CN104437616B - Stratiform containing mesopore titanium-silicon molecular sieve catalyst and its preparation method and application - Google Patents
Stratiform containing mesopore titanium-silicon molecular sieve catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to stratiform containing mesopore titanium-silicon molecular sieve catalyst and its preparation method and application, its twelve-ring hole with MWW high-silica zeolites and sinusoidal reticulated channel system, its interlayer has 2-10nm meso-hole structures, and four-coordination state titanium or there is the titanium of four-coordination state and the titanium of hexa-coordinate state simultaneously, include following steps：MWW high-silica zeolites containing template agent are that presoma is swelled, then through filtering, washing, dry；Progress is pillared, then filters, dries；Hydrolysis, inorganic wall and meso-hole structure are formed in MWW high-silica zeolite interlayers, filtered, wash, are dried again；High-temperature calcination, obtains the titaniferous MCM 36 of microporous mesoporous composite construction.The column-supporting agent that this method is mixed using new silicon source and titanium source carries out pillared method, has prepared the mesoporous pure HTS containing titanium component, eliminates the Bronsted acidity position of boron or aluminium in molecular sieve precursor.
Description
Technical field
It is more particularly to a kind of to be applied to carbon-to-carbon double bond and other at least one functions the present invention relates to a kind of catalyst
Dough compound epoxidation or the stratiform containing mesopore titanium-silicon molecular sieve catalyst of ammoxidation and its preparation method and application.
Background technology
MWW types molecular sieve has two mutual 10 independent membered ring channels, and the supercage of 12 yuan of rings is contained in one of duct
(0.71nm × 1.81nm), have in addition on the surface of crystal entrance be 12 yuan of rings bowl-shape hole (science, Science,
1994,264:1910).The type molecular sieve not only unique structure, and because it derives from stratiform presoma, structure has plastic
The characteristics of property and modifiability are strong.Si-Al molecular sieve-MCM-22 of the MWW structures synthesized with hydro-thermal method, as solid acid
Catalyst realizes industrial applications during the olefin alkylation of benzene prepares ethylbenzene and isopropylbenzene.And titaniferous MWW molecular sieves
It is always the challenge object of many research groups because synthesis condition is harsh.Corma etc. chemical communication (Chem Commun,
1999:779) method of middle grafting, titanium is grafted onto the MCM-22 of layer stripping, synthesizes Ti-ITQ-2.United States Patent (USP)
6114551 use TiC14Ti-MCM-22 has been made in the MCM-22 of gas phase same order elements dealuminzation.It is prepared by these secondary synthesis methods
Titanium silicon MWW structure molecular screens synthesis cost it is high, and Ti therein is easier to be lost in.United States Patent (USP) 6759540 and Wu
Deng in physical chemistry magazine B (J.Phys.Chem.B, 2001,105:2897) added in using hydro-thermal method in the gel of preparation
Boric acid does crystallization in motion agent, using hexamethylene imine or piperidines as structure directing agent, takes the lead in successfully synthesizing titanium silicon MWW molecular sieves
Ti-MWW.In order to solve the less problem of Ti-MWW molecular sieve pore passage diameters, Wu etc. is in JACS
(J.Am.Chem.Soc.,2008,130:8178) for connecting weaker between Ti-MWW molecular sieve layers the characteristics of, in aqueous solution of nitric acid
In, by Ti-MWW stratiforms presoma through silylating reagent dimethyldiethoxysilane reflow treatment, monolayer silicon is inserted into interlayer,
The IEZ-Ti-MWW molecular sieves of interlayer reaming are obtained after fired again.IEZ-Ti-MWW intactly remains MWW basic structure
Unit, silanization treatment to increase to 2.75nm by original about 2.5nm along the interlamellar spacing in c-axis direction, only makes interlamellar spacing
Increase 0.26nm.However, being that Ti-MWW or IEZ-Ti-MWW HTSs belong to microcellular structure molecular sieve.
The excellent molecule shape selectivity of micro porous molecular sieve and good catalytic perfomance, make its answering in petrochemical industry
With widely.But in the occasion for being related to bigger molecule reactant, the less pore size of micro porous molecular sieve makes macromolecular reaction
Thing is difficult to enter duct and close to active sites in its duct, so as to limit its application.Therefore, develop and be adapted to macromolecular reaction
Larger duct novel molecular sieve be always research target.Roth etc. is studied on surface and catalytic science
(Stud.Surf.Sci.Catal., 1995,94:301) in by precursor synthesis of MCM-22 layer column molecular sieve MCM-36,
It not only remains the micropore hole in the double sinusoidal ducts of two-dimentional 10 yuan of rings and the yuan of rings supercage hole of layer outer surface 12 in MCM-22 layer
Road system, and the formation of its interlayer 2nm meso-hole structures makes MCM-36 that there is bigger specific surface area and the big of interlayer acidic site to divide
Sub- accessibility.This makes MCM-36 compared with MCM-22 molecular sieves, such as wax catalysis cracking, isobutane alkylation,
Alkylating aromatic hydrocarbon, methanol convert in many reactions such as hydro carbons processed and all show more excellent catalytic reaction activity.
Although Ahn seminar of South Korea is in Chemistry Letters (Catal.Lett., 2007,113:160) opened in for Ti-MWW
The research of the pillared MWW molecular sieves for preparing mesoporous titaniferous of interlayer has been opened up, but research is only limitted to using Ti-MWW as presoma, completely
Indiscriminately imitate (Stud.Surf.Sci.Catal., 1995,94 such as Roth:301) method proposed prepares MCM-36.Due to Ti-MWW knots
Structure can not show a candle to MCM-22 stabilizations, and MWW structures receive serious destruction, this system under the strong basicity treatment conditions of swelling process
Standby titaniferous MCM-36 method is simultaneously unsuccessful.
In summary, so far, the titaniferous MWW for preparing introducing meso-hole structure of also no document report successful stabilization
Structure molecular screen.Therefore the HTS conduct that a kind of efficient method synthesizes containing mesopore structure based on MWW structures is developed
Macromolecule reactant epoxidation and the catalyst of ammoxidation, are to work as previous urgent problem.
The content of the invention
The present invention provides a kind of preparation of stratiform containing mesopore titanium-silicon molecular sieve catalyst for above-mentioned existing situation and answered
With technology, it can be remained as epoxidation and the catalyst of ammoxidation, the MCM-36 containing catalytic activity titanium component of gained
The twelve-ring hole of MWW structural integrities and sinusoidal reticulated channel system, and the meso-hole structure not less than 2nm is added, it is mesoporous
Introducing will be effectively promoted the transmission and diffusion of molecule, improve catalytic perfomance.
The present invention solves the technical scheme that is used of above-mentioned technical problem：Stratiform containing mesopore titanium-silicon molecular sieve catalyst,
Its twelve-ring hole with MWW high-silica zeolites and sinusoidal reticulated channel system, its interlayer have the mesoporous knots of 2-10nm
Structure, and four-coordination state titanium or there is the titanium of four-coordination state and the titanium of hexa-coordinate state simultaneously.
The preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst, includes following steps：
1) the MWW high-silica zeolites containing template agent are that presoma is swelled under high ph-values environment using sweller,
Then through filtering, washing, dry；
2) it is pillared in the MWW high-silica zeolites interlayer introducing pillaring agent progress being swelled, then filter, dry；
3) it is put into the further hydrolysis of progress in the aqueous solution instead by being introduced into the MWW high-silica zeolite solids of pillaring agent
Should, in the pillared inorganic wall of MWW high-silica zeolite interlayer shapes and corresponding meso-hole structure, filter, wash, dry again；
4) the obtained dried powder containing template agent, sweller and pillaring agent hydrolysate finally is carried out into high temperature to forge
Burn, obtain the titaniferous MCM-36 of micropore-mesopore composite construction.
By such scheme, step 4) obtained material is by acid treatment, by filtering, washing, being dried to obtain acid treatment production
Thing, is used as catalyst.
By such scheme, 0.5-1nm micropore is distributed with the titaniferous MCM-36 of described micropore-mesopore composite construction,
Its interlayer has 2-10nm's mesoporous.
The co-ordination state of titanium present in the MCM-36 samples wherein prepared includes four-coordination state, matches somebody with somebody there is also six
Position state.By controlling the ratio of titanium and silicon in pillaring agent, passing through step 4) dinectly bruning can prepare hexa-coordinate and four and match somebody with somebody
The different titaniferous MCM-36 samples of position ratio.The MCM-36 containing only four-coordination state titanium can be obtained by further acid treatment
Sample.
By such scheme, step 1) described in MWW high-silica zeolites sial or silicon boron ratio be 5-1000.
By such scheme, step 1) described in MWW high-silica zeolites sial or silicon boron ratio be 30-300.
By such scheme, step 1) described in sweller be organic cation quaternary ammonium salt aqueous solution or organic cation quaternary amine
Aqueous alkali or its mixture.
By such scheme, described organic cation quaternary ammonium salt aqueous solution is alkyl trimethyl ammonium salt type, dialkyl group diformazan
Base ammonium salt type or alkyl dimethyl benzyl ammonium salt type.
By such scheme, described organic cation quaternary ammonium salt aqueous solution is alkylpolyoxyethylene, tetra-alkyl-phosphonium halide
Ammonium, double octyl dimethy lammonium chlorides, double nonyl dimethy lammonium chlorides, single octyl dimethy lammonium chloride, single nonyl two
Methyl ammonium halide, tetraalkyl ammonium hydrogen sulfate, tetraalkyl ammonium acetate, double alkyl dimethyl ammonium halides, methyltrialkyl ammonium halide, two
Ethyl hexanol base ammonium halide or trialkyl methyl ammonium halide.
By such scheme, described organic cation quaternary amine alkali is TMAH, tetraethyl ammonium hydroxide, 4 third
Base ammonium hydroxide, TBAH, the aqueous solution of benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide, four
Ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, benzyltrimethylammonium hydroxide
Or the methanol solution of benzyltriethylammonium hydroxide.
By such scheme, step 1) described in the organic cation quaternary ammonium salt of swelling process, organic cation quaternary amine alkali and
The relative weight ratio of water is 1: (1~50): (50~500).
By such scheme, step 1) described in pH value range be 8~14.
By such scheme, step 1) described in swelling process control temperature to be 60~110 DEG C, be swelled the reaction time for 4
~36h.
By such scheme, step 1) described in swelling process control temperature to be 90~100 DEG C, be swelled the reaction time for 15
~24h.
By such scheme, step 2) described in pillared process be that the MWW high-silica zeolites that will be swelled add silicon source and titanium
In the pillaring agent colloidal sol of source composition, described pillaring agent is mixed according to the ratio of Ti/Si molar ratios 0.001~0.5, and stirring is equal
It is even, reactant mixture is obtained, 4~48h is reacted in 60~120 DEG C.By the content for reducing Ti in pillaring agent, it is possible to reduce prepare
Sample in hexa-coordinate state titanium content, accordingly increase the ratio of four-coordination titanium.
By such scheme, step 2) silicon source be silicic acid, silica gel, Ludox, silicochloroform, silicon tetrachloride or silicic acid
Tetraalkyl ester；Described titanium source is tetralkyl titanate, halogenated titanium or titanium oxide.
By such scheme, described silicic acid tetraalkyl ester is methyl silicate, silester, silicic acid propyl ester or the positive fourth of silicic acid
Ester.
By such scheme, step 2) described in pillared process be additionally added 1~5% template agent of reactant gross weight, institute
The template stated is N, N, N- trimethyl -1- adamantane, hexamethylene imine or piperidines.
By such scheme, step 3) described in hydrolytic process, use alkaline aqueous solution control ph for 5~12, it is hydrolyzed
The weight ratio of MWW high-silica zeolite solid of the alkaline aqueous solution added in journey with introducing pillaring agent is 1:(10~200), hydrolysis
Temperature control is at 20~80 DEG C, and hydrolysis time is controlled in 1~10h.
By such scheme, step 3) described in hydrolytic process alkaline aqueous solution be NH3, NaOH, KOH or Ca (OH)2It is water-soluble
Liquid, 0.01~1mol/l of its concentration.
By such scheme, step 4) described in calcination process be first isolation air conditionses under 200~550 DEG C roasting 3
~10h, then 400~700 DEG C of 3~20h of roasting under atmospheric environment.
By such scheme, described acid treatment is by step 4) obtained titaniferous MCM-36 by inorganic acid or organic acid at
Reason, titaniferous MCM-36 is 1 according to weight ratio with 0.5~5mol/l of concentration acid solutions:(5~100) mix, stir,
10min~1d is handled at 50~150 DEG C.
Through filtering, washing, being dried to obtain acid-treated product, treated product maintains interlayer as catalyst
The state of titanium is all four-coordination titanium in MWW molecular sieve basic structures in 2nm ducts and layer, obtained sample.
By such scheme, described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and described organic acid is formic acid, second
Acid, propionic acid or tartaric acid.
By such scheme, the high-silica zeolite containing template agent is MCM-22 types zeolite molecular sieve, MCM-49 types
It is any in zeolite molecular sieve, MCM-56 types zeolite molecular sieve, ERB-1 molecular sieves, SSZ-25 molecular sieves and PSH-3 molecular sieves
It is a kind of.
By such scheme, the preparation of the high-silica zeolite presoma containing template agent is the hydro-thermal using organic formwork agent
Synthetic method.
Above-mentioned stratiform containing mesopore HTS enters as steps described below as the application method of epoxidation catalysts
OK：
1) stratiform containing mesopore titanium-silicon molecular sieve catalyst, solvent, reactant and oxidant are added in reactor and stirred,
Wherein reactant：Catalyst：Oxidant：The weight ratio of solvent is 1:(0.03~0.15):(1.1~3):(1~10).
2) by step 1) in reaction system temperature be raised to 30~150 DEG C reaction 1~15h after, filter to isolate stratiform
Containing mesopore titanium-silicon molecular sieve catalyst, quantitative analysis is carried out by gained liquid form product application gas-chromatography.
By such scheme, described reactant is the aliphatic containing carbon-to-carbon double bond or alicyclic of 3~10 carbon atoms
Alkene or at least one other functional compounds.
By such scheme, described reactant is the alkene of 6~10 carbon atoms.More than 1 can be contained in alkene
Double bond, such as alkadienes or alkatrienes.Described other functional compounds be halogen, carboxyl, hydroxyl, ehter bond, carbonyl, phenolic group,
Amido, sulfenyl or nitro.
By such scheme, described oxidant is in hydrogen peroxide, TBHP and cumyl hydroperoxide
At least one.
By such scheme, described solvent is cycloalkane, such as hexamethylene, cyclodecane etc., alcohols, ketone, nitrile chemical combination
Thing or water.
The conversion ratio of corresponding raw material and the yield calculation formula of product are as follows：
The conversion ratio (%) of the reactant=(total moles of the reactant of the total mole number/addition for the gross product that reaction is produced
Number) × 100；
The selectivity (%) of purpose product=(gross product that the total mole number of purpose oxidation product/reaction is produced always rubs
That number) × 100；
Above-mentioned stratiform containing mesopore HTS enters as steps described below as the application method of ammoxidation reaction catalyst
OK：
1) stratiform containing mesopore titanium-silicon molecular sieve catalyst, solvent, aldehydes or ketones reactant and ammonia are added in reactor and stirred
Mix, wherein, aldehydes or ketones reactant：Ammonia：Catalyst：The weight ratio of solvent is 1:(1.1~3):(0.03~0.15):(1~10).
2) by step 1) in the temperature of reaction system when being raised to 30~150 DEG C, by aldehydes or ketones reactant：Hydrogen peroxide rubs
The ratio of your ratio=1.1~2 starts that the hydrogen peroxide that concentration is 1~50% is added dropwise, and time for adding is 1~5h, continues to react, mistake
Catalyst is isolated in filter, and gained liquid form product application gas-chromatography is carried out into quantitative analysis.
By such scheme, described aldehydes or ketones reactant is the aldehydes or ketones containing 3~8 carbon atoms；
By such scheme, described ammonia is gaseous ammonia, liquid ammonia or ammoniacal liquor, and ammonia concn is 1~50%；
By such scheme, described solvent is water or water and alcohols, the mixture of ketone；As methanol, ethanol, the tert-butyl alcohol,
The aqueous solution of normal propyl alcohol, isopropanol, sec-butyl alcohol or acetone.
The conversion ratio of corresponding raw material and the yield calculation formula of product are as follows：
The conversion ratio (%) of the reactant=(total moles of the reactant of the total mole number/addition for the gross product that reaction is produced
Number) × 100.
The selectivity (%) of purpose product=(gross product that the total mole number of purpose oxidation product/reaction is produced always rubs
That number) × 100.
Compared with prior art, the present invention has following remarkable advantage：
The present invention be swelled by the molecular sieve precursor to not titaniferous, it is dry, pillared, calcining and acid treatment, holding
Meso-hole structure and titanium elements are introduced in the crystal of molecular sieve on the premise of the microcellular structure of molecular sieve, is generated microporous mesoporous
The novel titanosilicate catalyst of composite construction.Mesoporous introducing, improves reactant and product in micro porous molecular sieve
Diffusion, due to the expansion and increase in duct so that the type catalyst goes for the oxidation of bigger molecule compound, ring
Oxidation, ammoxidation reaction.And catalyst inactivation caused by carbon deposit blocking duct can be alleviated significantly, improve the longevity of catalyst
Life.Octahedral, the inactive, extra-framework titanium introduced on molecular sieve can be removed by acid treatment, and can be taken off simultaneously
Except what is contained in molecular sieve precursor, the aluminium or boron of Bronsted acidity position are served as, it is to avoid the acidic site pair on molecular sieve
The influence of oxidation reaction, can improve the activity of catalyst.
The advantage of the catalyst is：Introduce meso-hole structure and high-activity titanium component simultaneously in MWW structure molecular screens, to containing
Have the aliphatic or alicyclic olefin of carbon-to-carbon double bond or the compound oxidation of other at least one functional groups, including epoxidation with
And ammoxidation reaction activity is high, selectivity of product is high, long lifespan, regenerating easily；Secondary hydro-thermal process is avoided to MWW structures
Destruction, simplifies preparation flow；The column-supporting agent that this method is mixed using new silicon source and titanium source carries out pillared method, prepares
Mesoporous pure HTS containing titanium component, eliminates the Bronsted acidity position of boron or aluminium in molecular sieve precursor.
Brief description of the drawings
Fig. 1 is the catalyst XRD diffraction patterns prepared；
Fig. 2 is (A) N for preparing catalyst2Adsorption desorption figure and (B) catalyst pores distribution map (being calculated by adsorption curve)；
Fig. 3 is the ultraviolet-visible spectrum for preparing catalyst.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment, this explanation will not be constituted to the present invention's
Limitation.
[embodiment 1] prepares molecular sieve MCM-22 presomas
The synthesis of MCM-22 presomas uses White Carbon black for silicon source, sodium metaaluminate (NaAlO2) it is silicon source, hexa-methylene is sub-
Amine (HMI) is template agent.Representative synthetic procedures are as follows：It is stirred vigorously down, by NaOH and NaAlO2It is dissolved into distilled water, slowly
Plus people's White Carbon black, finally add people HMI.Continue stirring 2h and obtain white gels.Mixture mole composition is n (Si):n(Al):n
(HMI):n(NaOH):n(H2O)=1:0.07:0.5:0.1:30.Gel is transferred to the 50mL containing polytetrafluoroethyllining lining not
In rust steel reactor, in 150 DEG C of crystallization 5d of temperature.Mixing speed 60r/min.After crystallization terminates, room temperature is cooled to, by reaction solution
Suction filtration, and rinsed repeatedly with distilled water, until cleaning solution is neutrality.Gained white filter cake obtains MCM- in 100 DEG C of dry 12h of temperature
22 presoma MCM-22 (P).
[embodiment 2] prepares molecular sieve ERB-1 presomas
The synthesis of ERB-1 presomas uses White Carbon black for silicon source, boric acid (H3BO3) it is boron source, piperidines (PI) is template agent.
Representative synthetic procedures are as follows：It is stirred vigorously down, NaOH and boric acid is dissolved into distilled water, slowly add people's White Carbon black, finally adds
People PI.Continue stirring 2h and obtain white gels.Mixture mole composition is n (Si):n(B):n(PI):n(NaOH):n(H2O)=1:
2:1.4:0.12:25.Gel is transferred in the 50mL stainless steel cauldrons containing polytetrafluoroethyllining lining, in 150 DEG C of crystalline substances of temperature
Change 5d.Mixing speed 60r/min.After crystallization terminates, room temperature is cooled to, is rinsed repeatedly by reaction solution suction filtration, and with distilled water, directly
It is neutrality to cleaning solution.Gained white filter cake obtains ERB-1 presomas ERB-1 (P) in 100 DEG C of dry 12h of temperature.
[embodiment 3] prepares MCM-22 molecular sieves
The MCM-22 (P) that [embodiment 1] is obtained is put into tubular quartz stove, (SV=1240h under nitrogen atmosphere-1) with 3
DEG C/min speed is warming up to 600 DEG C.The air of identical air speed is switched to after 30min, continues calcining 12h and obtains MCM-22 molecules
Sieve.
[embodiment 4] prepares molecular sieve ERB-1 molecular sieves
The ERB-1 (P) that [embodiment 2] is obtained is put into tubular quartz stove, (SV=1240h under nitrogen atmosphere-1) with 3
DEG C/min speed is warming up to 600 DEG C.The air of identical air speed is switched to after 30min, continues calcining 12h and obtains ERB-1 molecular sieves.
[embodiment 5] synthesis MCM-22 is that presoma prepares Si/Ti-MCM-36
The drying that [embodiment 1] is obtained:MCM-22 (P) be added to cetyl trimethylammonium bromide solution (CTMABr,
Mass fraction is 25%) and four n-propyl ammonium hydroxide (TPAOH) are according to mass ratio TPAOH:CTMABr:H2O=1:4:230 enter
In the mixed liquor of row mixing, the pH value for controlling solution is 13.5,36h is stirred at reflux in 100 DEG C, then mistake after 4h is stirred at room temperature
Filter, is washed with a small amount, dries naturally.Sample after being swelled is added to the positive ethyl ester of silicic acid and tetrabutyl titanate is rubbed with Si/Ti
In your colloid than 40 mixing, stir filtered after 25h in 80 DEG C under nitrogen protection, be dried overnight.Finally by sample and go from
Sub- water is with 1:10 mass ratio mixing, pH=9 is controlled in 60 DEG C with 0.1mol/l NaOH, hydrolyzes 6h, and rear filtering is dried overnight；
And then 550 DEG C are warming up in N with 2 DEG C/min speed in tube furnace23h is calcined under environment；Again with 2 DEG C/min speed liter
Temperature is calcined 10h to 600 DEG C under atmospheric environment, names as 40Si/Ti-MCM-36 (M).
[embodiment 6] synthesis ERB-1 is that presoma prepares Si/Ti-MCM-36
The ERB-1 (P) for the drying that [embodiment 2] is obtained be added to cetyl trimethylammonium bromide solution (CTMABr,
Mass fraction is 25%) and four n-propyl ammonium hydroxide (TPAOH) are according to mass ratio TPAOH:CTMABr:H2O=1:4:230 enter
In the mixed liquor of row mixing, the pH value for controlling solution is 13.5,24h is stirred at reflux in 100 DEG C, then mistake after 4h is stirred at room temperature
Filter, is washed with a small amount, dries naturally.Sample after being swelled is added to the positive ethyl ester of silicic acid and tetrabutyl titanate is rubbed with Si/Ti
In your colloid than 40 mixing, stir filtered after 25h in 80 DEG C under nitrogen protection, be dried overnight.Finally by sample and go from
Sub- water is with 1:10 mass ratio mixing, 0.1mol/l NH are used in 80 DEG C3PH=9 is controlled, 6h is hydrolyzed, rear filtering is dried overnight；
And then 550 DEG C are warming up in N with 2 DEG C/min speed in tube furnace23h is calcined under environment；Again with 2 DEG C/min speed liter
Temperature is calcined 10h to 600 DEG C under atmospheric environment, names as 40Si/Ti-MCM-36 (E).
The Si/Ti-MCM-36 that [embodiment 7] acid treatment is prepared by presoma of MCM-22
The Si/Ti-MCM-36 molecular screen primary powders that [embodiment 5] is obtained and the HNO that concentration is 2mol/l3According to weight ratio
1:50 mixing, stir, 6h are handled under the conditions of 100 DEG C, filter, wash, being dried to obtain acid-treated product A-40Si/Ti-
MCM-36(M)。
The Si/Ti-MCM-36 that [embodiment 8] acid treatment is prepared by presoma of ERB-1
The Si/Ti-MCM-36 molecular screen primary powders that [embodiment 6] is obtained and the HNO that concentration is 4mol/l3According to weight ratio
1:50 mixing, stir, 6h are handled under the conditions of 100 DEG C, filter, wash, being dried to obtain acid-treated product A-40Si/Ti-
MCM-36(E)。
[embodiment 9] synthesis ERB-1 is that presoma prepares Si/Ti-MCM-36
The ERB-1 (P) for the drying that [embodiment 2] is obtained be added to cetyl trimethylammonium bromide solution (CTMABr,
Mass fraction is 25%) and four n-propyl ammonium hydroxide (TPAOH) are according to mass ratio TPAOH:CTMABr:H2O=1:4:230 enter
In the mixed liquor of row mixing, the pH value for controlling solution is 13.5,36h is stirred at reflux in 100 DEG C, then mistake after 4h is stirred at room temperature
Filter, is washed with a small amount, dries naturally.Sample after being swelled is added to the positive ethyl ester of silicic acid and tetrabutyl titanate is rubbed with Si/Ti
In your colloid than 20 mixing, stir filtered after 25h in 80 DEG C under nitrogen protection, be dried overnight.Finally by sample and go from
Sub- water is with 1:10 mass ratio mixing, pH=9 is controlled in 80 DEG C with 0.1mol/l NaOH, hydrolyzes 6h, and rear filtering is dried overnight；
And then 550 DEG C are warming up in N with 2 DEG C/min speed in tube furnace23h is calcined under environment；Again with 2 DEG C/min speed liter
Temperature is calcined 10h to 600 DEG C under atmospheric environment, names as 20Si/Ti-MCM-36 (E).
[embodiment 10] synthesis ERB-1 is that presoma prepares Si/Ti-MCM-36
The ERB-1 (P) for the drying that [embodiment 2] is obtained be added to cetyl trimethylammonium bromide solution (CTMABr,
Mass fraction is 25%) and four n-propyl ammonium hydroxide (TPAOH) are according to mass ratio TPAOH:CTMABr:H2O=1:4:230 enter
In the mixed liquor of row mixing, the pH value for controlling solution is 13.5,24h is stirred at reflux in 100 DEG C, then mistake after 4h is stirred at room temperature
Filter, is washed with a small amount, dries naturally.Sample after being swelled is added to the positive ethyl ester of silicic acid and tetrabutyl titanate is rubbed with Si/Ti
In your colloid than 120 mixing, stir filtered after 25h in 90 DEG C under nitrogen protection, be dried overnight.Finally by sample and go from
Sub- water is with 1:10 mass ratio mixing, 0.1mol/l NH are used in 80 DEG C3PH=9 is controlled, 6h is hydrolyzed, rear filtering is dried overnight；
And then 550 DEG C are warming up in N with 2 DEG C/min speed in tube furnace23h is calcined under environment；Again with 2 DEG C/min speed liter
Temperature is calcined 10h to 600 DEG C under atmospheric environment, names as 120Si/Ti-MCM-36 (E).
The crystal structure of molecular sieve is carried out using X ' the Pert PRO types X-ray diffractometers of PANalytical companies
Analysis；Using the type N2 Sorption Analyzers of TriStar 3000 of Microstar (Micrometerics) company to the pore structure of catalyst
Analyzed, be as a result listed in Fig. 1,2.
From the big angle in Fig. 1 and small angle XRD diffraction maximums, MCM-22, ERB-1 and its presoma are about at 2 θ angles
7.2 °, 25.1 ° and 26.1 ° (interplanar distance d values are respectively 1.23,0.355 and 0.343nm) places occur in that sign layer molecule
The sharp and strong characteristic diffraction peak of (100), (220) and (310) crystal face is sieved, shows MCM-22, ERB-1 and its presoma of synthesis
All there is the layer structure of MWW section bar material.Unlike, 2 θ angles are about to occur at 6.7 ° in MCM-22 and ERB-1 presomas
The diffraction maximum of (002) crystal face is characterized, is disappeared in MCM-22 and ERB-1.This is that MCM-22 presomas are acted in high-temperature roasting
Under, its interlayer is connected by original Si (Al)-OH groups with weaker H keys, is changed into through dehydration with stronger oxygen bridge Si
(Al)-O-Si keys are connected, and interlayer is caused along c to (interlamellar spacing shrinks 0.2nm) is shunk.In addition, with MCM-22 and ERB-1 forerunners
The diffraction maximum of body phase ratio, MCM-22 and ERB-1 at (101) and (102) crystal face is except being slightly displaced, it does not occur in addition to intensity increase
He significantly changes.By being swelled, dry, pillared, calcining and the obtained Si/Ti-MCM-36 of acid treatment, with precursor MCM-22
Compared with ERB-1 XRD spectra, 2 about 6.5 ° of θ angles (d values about 1.35nm) places characterize the diffraction maximum of (002) crystal face in Si/
Disappeared in TiMCM-36, the substitute is and occur in that sign (001) is brilliant at θ=2 ° of small angular region about 2 (d values about 4.4nm) place
The mesoporous phase character diffraction maximum in face.This be precursor MCM-22 and ERB-1 layer along c-axis extension expansion make (h k l) crystal face send out
The result of obvious displacement is given birth to.The unit cell parameter c of MCM-36 interplanar distance d values including MCM-22 and ERB-1 (is
2.51nm) with MCM-36 interlamellar spacing.Thus can confirm, MCM-22 and ERB-1 presomas through be swelled and using amorphous ti silica as
Diameter 2nm or so meso-hole structure has been formd after pillaring agent is pillared in its interlayer.At the same time, precursor be swelled with it is pillared
During (hk0) crystal face do not change, therefore, characterize stratified material (100), (220) and (310) crystal face three feature diffraction
Peak is retained in synthesis Si/Ti-MCM-36, i.e. Si/Ti-MCM-36 intactly remains MCM-22 and ERB-1 forerunners
MWW and micropore canals structure in the layer and its layer of body.In addition, presoma MCM-22 and ERB-1 distinguishes at about 8 ° and 10 ° of 2 θ angles
Characterize its interlayer (101) and (102) crystal face clearly diffraction maximum.The Si/Ti-MCM-36's obtained using MCM-22 as presoma
(101) and (102) diffraction maximum at 8 ° and 10 ° of XRD spectra merges and in a broadband diffraction peak, illustrated in pillared obtained Si/
MWW layers are that random heap falls in Ti-MCM-36；And the Si/Ti-MCM-36 that ERB-1 presomas are obtained is still in about 8 ° and 10 °
Place remains (101) and (102) crystal face of separation clearly diffraction maximum, it was demonstrated that it is pillared obtain layer by layer between remain on and advise
Heap then falls.
Fig. 2 N2The catalyst pores distribution map that adsorption desorption is obtained, it is seen that MCM-22 and ERB-1 molecular sieve precursors are not present
Hole more than 2nm or so, the Si/Ti-MCM-36 obtained by processing generates the mesoporous of 2nm or so.
The method for the titanium-silicon molecular sieve catalyst synthesizing epoxy compound that embodiment 11~20 is prepared for implementation
[embodiment 11] catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 6], and reactant is cyclohexene.
In the three-necked flask that the volume with thermometer, reflux condensing tube and magnetic stirring apparatus is 10ml, 0.83g is added
Cyclohexene, adds 2.2g n-decanes, adds 1.5g TBHPs (TBHP, 5.5mol/l are in n-decane solvent),
Catalyst 50mg, reactant are added in flask：The mol ratio of oxidant is 1:1.Heat and be stirred vigorously under 80 DEG C of water-baths.From
Reaction starts after timing, reaction 10h, stops heating, and reactant mixture is cooled down immediately and stops reaction.Then filtering reaction mixing
Thing, catalyst and reacted liquid are separated and weighed, using gas-chromatography (Shimadzu GC14B, DB-1 capillary column 30m ×
0.25mm × 0.25 μm, is quantified by internal standard of toluene) analysis filtrate in organic matter concentration.Analysis result shows, reactant
Cyclohexene conversion rate reach 90% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach 84.1%.
Embodiment 12~20
Except for the following differences, remaining is identical with [embodiment 11].
[embodiment 12]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 7], and reactant is cyclohexene.
Analysis result shows, the cyclohexene conversion rate of reactant reach 85% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
70.3%.
[embodiment 13]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 8], and reactant is cyclohexene.
Analysis result shows, the cyclohexene conversion rate of reactant reach 98.5% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
To 85.3%.
[embodiment 14]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 9], and reactant is cyclohexene.
Analysis result shows, the cyclohexene conversion rate of reactant reach 84.5% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
To 75.3%.
[embodiment 15]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 10], and reactant is cyclohexene.
Analysis result shows, the cyclohexene conversion rate of reactant reach 88% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
87.8%.
[embodiment 16]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 10], and reactant is cyclo-octene.
Analysis result shows, the cyclo-octene conversion ratio of reactant reach 90% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
98%.
[embodiment 17]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 10], and reactant is cyclohexene, and solvent is acetonitrile.
Analysis result shows, the cyclohexene conversion rate of reactant reach 89% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
86.2%.
[comparative examples 18]
In addition to catalyst is TS-1, other are with [embodiment 11]
Analysis result shows, the cyclohexene conversion rate of reactant reach 30% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
84.2%.
[comparative examples 19]
In addition to catalyst is Ti-MWW, other are with [embodiment 11]
Analysis result shows, the cyclohexene conversion rate of reactant reach 50% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
85.1%.
[comparative examples 20]
In addition to catalyst is IEZ-Ti-WWW, other are with [embodiment 15]
Analysis result shows, the cyclohexene conversion rate of reactant reach 60% and the selectivity of product 7-oxa-bicyclo[4.1.0 reach
86.7%.The method for the titanium-silicon molecular sieve catalyst catalytic ammoxidation reaction that embodiment 21~25 is prepared for implementation
[embodiment 21]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 6], reactant cyclohexanone.
Cyclohexanone oxamidinating reaction is carried out in the 25mL there-necked flasks equipped with reflux condenser and microsyringe.Typically
Course of reaction is：5g H are sequentially added in reaction system2O, 10mmol cyclohexanone, the ammoniacal liquor of 12mmol 25% and 50mg catalysis
Agent, question response temperature is raised to after 60 DEG C, is at the uniform velocity added 12mmol 5% hydrogen peroxide in 1h with microsyringe, then
Continue isothermal reaction 0.5h.The analysis of product uses gas chromatographic analysis (Shimadzu GC14B, DB-1 capillary column 30m × 0.25mm
×0.25μm).Analysis result shows, the cyclohexanone conversion ratio of reactant reach 99.5% and the selectivity of product cyclohexanone oxime reach
To 99.9%.
Embodiment 22~25
Except for the following differences, remaining is identical with [embodiment 11].
[embodiment 22]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 7], reactant cyclohexanone.
Analysis result shows, the cyclohexanone conversion ratio of reactant reach 99.2% and the selectivity of product cyclohexanone oxime reach
99.9%.
[embodiment 23]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 8], reactant cyclohexanone.
Analysis result shows, the cyclohexanone conversion ratio of reactant reach 99.8% and the selectivity of product cyclohexanone oxime reach
99.9%.
[embodiment 24]
Catalyst is titanium-silicon molecular sieve catalyst prepared by [embodiment 9], reactant cyclohexanone.
Analysis result shows, the cyclohexanone conversion ratio of reactant reach 99.0% and the selectivity of product cyclohexanone oxime reach
99.9%.
[comparative examples 25]
In addition to catalyst is TS-1, other are with [embodiment 21]
Analysis result shows, the cyclohexanone conversion ratio of reactant reach 17.0% and the selectivity of product cyclohexanone oxime reach
71.5%.
[comparative examples 26]
In addition to catalyst is Ti-WWW, other are with [embodiment 21]
Analysis result shows, the cyclohexanone conversion ratio of reactant reach 86.0% and the selectivity of product cyclohexanone oxime reach
99.9%.
It was found from above-described embodiment result, using the conjunction of the titanium-silicon molecular sieve catalyst application epoxide of the present invention
Into, the selectivity of epoxide is not only increased, and the conversion ratio of epoxy olefins is improved simultaneously.Particularly to molecule power
The macromolecular being relatively large in diameter is learned, e.g., cyclohexene and cyclo-octene, reactant molecule are bigger, synthesized contains meso-hole structure and MWW
Lamellar zeolite Si/Ti-MCM-36 catalytic effect is more superior.Type catalyst aims ammoxidation of cyclohexanone reaction equally has
Efficient and high selectivity, better than micropore titanium silicon molecular sieve.
Claims (32)
1. stratiform containing mesopore titanium-silicon molecular sieve catalyst, it has the twelve-ring hole of MWW high-silica zeolites and sine netted
Pore canal system, its interlayer has 2-10nm meso-hole structures, and has the titanium and hexa-coordinate state of four-coordination state simultaneously
Titanium, it is following preparation method products therefroms, includes following steps：
1) the MWW high-silica zeolites containing template are that presoma is swelled under high ph-values environment using sweller, Ran Houjing
Filter, wash, dry；The described MWW high-silica zeolites containing template are ERB-1 molecular sieves；
2) it is pillared in the MWW high-silica zeolites interlayer introducing pillaring agent progress being swelled, then filter, dry；Described is pillared
Process is additionally added 1~5% template of reactant gross weight, and described template is N, N, N- trimethyl -1- adamantane, six
Methylene imine or piperidines；
3) it is put into the aqueous solution by being introduced into the MWW high-silica zeolite solids of pillaring agent and carries out further hydrolysis,
The pillared inorganic wall of MWW high-silica zeolite interlayer shapes and corresponding meso-hole structure, filter, wash, dry again；
4) the obtained dried powder containing template, sweller and pillaring agent hydrolysate is finally subjected to high-temperature calcination, obtained
To the titaniferous MCM-36 of micropore-mesopore composite construction.
2. the preparation method of the stratiform containing mesopore titanium-silicon molecular sieve catalyst described in claim 1, includes following steps：
1) the MWW high-silica zeolites containing template are that presoma is swelled under high ph-values environment using sweller, Ran Houjing
Filter, wash, dry；The described high-silica zeolite containing template is ERB-1 molecular sieves；
2) it is pillared in the MWW high-silica zeolites interlayer introducing pillaring agent progress being swelled, then filter, dry；Described is pillared
Process is additionally added 1~5% template of reactant gross weight, and described template is N, N, N- trimethyl -1- adamantane, six
Methylene imine or piperidines；
3) it is put into the aqueous solution by being introduced into the MWW high-silica zeolite solids of pillaring agent and carries out further hydrolysis,
The pillared inorganic wall of MWW high-silica zeolite interlayer shapes and corresponding meso-hole structure, filter, wash, dry again；
4) the obtained dried powder containing template, sweller and pillaring agent hydrolysate is finally subjected to high-temperature calcination, obtained
To the titaniferous MCM-36 of micropore-mesopore composite construction.
3. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
4) material obtained, by filtering, washing, be dried to obtain acid-treated product, is used as catalyst by acid treatment.
4. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that described
Micropore-mesopore composite construction titaniferous MCM-36 on 0.5-1nm micropore is distributed with, its interlayer has 2-10nm Jie
Hole.
5. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
1) sial or silicon boron ratio of the MWW high-silica zeolites described in are 5-1000.
6. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 5, it is characterised in that step
1) sial or silicon boron ratio of the MWW high-silica zeolites described in are 30-300.
7. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
1) sweller described in is organic cation quaternary ammonium salt aqueous solution and the mixture of organic cation quaternary amine aqueous alkali.
8. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 7, it is characterised in that described
Organic cation quaternary ammonium salt aqueous solution be alkyl trimethyl ammonium salt type, dialkyl dimethyl ammonium salt type or alkyldimethylbenzylammonium
Ammonium salt type.
9. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 8, it is characterised in that described
Organic cation quaternary ammonium salt aqueous solution be alkylpolyoxyethylene, quaternary alkylammonium halides, double octyl dimethy lammonium chlorides,
Double nonyl dimethy lammonium chlorides, single octyl dimethy lammonium chloride, single nonyl dimethy lammonium chloride, tetraalkyl hydrogen sulfate
Ammonium, tetraalkyl ammonium acetate, double alkyl dimethyl ammonium halides, methyltrialkyl ammonium halide, diethylaluminum ethoxide base ammonium halide or three alkane
Ylmethyl ammonium halide.
10. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 7, it is characterised in that described
Organic cation quaternary amine alkali be TMAH, tetraethyl ammonium hydroxide, TPAOH, tetrabutylammonium hydroxide
The aqueous solution of ammonium, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide, TMAH, tetraethyl hydrogen-oxygen
Change the first of ammonium, TPAOH, TBAH, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide
Alcoholic solution.
11. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 7, it is characterised in that step
1) the relative weight ratio of the organic cation quaternary ammonium salt of the swelling process described in, organic cation quaternary amine alkali and water is 1: (1~
50): (50~500).
12. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
1) pH value range described in is 8~14.
13. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
1) swelling process described in controls temperature to be 60~110 DEG C, is swelled the reaction time for 4~36h.
14. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 13, it is characterised in that step
It is rapid 1) described in swelling process control temperature to be 90~100 DEG C, be swelled the reaction time for 15~24h.
15. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
2) the pillared process described in is that the MWW high-silica zeolites that will be swelled are added in the pillaring agent colloidal sol that silicon source is constituted with titanium source, institute
The pillaring agent stated is mixed according to the ratio of Ti/Si molar ratios 0.001~0.5, is stirred, is obtained reactant mixture, in 60
~120 DEG C of 4~48h of reaction.
16. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 15, it is characterised in that step
Rapid 2) described silicon source is silicic acid, silica gel, Ludox, silicochloroform, silicon tetrachloride or silicic acid tetraalkyl ester；Described titanium source is
Tetralkyl titanate, halogenated titanium or titanium oxide.
17. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 16, it is characterised in that institute
The silicic acid tetraalkyl ester stated is methyl silicate, silester, silicic acid propyl ester or silicic acid N-butyl.
18. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
3) hydrolytic process described in, uses alkaline aqueous solution control ph for 5~12, the alkaline aqueous solution added in hydrolytic process is with drawing
The weight ratio for entering the MWW high-silica zeolite solids of pillaring agent is 1:(10~200), hydrolysis temperature is controlled at 20~80 DEG C, hydrolysis
Time control is in 1~10h.
19. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 18, it is characterised in that step
It is rapid 3) described in hydrolytic process alkaline aqueous solution be NH3, NaOH, KOH or Ca (OH)2The aqueous solution, 0.01~1mol/ of its concentration
l。
20. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that step
4) calcination process described in is first 200~550 DEG C of 3~10h of roasting under isolation air conditionses, then 400 under atmospheric environment
~700 DEG C of 3~20h of roasting.
21. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 3, it is characterised in that described
Acid treatment be by step 4) obtained titaniferous MCM-36 is by inorganic acid or organic acid treatment, titaniferous MCM-36 and concentration 0.5
~5mol/l acid solutions are 1 according to weight ratio:(5~100) mix, stir, at 50~150 DEG C handle 10min~
1d。
22. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 21, it is characterised in that institute
The inorganic acid stated is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and described organic acid is formic acid, acetic acid, propionic acid or tartaric acid.
23. the preparation method of stratiform containing mesopore titanium-silicon molecular sieve catalyst according to claim 2, it is characterised in that described
The preparation of MWW high-silica zeolite presomas containing template is the hydrothermal synthesis method using organic formwork agent.
24. the layered containing mesopore titanium-silicon molecular sieve catalyst of claim 1 is as the application method of epoxidation catalysts,
Carry out as steps described below：
1) stratiform containing mesopore titanium-silicon molecular sieve catalyst, solvent, reactant and oxidant are added in reactor and stirred, wherein
Reactant：Catalyst：Oxidant：The weight ratio of solvent is 1:(0.03~0.15):(1.1~3):(1~10)；
2) by step 1) in reaction system temperature be raised to 30~150 DEG C reaction 1~15h after, filter to isolate stratiform containing Jie
Hole titanium-silicon molecular sieve catalyst, quantitative analysis is carried out by gained liquid form product application gas-chromatography.
25. application method according to claim 24, it is characterised in that described reactant is containing for 3~10 carbon atoms
There are the aliphatic or alicyclic olefin or at least one other functional compounds of carbon-to-carbon double bond.
26. application method according to claim 25, it is characterised in that described reactant is the alkene of 6~10 carbon atoms
Hydrocarbon.
27. application method according to claim 24, it is characterised in that described oxidant is hydrogen peroxide, tert-butyl group mistake
At least one of hydrogen oxide and cumyl hydroperoxide.
28. application method according to claim 24, it is characterised in that described solvent be cycloalkane, alcohols, ketone,
Nitrile compounds or water.
29. the layered containing mesopore titanium-silicon molecular sieve catalyst of claim 1 is as the application method of ammoxidation reaction catalyst,
Carry out as steps described below：
1) stratiform containing mesopore titanium-silicon molecular sieve catalyst, solvent, aldehydes or ketones reactant and ammonia are added in reactor and stirred, its
In, aldehydes or ketones reactant：Ammonia：Catalyst：The weight ratio of solvent is 1:(1.1~3):(0.03~0.15):(1~10)；
2) by step 1) in the temperature of reaction system when being raised to 30~150 DEG C, by aldehydes or ketones reactant：Hydrogen peroxide mol ratio
=1.1~2 ratio starts that the hydrogen peroxide that concentration is 1~50% is added dropwise, and time for adding is 1~5h, continues to react, filtering point
Catalyst is separated out, gained liquid form product application gas-chromatography is subjected to quantitative analysis.
30. application method according to claim 29, it is characterised in that described aldehydes or ketones reactant is to contain 3~8
The aldehydes or ketones of carbon atom.
31. application method according to claim 29, it is characterised in that described ammonia is gaseous ammonia, liquid ammonia or ammoniacal liquor,
Described ammonia concn is 1~50%.
32. application method according to claim 29, it is characterised in that described solvent is water or water and alcohols, ketone
Mixture.
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| RU2761301C2 (en) * | 2016-12-20 | 2021-12-07 | Басф Се | Use of acid treatment for reducing plasticity of composition containing titanium-containing zeolite material having mww structural type |
| EP3558516A1 (en) * | 2016-12-20 | 2019-10-30 | Basf Se | A process for preparing an extrudable composition comprising a titanium-containing zeolitic material having framework type mww |
| CN107188194B (en) * | 2017-05-04 | 2019-07-23 | 郑州大学 | A method of preparing high catalytic activity Ti-MWW molecular sieve |
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