adjusted.Dense with weight Degree be the cumene solution of the cumyl hydroperoxide (CHP) of 40% be oxidant, the addition of 40wt%CHP oxidation solution is 350g, the addition of propylene is 195g, and the addition of molecular sieve catalyst is 10 g, and reaction temperature is 90 DEG C, reaction pressure 3.5MPa, the response time is 3h.The catalytic performance test of molecular sieve catalyst the results are shown in Table 2.
In table 2, the result of embodiment 10～12 corresponds respectively to the molecular sieve catalyst as prepared by embodiment 4～6.
Embodiment 13～15
Molecular sieve catalyst prepared by embodiment 1～3 is carried out performance evaluation: at a band mechanical agitation and external jacket electric furnace Carrying out in the 1L stainless steel autoclave of heating, the outer set electric furnace automatic temp controller that adds of reaction temperature is adjusted.Dense with weight Degree be the ethylbenzene solution of the hydrogen peroxide ethylbenzene (EBHP) of 30% be oxidant, the addition of 30wt%EBHP oxidation solution is 350g, The addition of 1-butylene is 215g, and the addition of molecular sieve catalyst is 7.5 g, reaction temperature 90 DEG C, reaction pressure 2.5MPa, Response time 3h.The catalytic performance test of molecular sieve catalyst the results are shown in Table 3.
In table 3, the result of embodiment 13～15 corresponds respectively to the molecular sieve catalyst as prepared by embodiment 1～3.
Comparative example 1
Under the gentle agitation of room, join template cetyl front three by accounting for the silicon source tetraethyl orthosilicate intending adding total amount 70% The mixed solution of base ammonium bromide, mineralizer tetraethyl ammonium hydroxide and water is hydrolyzed, forms colourless transparent solution I；Will be surplus Yu 30% silicon source tetraethyl orthosilicate and titanium source butyl titanate carry out being mixed thoroughly to form mixed solution II；At-5 DEG C with fast Under speed stirring, solution II is slowly added in solution I, forms light yellow transparent solution, and continue to stir 1 hour, be designated as molten Liquid III；Solution III is transferred to carry out in stainless steel autoclave Crystallizing treatment, crystallization temperature 140 DEG C, crystallization time 72 hours；Will The pH value that molecular sieve after crystallization carries out filtering, wash to filtrate is 7～8, then dries 12 hours at 110 DEG C, 550 DEG C of roastings 5 hours, i.e. prepare contrast molecular sieve catalyst.
During above-mentioned system with molecular sieve for preparing is standby, the component relationship of the amount of each material is [(CH3)3CH3 (CH2)15N+]Br- : [(CH3CH2)4NH4]+OH-:Si(OC2H5)4: Ti(OC4H9)4:H2O=0.3:0.4:1:0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrum spectrogram of this molecular sieve catalyst has stronger absworption peak at about 220 nm, Also with the presence of a more weak absworption peak at 260nm.Its infrared (FT-IR) spectrum spectrogram is at 960cm-1Place has one significantly to absorb Peak.The aperture size in the hole of more than 85% is more than 2nm.
Comparative example 2
Compared with comparative example 1, simply template cetyl trimethylammonium bromide is replaced with Tetradecyl Trimethyl Ammonium Bromide, Mineralizer tetraethyl ammonium hydroxide replaces with Tetramethylammonium hydroxide, and other is constant.
The component relationship of the amount of each material is [(CH3)3CH3 (CH2)13N+]Br- : [(CH3)4NH4]+OH-:Si (OC2H5)4: Ti(OC4H9)4:H2O=0.3:0.4:1:0.04:10(mol ratio).
Ultraviolet-visible (UV-Vis) spectrogram of this molecular sieve catalyst has stronger absworption peak at about 220 nm, Also with the presence of a more weak absworption peak at 260nm.Its infrared spectrum spectrogram (FT-IR) is at 960cm-1Place has one significantly to absorb Peak.The aperture size in the hole of more than 80% is more than 2nm.
Comparative example 3,4
Molecular sieve catalyst as prepared by comparative example 1,2 is carried out catalytic performance test by the evaluation methodology of embodiment 7～9, Evaluation result is shown in Table 1.In table 1, the result of comparative example 3,4 corresponds respectively to the molecular sieve catalyst as prepared by comparative example 1,2.
Comparative example 5,6
By the evaluation methodology of embodiment 10～12, the molecular sieve catalyst as prepared by comparative example 1,2 is carried out catalytic performance comment Valency, evaluation result is shown in Table 2.In table 2, the result of comparative example 5,6 corresponds respectively to the molecular sieve catalytic as prepared by comparative example 1,2 Agent.
Table 1
As can be seen from the above table, the molecular sieve catalyst of embodiment 1～3 compared with the molecular sieve catalyst of comparative example 1 and 2, its Catalyst performance is better than comparative example, EBHP conversion ratio and expoxy propane and selects equal ＞ 99%.
Table 2
As can be seen from the above table, the molecular sieve catalyst of embodiment 4～6 compared with the molecular sieve catalyst of comparative example 1 and 2, its Catalyst performance is better than comparative example, EBHP conversion ratio and expoxy propane and selects equal ＞ 99%.
Table 3
As can be seen from the above table, the catalyst performance of the molecular sieve catalyst of embodiment 1～3 is more excellent, its EBHP conversion ratio and ring Oxygen butane selects equal ＞ 99%.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The skill of the industry The art personnel simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these Changes and improvements both fall within scope of the claimed invention.Claimed scope by appending claims and Its equivalent defines.

Claims (2)

1. the synthetic method of a molecular sieve catalyst, it is characterised in that: described synthetic method comprises the steps:
(1) by silicon source Si (OR1)4、(R2O)3Si-(CH2)n1-Si(OR3)3(R4)n2Si(OR5)4-n21/4～4/5 He of total amount All template [(CH3)3CH3(CH2)n3N+]X-, mineralizer [(CH3C n4H 2n4)4NH4]+OH-And the mixture of water and ethanol exists Mixed hydrolysis is carried out under room temperature；
(2) after hydrolysis terminates, by titanium source Ti (OR6)4After being slowly added into hydrolysis under fast stirring with the mixture in excess silicon source Silicon hydroxide solution in, carry out plastic, gelling temperature-5～60 DEG C；
(3) colloid is transferred to carry out in crystallizing kettle crystallization, crystallization temperature 100～160 DEG C, crystallization time 1～72 hours；
(4) carry out the molecular sieve after crystallization washing, filter and roasting is to remove template, sintering temperature 500～600 DEG C, roast Burn 4～6 hours, obtain composite holes molecular sieve catalyst.
The synthetic method of molecular sieve catalyst the most according to claim 1, it is characterised in that: described step (1) adds Zhan Gui source, silicon source total amount 1/3～3/4；Gelling temperature in described step (2) is 10～30 DEG C；In described step (3) Crystallization temperature is 120 DEG C, and crystallization time is 12～40 hours；Sintering temperature in described step (4) is 550 DEG C.
CN201610689607.4A 2016-08-19 2016-08-19 Method for preparing molecular sieve based catalyst Pending CN106311324A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610689607.4A CN106311324A (en) 2016-08-19 2016-08-19 Method for preparing molecular sieve based catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610689607.4A CN106311324A (en) 2016-08-19 2016-08-19 Method for preparing molecular sieve based catalyst

Publications (1)

Publication Number Publication Date
CN106311324A true CN106311324A (en) 2017-01-11

Family

ID=57744207

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610689607.4A Pending CN106311324A (en) 2016-08-19 2016-08-19 Method for preparing molecular sieve based catalyst

Country Status (1)

Country Link
CN (1) CN106311324A (en)

Similar Documents

Publication Publication Date Title
CN101757945B (en) Titanium-silicon molecular sieve TS-1 catalyst for catalyzing ketone oximation reaction
JP6337144B2 (en) Mesoporous material-coated cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof
CN102858758A (en) Process for the manufacture of propylene oxide
CN105367520B (en) The method for preparing expoxy propane
JP2017521227A5 (en)
CN109772459B (en) Chiral polyacid-based metal organic framework material and preparation method and application thereof
JP2012232891A (en) Titanium-silicalite molecular sieve, method for preparing the same and method for preparing cyclohexanone oxime using the molecular sieve
CN105540608B (en) A kind of Y Beta composite molecular screens of pair of meso-hole structure and preparation method thereof
CN102895994A (en) Ti-SBA-15 molecular sieve, modified Ti-SBA-15 molecular sieve, their preparation methods and preparation method of epoxy propane
CN106391106B (en) A kind of preparation method of the core-shell structure molecular sieve containing metal
CN108273547A (en) A method of carried molecular sieve catalyst is prepared using vacuum impregnation technology
CN109231233A (en) A kind of green synthesis method of Ti-MWW molecular sieve and application
CN106111185A (en) A kind of titanium-silicon molecular sieve catalyst and its preparation method and application
CN108821304A (en) High activity multi-stage porous Titanium Sieve Molecular Sieve and its preparation method and application
Corma et al. Ti-ferrierite and TiITQ-6: synthesis and catalytic activity for the epoxidation of olefins with H 2 O 2
CN104437636B (en) Titaniferous porous silica Si catalyst, preparation method and its usage
CN106315608A (en) Method for preparing efficient titanium silicalite molecular sieve catalyst
CN106040294B (en) A kind of preparation method of SBA-15/SAPO-34 nucleocapsid molecular sieves for methanol to propylene reaction
CN106268941A (en) A kind of preparation method of the titanium-silicon molecular sieve catalyst containing organo-functional group
CN106348311A (en) Preparation method of titanium-silicalite-molecular-sieve catalyst
CN106311324A (en) Method for preparing molecular sieve based catalyst
CN102807538B (en) Method for preparing propylene oxide
CN102807537B (en) Method for preparing propylene oxide
CN106378182A (en) An efficient titanium silicalite molecular sieve catalyst
CN106316991A (en) Application of titanium silicalite molecular sieve catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170111

WD01 Invention patent application deemed withdrawn after publication