CN109231233A - A kind of green synthesis method of Ti-MWW molecular sieve and application - Google Patents

A kind of green synthesis method of Ti-MWW molecular sieve and application Download PDF

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CN109231233A
CN109231233A CN201811234587.7A CN201811234587A CN109231233A CN 109231233 A CN109231233 A CN 109231233A CN 201811234587 A CN201811234587 A CN 201811234587A CN 109231233 A CN109231233 A CN 109231233A
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titanium
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CN109231233B (en
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陈晓晖
张明逸
黄清明
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Fuzhou University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/06Preparation 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
    • C01B39/08Preparation 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
    • C01B39/085Group IVB- metallosilicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049Crystalline 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
    • B01J29/7088MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/46Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a kind of green synthesis method of Ti-MWW molecular sieve and applications.The thought of the synthetic method is derived from mechanical milling method, the combination of dry gum method and crystal seed method.Firstly, titanium source and silicon source are added in ball grinder according to a certain percentage, ball milling is carried out, forms titanium silicon compound.Then, crystal seed, boric acid are added into tank, continues to grind, obtains dry glue.The dry glue of acquisition is placed in crystallization in template steam again, obtains Ti-MWW precursor.Finally, being post-processed to obtain the Ti-MWW molecular sieve of finished product to precursor.This method is compared with conventional hydrothermal method, and the dosage of boric acid reduces 86%, and the dosage of template reduces about 50%, and the dosage of water reduces about 85%, is compared with the traditional method conversion ratio with higher and selectivity, meets Green Chemistry and industrial requirement.

Description

A kind of green synthesis method of Ti-MWW molecular sieve and application
Technical field
The invention belongs to petrochemical catalyst synthesis and application fields, specifically, being related to Ti-MWW molecular sieve Green synthesis method and application belong to Inorganic synthese field.
Background technique
Nineteen ninety, Mobil Corporation (US, 4954325) in its patent report the synthesis of MCM-22 molecular sieve for the first time. 1999, the method for Corma etc. (Chem Commun, 1999 (9): 779-780) grafting synthesized Ti-ITQ-2;2000 Year, it is mentioned in the patent (US, 6114551) of Mobil Corporation and uses TiCl4Ti- has been made in the MCM-22 of gas phase same order elements dealuminzation MCM -22, mending the main problem of the Titanium Sieve Molecular Sieve of titanium method preparation using this rear synthesis is the Ti ratio under liquid-phase reaction condition It is easier to be lost.
Classical hydrothermal synthesis method is the relatively conventional method of synthesis of molecular sieve, it is divided into a step hydrothermal synthesis and secondary hydro-thermal Synthesis.Wu etc. (Chem Lett, 2000,29, (7): 774~775) being added boric acid as crystallization promoting agent in preparing gel, Use hexamethylene imine (HMI) or piperidines (PI) that a hydro-thermal method is successfully used to synthesize Ti-MWW molecular sieve as template. Wu etc. (Chem Commun, 2002 (10): 1026-1027) successfully synthesizes Ti-MWW using the reversible two-step fabrication of structure, first Borosilicate MWW molecular sieve (ERB-1) is first synthesized with hydro-thermal method, by roasting, the MWW molecular sieve (Si/ of almost pure silicon is obtained after pickling B>1000).The template aqueous solution containing titanium source is added, is stirred, has obtained Ti-MWW molecular sieve stratiform presoma after crystallization.Most Afterwards, to its pickling, roasting, Ti-MWW is obtained.For classical hydro-thermal major problem is that, toxic template, boric acid, water etc. originals Expect that dosage is larger, synthesis process generates more waste water, increases the load of environment, and it is also its great asking of facing that synthesis cycle is long Topic.Meanwhile the synthesis process of molecular sieve is more demanding for the operation of experimenter.
Wu etc. synthesizes Ti-MWW using dry gum method (Catalysis Today, 2005,99 (1-2): 233-240.). After mixing evenly by silicon source, titanium source and boric acid aqueous solution, heating obtains dry glue, then makees in hexamethylene imine or piperidines steam Product is obtained with lower crystallization.Since the skeleton Ti content as activated centre is low and zeolite crystal size is original molecule sieve 10-20 times so that reactant diffusion rate in the duct of molecular sieve substantially reduces, cause catalytic activity not high, just oneself Conversion ratio only has 6.5% or so in the epoxidation of alkene.
Currently, a kind of higher Ti-MWW molecular sieve of available catalytic activity is found not yet, meanwhile, it can effectively solve The problems such as exorbitant expenditure of the raw materials such as certainly toxic template, boric acid, water, manufacturing cycle is too long, and it is environmentally friendly, facilitate reality Test the synthetic method of personnel's operation.By combining one step dry gum method synthesis of molecular sieve of mechanico-chemical reaction, can be effectively synthesized out The higher Ti-MWW of catalytic activity.Compared with conventional hydrothermal method, raw material materials are reduced, and the dosage of boric acid reduces 86%, template Dosage reduces about 50%, and the dosage of water reduces about 85%, and the waste water accordingly generated is also reduced.More traditional dry gum method, synthesis cycle contracting Short half, green and for environmental-friendly operate convenient for experimenter.
Summary of the invention
The purpose of the present invention is intended to provide a kind of step dry gum method synthesis Ti-MWW molecular sieve of combination machinery chemical route Method.It is characterized in that first grinding using planetary ball mill to silicon source and titanium source, titanium silicon compound is obtained.Again to it Middle addition boric acid and crystal seed, grinding obtain dry powder.Then, Ti-MWW is synthesized using dry gum method.Finally, being carried out to Ti-MWW precursor Post-processing, obtains Ti-MWW molecular sieve.
The green synthesis method of Ti-MWW of the present invention a kind of the following steps are included:
The synthesis of first step titanium silicon compound
Silicon source and titanium source are mixed in a certain ratio and are placed in ball grinder, ball mill is operated.Wherein, silicon source is (with SiO2Meter) it is white One or both of carbon black, silica gel.Titanium source is (with TiO2Meter) it is one or both of titanium sulfate, titanium dioxide.Ball mill Revolving speed be 200 ~ 800rpm, runing time be 12 ~ 120h.Silicon and titanium molar ratio are 10 ~ 60.
The preparation of second step dry glue
Crystal seed, boric acid are added in grinding pot by a certain percentage, continue to grind, obtains so-called dry glue.Wherein, crystal seed is boracic MWW, one or more of MWW, the Ti-MWW of synthesis of boron removal, quality is the 1 ~ 50% of silicon source quality.Silicon boron molar ratio Be 1 ~ 15, runing time be 1 ~ for 24 hours, revolving speed be 200 ~ 400rpm.
Third crystallization
Dry glue is placed in small container, template and water are placed in by a certain percentage in the autoclave containing polytetrafluoro liner, And small container is placed in liner.Under certain temperature, in the mixed vapour of template and water, static crystallization.Wherein, template For piperidines or hexamethylene imine, crystallization temperature is 140 ~ 180 DEG C, and crystallization time is 24 ~ 168h, mole of silicon source and template Than are as follows: 1 ~ 2.5, the ratio of silicon source and water are as follows: 0.1 ~ 0.8.
The post-processing of 4th step
The Ti-MWW molecular sieve of synthesis is first handled with acid, is then roasted at a certain temperature.Finally, finished product is obtained Ti-MWW molecular sieve.Wherein, the acid that pickling uses be nitric acid or sulfuric acid, concentration be 1 ~ 6mol/L, pickling time be 6 ~ 24h;Maturing temperature is 500 ~ 650 DEG C, and calcining time is 6 ~ 12h.
The present invention is characterized in that compared in Ti-MWW preparation process with classical hydrothermal synthesis method, boric acid, piperidines, water Dosage is preferred are as follows: silicon source and the molar ratio of boric acid are 1~12, and silicon source and template molar ratio are 1 ~ 1.8, mole of silicon source and water Than are as follows: 0.1 ~ 0.6.
The Ti-MWW molecular sieve that synthetic method provided by the invention obtains is applied as catalyst in propylene, n-hexylene, alkene In the epoxidation reaction of propyl alcohol.Wherein, Ti-MWW is higher by twice in the epoxidised yield of n-hexylene than traditional dry gum method, with classics Hydro-thermal method is suitable.
This method has following remarkable advantage compared with prior art:
1, relative to conventional synthesis process, there is particular/special requirement for organic titanium source hydrolysis degree, may be generated in synthesis process Anatase phase titanium dioxide, unfavorable to reacting, synthesis process is for high operation requirements.Present invention combination mechanico-chemical reaction, will Silicon source and titanium source, which are previously placed in ball mill, carries out ball milling, forms unformed titanium silicon compound, easy to operate, easily controllable.
2, during conventional synthesis, a large amount of boron in raw material is being filtered, is being washed there is no completely into Ti-MWW skeleton During washing, as deionized water elutes.The present invention can reduce the dosage of starting boronic acid, and silicon boron ratio is preferably in raw material 1~12, synthesize the identical Ti-MWW molecular sieve of structure.
3, relative to classical hydro-thermal method, in crystallization process, reduce the dosage of template and the use of water in raw material The molar ratio of amount, silicon source and template is preferred are as follows: and 1 ~ 1.8, the molar ratio of silicon source and water is preferred are as follows: 0.1 ~ 0.6.The invention is not only Production cost is reduced, also avoids generating a large amount of waste water, reduces the load of environment, while also reducing reaction kettle internal cause pressure Excessive and generation safety problem is a kind of safe, green, environmentally friendly synthetic method.
4, traditional dry gum method synthesis process, the Zeolite synthesis period is 336h, and mechanical lapping is used to react a step dry glue Method synthesizes Ti-MWW, only needs 168h, shortens half the time, reduces production cost.
Detailed description of the invention
Fig. 1 is the XRD spectra for the product Ti-MWW molecular sieve that embodiment 1 obtains.
In Fig. 1, molecular sieve has typical MWW structure, in 2 θ=7.22 °, 7.90 °, and 9.54 °, 14.42 °, 16.14 °, There is characteristic peak at 22.64 °, 23.72 °, 26.14 °.X-ray powder diffraction instrument (XRD, PANalytical Axios Petro Diffractometer) using Cu-K α be radiographic source instrument, test condition be voltage 45kV, electric current 40mA, scanning range be 5 °~ 45 ° of sweep speeds are 0.1458 °/s.
Specific embodiment
Ti-MWW molecular sieve is synthesized to one step dry gum method of mechanico-chemical reaction of the present invention below by specific example It is described further.
Embodiment 1
Step 1: the preparation of titanium silicon compound.Take the Shanghai white carbon black 100g(Shan Bo Industrial Co., Ltd.), titanium dioxide 2.659g (Aladdin reagent), wherein silicon source and titanium source are 50 in molar ratio.It is mixed and is placed in ball grinder, ball mill is Nanjing spy wheel New instrument Co., Ltd, revolving speed 800rpm, runing time 48h.
Step 2: the preparation of dry glue.The crystal seed for being equivalent to silicon source quality 10%, i.e. 10g crystal seed are taken, boric acid 20.6g is added In grinding pot, continue to grind, revolving speed 300rpm, runing time 2h, obtained dry glue.Wherein, Si/B=5, crystal seed are boron removal MWW(Microporous Materials, 1995,4 (2-3): 221-230).
Step 3: crystallization.It takes 20g dry glue to be placed in small container, then takes 15g piperidines (PI, wako), 11.3g water is placed in and contains There is in the autoclave of polytetrafluoro liner (Jin Jun chemical machinery Co., Ltd, model 500ml steam heat reaction kettle) simultaneously Small container is placed in liner.Then at 150 DEG C, in the mixed vapour of piperidines and water, static crystallization 72h.Wherein, Si/PI= 1.4, Si/H2O=0.4。
Step 4: post-processing.Ti-MWW molecular sieve precursor is taken, with 2mol/L nitric acid treatment 12h, is then roasted at 550 DEG C Burn 6h.Finally, the Ti-MWW molecular sieve of finished product is obtained.
Embodiment 2~6
Except for the following differences, remaining is with embodiment 1, and for the ratio of substance in addition to special remarks, other is all mole for implementation process Than.
Embodiment 2: silicon source is silica gel in the first step, and titanium source is titanium sulfate, Si/Ti=60, drum's speed of rotation 700rpm, Runing time is 72h;Si/B=8 in second step, crystal seed are the 30% of silicon source quality, and the revolving speed of ball mill is 200rpm, when operation Between be 1h;Si/PI=1 in third step, Si/H2O=0.5, crystallization temperature are 170 DEG C, crystallization time 48h;Nitric acid is dense in 4th step Degree is 1mol/L, and the acid processing time is 10h, and maturing temperature is 500 DEG C, calcining time 6h.
Embodiment 3: in the first step, titanium source is titanium sulfate, Si/Ti=40, drum's speed of rotation 700rpm;In second step, Si/B=12, the revolving speed of ball mill are 300rpm, and runing time 12h, crystal seed is the MWW of boracic, and crystal seed is silicon source quality 20%;Si/H in third step2O=0.6;Concentration of nitric acid is 4mol/L in 4th step, and the acid processing time is 12h, maturing temperature 650 DEG C, calcining time 12h.
Embodiment 4: in the first step, silicon source is silica gel, and titanium source is titanium sulfate, Si/Ti=20, drum's speed of rotation 400rpm, Runing time is 96h;Si/B=15 in second step, crystal seed Ti-MWW, quality are the 50% of silicon source quality, and the revolving speed of ball mill is 200rpm, runing time are for 24 hours;Si/HMI(hexamethylene imine in third step)=1.6, Si/H2O=0.1, crystallization temperature are 180 DEG C, crystallization time 120h;Sulfuric acid washing, sulfuric acid concentration 4mol/L are used in 4th step, the acid processing time is 10h, roasting Temperature is 600 DEG C, calcining time 10h.
Embodiment 5: in the first step, Si/Ti=30, drum's speed of rotation 600rpm, runing time 120h;In second step Si/B=4, the revolving speed of ball mill are 300rpm, runing time 4h;Si/PI=1.2 in third step, Si/H2O=0.1, crystallization temperature Degree is 170 DEG C, crystallization time 168h;Concentration of nitric acid is 4mol/L in 4th step, and the acid processing time is 18h, maturing temperature 600 DEG C, calcining time 10h.
Embodiment 6: in the first step, Si/Ti=10, drum's speed of rotation 200rpm, runing time 120h;In second step, Si/B=1, crystal seed are the 1% of silicon source quality, and the revolving speed of ball mill is 400rpm, runing time 6h;In third step, Si/PI= 1.8, Si/H2O=0.3, crystallization temperature are 140 DEG C, and crystallization time is for 24 hours;Concentration of nitric acid is 6mol/L in 4th step, when acid is handled Between be 20h, maturing temperature be 650 DEG C, calcining time 6h.
Comparison case illustrates what the Ti-MWW of traditional dry gum method and hydro-thermal method synthesis was synthesized with one step dry gum method of mechanical lapping The difference of Ti-MWW.
Comparative example 1
This comparative example illustrates the conventional dry proposed according to Wu et al. (Catalysis Today, 2005,99 (1): 233-240) Glue method synthesizes Ti-MWW molecular sieve.Ti-MWW is prepared according to a dry gum method, butyl titanate is added to hydrogen peroxide first In, form solution A;White carbon black, boric acid are mixed with crystal seed later, deionized water is added and forms solution B, by A, two kinds of solution of B Mixing, stirring.Then it is evaporated at 80 DEG C, obtains dry glue.Dry glue is placed in piperidines steam again, with 170 DEG C of crystallization 168h.It is right Crystallization liquid is washed, is dried, and 2mol/L HNO is then used3Pickling 12h.Finally, roasting 6h at 550 DEG C, Ti-MWW is obtained Molecular sieve.Wherein, crystal seed is the B-MWW of boron removal, is matched as Si/Ti=30, Si/B=2, SiO2: H2O:PI=1:2.5:0.69. Crystal seed is the 10% of silicon source quality.
Comparative example 2
This comparative example explanation according to Wu et al. (Journal of Physical Chemistry B, 2001,105 (15): 2897-2905.) the conventional hydrothermal method proposed prepares Ti-MWW molecular sieve.Firstly, piperidines is dissolved in deionized water at room temperature In, and it is divided into two parts of A, B.Butyl titanate is added into A, boric acid is added into B.Then, A, B is added in white carbon black etc. point In two solution.A, B solution are mixed again, stirring.The gel of synthesis is placed in autoclave, with 100rpm, 170 DEG C of dynamics Crystallization 168h.Then by crystallization product washing, dry, then with 2mol/L HNO3Pickling 12h.Finally, being roasted at 600 DEG C 10h obtains Ti-MWW molecular sieve.Wherein, SiO2: TiO2: B2O3: PI:H2O=1:0.02:0.67:1.4:19.
By the catalyst of 6 gained catalyst of above-described embodiment 1- embodiment and comparative example 1-2 carry out active testing, with just oneself The epoxy of alkene turns to probe reaction, condition are as follows: the n-hexylene of 10mmol, the hydrogen peroxide of 10mmol, the solvent of 10ml, 0.1g Ti-MWW, reaction temperature are 60 DEG C, reaction time 2h.
Analysis method: chromatography model: Agilent6890, chromatographic column: HP-5MS, 30m, 0.32mm, 0.25um, internal standard compound For cyclohexanone.
Gas condition: hydrogen flowing quantity: 40ml/min, air mass flow: 450ml/min, split ratio 30, sample volume are 1 micro- It rises.
Using 50 DEG C of temperature programming initial temperature, residence time 2min, 5 DEG C/min of heating rate, 250 DEG C of final temperature, Residence time 1 minute.The epoxidised reaction result of 1- hexene is as shown in table 1, and embodiment 2 ~ 6 and comparative example 1, comparative example 2 obtain Ti-MWW XRD diagram it is consistent with Fig. 1.
As it can be seen from table 1 the activity of the activity and conventional hydrothermal method of Ti-MWW obtained by one step dry gum method of mechanical lapping connects Closely, the activity of more traditional dry gum method is high very much.
Table 1
Embodiment described above is only several embodiments of the invention, and description is more specific and detailed, but can not understand For limitations on the scope of the patent of the present invention, used in chemicals be the pure above chemicals of commercially available chemistry, not into one Step processing.It should be pointed out that those skilled in the art, based on by present inventive concept on, can make several It improves, these are all belonged to the scope of protection of the present invention.Therefore, the scope of protection of the patent of the present invention is with the attached claims It is quasi-.

Claims (10)

1. a kind of green synthesis method of Ti-MWW molecular sieve, it is characterised in that the following steps are included: the synthesis of titanium silicon compound, The crystallization product of preparation is carried out pickling, forged by the preparation of dry glue, dry glue static crystallization in the mixed vapour of template and water It burns.
2. the green synthesis method of Ti-MWW molecular sieve according to claim 1, it is characterised in that: the conjunction of titanium silicon compound At being to be ground using planetary ball mill to titanium source and silicon source, wherein revolving speed is 200 ~ 800rpm, runing time is 12 ~ 120h, silicon titanium molar ratio are 10 ~ 60.
3. synthetic method according to claim 1, it is characterised in that: the preparation of dry glue is by crystal seed, boric acid by certain ratio Example be added titanium silicon compound in, crystal seed be silicon source quality 1% ~ 50%, silicon boron molar ratio be 1 ~ 15, ball mill runing time be 1 ~ For 24 hours, revolving speed is 200 ~ 400rpm.
4. synthetic method according to claim 1, it is characterised in that: dry glue is placed in polytetrafluoroethylcontainer container, template Agent and water are placed in by a certain percentage in the autoclave equipped with polytetrafluoro liner, and polytetrafluoroethylcontainer container is placed in liner In, under certain temperature, in the mixed vapour of template and water, static crystallization.
5. synthetic method according to claim 1, it is characterised in that: the acid that pickling uses is nitric acid or sulfuric acid, concentration For 1 ~ 6mol/L, pickling time is 6 ~ for 24 hours;Maturing temperature is 500 ~ 650 DEG C, and the time is 6 ~ 12h.
6. the Ti-MWW molecular sieve that synthetic method according to claim 1 obtains as catalyst, can be applicable to propylene, just Hexene, allyl alcohol epoxidation reaction in.
7. synthetic method according to claim 2, it is characterised in that: titanium source be one of titanium sulfate, titanium dioxide or Two kinds;Silicon source is one or both of white carbon black, silica gel.
8. synthetic method according to claim 3, it is characterised in that: crystal seed is MWW, Ti-MWW of the MWW of boracic, boron removal One or more of.
9. synthetic method according to claim 4, it is characterised in that: template is piperidines or hexamethylene imine;Silicon source With the molar ratio of template are as follows: 1 ~ 1.8;The molar ratio of silicon source and water are as follows: 0.1 ~ 0.6.
10. synthetic method according to claim 4, it is characterised in that: crystallization temperature is 140 ~ 180 DEG C, and crystallization time is 24~168h。
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CN109651090B (en) * 2019-01-26 2021-12-03 福州大学 Method for preparing 2, 5-dimethylphenol by catalyzing hydroxylation of p-xylene with Bi-MWW
CN110054198A (en) * 2019-05-26 2019-07-26 福州大学 A kind of preparation method of Ti-MWW molecular sieve
CN111847474A (en) * 2020-07-17 2020-10-30 浙江恒澜科技有限公司 Ti-ITQ-24 zeolite molecular sieve and in-situ synthesis method and application thereof
CN112537776A (en) * 2020-12-23 2021-03-23 中触媒新材料股份有限公司 Preparation method of Ti-ZSM-5 molecular sieve

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