CN102627291A - Fluorine-containing titanium-silicon molecular sieve with MWW (Manual Wire Wrap) structure and preparation method and application thereof - Google Patents
Fluorine-containing titanium-silicon molecular sieve with MWW (Manual Wire Wrap) structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-containing titanium-silicon molecular sieve with a MWW (Manual Wire Wrap) structure and a preparation method and an application thereof. In the molecular sieve, a fluorine atom is connected with a framework silicon atom in the form of a chemical bond, an XRD (X-Ray Diffraction) spectrogram contains a characteristic spectral line of the molecular sieve with the MWW structure, and characteristic peaks of -150+/-5ppm and -143+/-5ppm appear in a 19FMAS-NMR (19 File Management Assistant For Server-Nuclear Magnetic Resonance) spectrogram; the preparation method comprises the following steps of: synthesizing a boron-containing parent body, post-treating, baking and the like; and the molecular sieve serving as a catalyst is applied to catalytic oxidation reactions of compounds containing carbon-carbon double bonds and at least one other functional group as well as reactions for catalytically synthesizing oxime. The molecular sieve has a complete crystalline state structure; according to the electronic effect of framework fluorine, the molecular sieve and higher catalytic oxidation capability; a preparation process is simple, and is easy for industrial production; synthesis of corresponding epoxides or catalytic synthesis of oxime from compounds containing carbon-carbon double bonds and at least one other functional group can be catalyzed at higher activity and high selectivity; and a reaction process is environmentally-friendly.
Description
Technical field
The present invention relates to the synthetic and Application in Chemical Engineering technical field of inorganic chemistry; Relate to a kind of MWW of having structure fluorine-containing HTS, the specifically a kind of MWW of having structure, fluorine are implanted fluorine-containing HTS of framework of molecular sieve and preparation method thereof and this molecular sieve as the application of catalyzer in catalytic oxidation that contains carbon-to-carbon double bond and at least a other functional compounds and the synthetic oxime reaction of catalysis.
Background technology
The MWW molecular sieve be one type of molecular sieve with sinusoidal 10 Yuans ring reticulated cell systems, 12 Yuans annular distance caves and supercage hole series structure (science, Science, 1994,264:1910).To there be the aluminium atom of catalytic activity to introduce the MWW framework of molecular sieve, form MCM-22 molecular sieve (US 4,954,325).Because special pore passage structure, as the acidic catalyst active ingredient, the MCM-22 molecular sieve shows catalytic performances such as excellent catalytic cracking (US 4,983,276), alkene and benzene alkylation (US 4,992,606, US 4,992,615, US 5,334,795).The MWW molecular sieve is used for the technology industriallization of alkene and benzene alkylation reaction as the acidic catalyst active ingredient.
Introduce the MWW framework of molecular sieve to transition metal titanium atom, form HTS with the characteristic of appraising at the current rate.HTS has the oxidation-reduction catalysis function and selects the shape function, thereby has good directional catalyzing oxidation susceptibility.HTS has caused the extensive concern of world catalyticing research person and industry member as the Green Chemistry new catalyst of selective oxidation of new generation.The TS-1 molecular sieve is the HTS (US 4,410,501) with MFI structure, demonstrates excellent hydrocarbon selective catalytic oxidation performance.The TS-1 molecular sieve is used for the synthetic technology industriallization to biphenol and ammoxidation of cyclohexanone synthesizing cyclohexane 1 ketoxime of phenol hydroxylation as the oxidation activity component.
Introduce the MWW framework of molecular sieve to the transition metal titanium atom, form the Ti-MWW molecular sieve, 2000 at first in chemical wall bulletin (Chemistry Letters, 2000:774) public reported.Reporting, is catalyzer with the Ti-MWW molecular sieve, is oxygenant with the hydrogen peroxide, can the synthetic cyclohexene oxide of catalysis.Yet the productive rate of expected product is very low, and the selectivity that generates epoxide especially is not high, and the highest have only 84%.
CN1466545A discloses a kind of MWW type titanosilicate and preparation and the application in producing epoxide.The composition structural formula of MWW type titanosilicate is: xTiO
2YM
2O
3(1-x-2y) SiO
2, wherein M represents at least a element in aluminium, boron, chromium, gallium, the iron.This titanosilicate has the X-ray diffraction spectrogram of MWW structure molecular screen.This titanosilicate prepares process basically with chemical wall bulletin (Chemistry Letters, 2000:774) the preparation process of public reported.With this titanosilicate is catalyzer, under the condition that oxygenant (like hydrogen peroxide) exists, can catalyzed oxidation contains the compound production respective rings oxide compound of carbon-to-carbon double bond and at least a other functional group.From the disclosed reaction result of embodiment, when being reactant with the vinyl carbinol, its peak rate of conversion is 87.0%; Selectivity is 99.9%; When being reactant so that chlorine third is rare, the productive rate of its epoxide is 53.1%, when being reactant with the diallyl ether; The productive rate of its epoxide is 16.7%, and optionally data are not provided.The characteristic peak of the infrared Fourier transform (FTIR) of undeclared this titanosilicate in the disclosed patent.
WO03/074421 A1 discloses a kind of titanosilicate and preparation and the application in the oxidation operation reaction.The composition structural formula of this titanosilicate is: xTiO
2(1-x) SiO
2This titanosilicate has the X-ray diffraction spectrogram of MWW structure molecular screen; And the characteristic peak that occurs 930 ± 15cm in its FTIR spectrogram; (Chemistry Letters, 2000:774) the FTIR characteristic peak of disclosed Ti-MWW molecular sieve is at 960cm and at chemical wall bulletin.With this titanosilicate is catalyzer, under the condition that oxygenant (like hydrogen peroxide) exists, can contain the synthetic respective rings oxide compound of compound or the diol compound of carbon-to-carbon double bond and can catalysis synthesize oxime by catalyzed oxidation.
CN1709574 discloses the titanium-silicon molecular sieve catalyst with MWW structure.This titanium-silicon molecular sieve catalyst is characterised in that; Titanium-silicon molecular sieve catalyst titaniferous, silicon, boron, oxygen and fluorine element; With titanium, silicon, boron, oxygen element is its backbone element; Fluorine atom links to each other with its skeleton surface silicon atoms with the mode of chemical bond, and its mole composition is expressed as xTiO with the anhydrous form of oxide compound
2: yB
2O
3: zF:SiO
2, wherein, x=0.0005～0.04, y=0～0.1, z=0.001～0.04, its XRD spectra contains the characteristic spectral line of MWW structure molecular screen, occurs the characteristic peak of 930 ± 15cm in its FTIR spectrogram, its
19The characteristic peak that occurs-125 ± 5ppm in the F MAS-NMR nmr spectrum.It is the key feature of this HTS that fluorine element links to each other with its skeleton surface silicon atoms with the mode of chemical bond.Yet, research show (JACS, Journal of The America Chemical Society, 2011,133,3288-3291), fluorine and Si bonded mode have three kinds, are respectively SiF
6 2-, O
4/2Si-F, O
3/2Si-F, corresponding
19Appearance-128.6ppm in the F MAS-NMR nmr spectrum ,-150.3ppm and-characteristic peak of 143ppm, wherein have only O
4/2Si-F, O
3/2On behalf of fluorine, Si-F be and framework of molecular sieve Si bonding.Can know, the HTS of this disclosure of the Invention, fluorine and Si combination are SiF
6 2-, promptly fluorine is with SiF
6 2-Form be present in the surface of HTS, be not present in the HTS skeleton.
Summary of the invention
One of the object of the invention provides the fluorine-containing HTS of a kind of MWW of having structure, and its characteristics are that fluorine atom links to each other with its framework silicon atom with the mode of chemical bond, and its XRD spectra contains the characteristic spectral line of MWW structure molecular screen, its
19The characteristic peak that occurs-150 ± 5ppm and-143 ± 5ppm in the F MAS-NMR nmr spectrum.
Two of the object of the invention provides the preparation method of above-mentioned molecular sieve.The technical scheme that realizes this purpose comprises following operation steps: boracic parent synthetic, aftertreatment and roasting obtain product, have the fluorine-containing HTS of MWW structure.
Specify technical scheme of the present invention at present.
A kind of preparation method with the fluorine-containing HTS of MWW structure, its characteristics are, operation steps:
Synthesizing of the first step boracic parent
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is (0.001～0.2): 1: (0.1～5): (0.1～5): (5～150) preparation feedback mixture, and described titanium source is tetralkyl titanate, halogenated titanium, titanium oxide, described silicon source is silicic acid, silica gel, silicon sol, silicic acid tetraalkyl ester; Described boron source is boric acid, borate, and described organic formwork agent is piperidines, hexamethylene imine or both mixtures, earlier the titanium source is joined in the aqueous solution of organic formwork agent; Stir, add the boron source, stir; Add the silicon source, obtain reaction mixture, described reaction mixture was in 130～200 ℃ of hydrothermal crystallizings 5 hours～20 days; Through filtration, washing, drying, obtain the boracic parent;
The second step aftertreatment
Boracic parent that the first step is obtained and fluorine-containing acidic solution are 1 according to weight ratio: (5～50) preparation feedback mixture, wherein fluorine: SiO in the boracic parent
2Mol ratio be (0.01～0.3): 1, the acid concentration of acidic solution is 0.01～5 mol/l, described fluorine source is Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid and silicofluoride; Described acid is mineral acid or organic acid; Mineral acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and organic acid is formic acid, acetate, propionic acid or tartrate, and ℃ processing is 10 minutes～20 hours in room temperature～120; Through filtration, washing, drying, obtain after-treatment products;
The 3rd one-step baking
Second product that obtain of step in 400～700 ℃ of roastings 3～20 hours, is obtained product, have the fluorine-containing HTS of MWW structure.
Preparing method of the present invention is further characterized in that, in the first step, and the TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is (0.005～0.1): 1: (0.15～2): (0.5～3): (15～50) preparation feedback mixture, in 150～190 ℃ of hydrothermal crystallizings 15 hours～10 days; In second step, boracic parent that the first step is made and fluorine-containing acidic solution are 1 according to weight ratio: (10～30) preparation feedback mixture, the wherein fluorine in the fluorine source in molar ratio: SiO in the boracic parent
2Be (0.015～0.15): 1, the acid concentration of acidic solution is 0.5～2 mol/l, handles 4～10 hours in 90～105 ℃.
Three of the object of the invention provide the fluorine-containing HTS of the above-mentioned MWW of having structure be catalyzer to be used for the compound that contains carbon-to-carbon double bond and at least a other functional group be reactant, the method for synthetic respective rings oxide compound of catalyzed oxidation or the synthetic oxime of catalysis.This method has the following advantages: reactive behavior is higher, environmental friendliness, selectivity of product high.
Specify the application of molecular sieve of the present invention at present.
It is reactant that the fluorine-containing HTS of a kind of MWW of having structure is used for the compound that contains carbon-to-carbon double bond and at least a other functional group as catalyzer; The method of the synthetic respective rings oxide compound of catalyzed oxidation; Its characteristics are; Catalyzer is for having the fluorine-containing HTS of MWW structure, operation steps:
The first step is added to catalyzer, solvent, reactant and oxygenant in the reactor drum successively; Stir; Reactant: catalyzer: the weight ratio of solvent is 1:0.03～0.15:1～10; Reactant: the mol ratio of oxygenant is 1:1～3; Described reactant is the compound that contains carbon-to-carbon double bond and at least a other functional group; Other functional group is at least a in alkyl, thiazolinyl, alkynyl, aryl, aryl, hydroxyl, ether, epoxy group(ing), halogeno-group, aldehyde radical, ketone group, carbonyl, ester group, carboxamido-group, cyanate ester based, NCO, thiocyanate groups, amido, diazo, nitro, itrile group, nitroso-group, sulfenyl, sulfoxide group, sulfuryl, thiol group, ortho acid ester group, imido grpup and the urea groups; Described oxygenant is at least a in hydrogen peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, cumyl hydroperoxide, ethylbenzene base hydrogen peroxide and the cyclohexyl hydroperoxide, and described solvent is alcohols, ketone, nitrile and water;
Second step reacted after 1～5 hour when the temperature of reaction of the reaction system of the first step is raised to 30～150 ℃, isolated catalyzer by the conventional filtration method, pressed routine operation then, separate with the corresponding epoxide of reactant.
Technique scheme is further characterized in that; In the first step; Reactant: contain catalyzer: the weight ratio of solvent is 1:0.05～0.10:1～5; Reactant: the mol ratio of oxygenant is 1:1～1.5, and described reactant is the compound that contains carbon-to-carbon double bond and at least a other functional group, and other functional group is at least a in alkyl, aryl, hydroxyl, ether, epoxy group(ing), halogeno-group, ester group, amido, nitro, itrile group, the sulfenyl; Described oxygenant is at least a in hydrogen peroxide, tertbutyl peroxide, the cumyl hydroperoxide, and described solvent is nitrile and water; In second step, when temperature of reaction is raised to 50～90 ℃, reacted 2～3 hours.
The fluorine-containing HTS of a kind of MWW of having structure is used for the working method that oxime is synthesized in catalysis as catalyzer, and its characteristics are that catalyzer is for having the fluorine-containing HTS of MWW structure, operation steps:
The first step is added to catalyzer, solvent, ketone or aldehyde, ammonia in the reactor drum successively; Stir, ketone or aldehyde: catalyzer: the weight ratio of solvent is 1:0.03～0.15:1～10, ketone or aldehyde: the mol ratio of ammonia is 1:1～3; Ketone is that carbonatoms is not more than 8 ketone; Aldehyde is that carbonatoms is not more than 6 aldehyde, and solvent can be the mixture of water or water and one of methyl alcohol, ethanol, the trimethyl carbinol, n-propyl alcohol, Virahol and sec-butyl alcohol, and the content of water is at least 10% of total solution weight; Ammonia is gaseous ammonia or ammoniacal liquor, and the concentration of ammoniacal liquor is 1～50%;
Second step is when the temperature of reaction of the reaction system of the first step is raised to 30～150 ℃; In ketone or aldehyde: it is 1～50% hydrogen peroxide that the ratio of the mol ratio=1:1 of hydrogen peroxide～2 begins to drip concentration; The dropping time is 1～5 hour, dropwises continued reaction 0～3 hour;
After three-step reaction finishes, isolate catalyzer by the conventional filtration method, then by routine operation separate oxime.
Technique scheme is further characterized in that in the first step, ketone or aldehyde: catalyzer: the weight ratio of solvent is 1:0.05～0.10:1～5, ketone or aldehyde: the mol ratio of ammonia is 1:1～2, and the concentration of ammonia is 20～30%, and solvent is a water; Temperature of reaction is raised to 50～90 ℃, ketone or aldehyde in second step: the mol ratio of hydrogen peroxide is 1:1～1.3, and concentration of hydrogen peroxide is 20～40%, and the dropping time is 1～2 hour, dropwises continued reaction 0～1 hour.
Compared with prior art, the present invention has following remarkable advantage:
(1) have the fluorine-containing HTS of MWW structure and have complete crystalline structure, fluorine atom is with the mode and the framework of molecular sieve silicon atom bonding of chemical bond;
(2) owing to the electronic effect of skeleton fluorine, fluorine-containing HTS has stronger catalyzed oxidation ability;
(3) to prepare process simple for molecular sieve, is easy to suitability for industrialized production;
(4) more high reactivity, highly selective catalysis contain the synthetic corresponding epoxide of compound or the synthetic oxime of catalysis of carbon-to-carbon double bond and at least a other functional group;
(5) reaction process environmental friendliness.
Description of drawings
The XRD spectra that Fig. 1 obtains for the embodiment of the invention 1 with the fluorine-containing HTS of MWW structure;
Fig. 2 obtains for the embodiment of the invention 1 has the fluorine-containing HTS of MWW structure
19F MAS-NMR nmr spectrum.
Embodiment
All embodiment all operate by the operation steps of said technical scheme.
Embodiment 1～13 is for having the preparation method of the fluorine-containing HTS of MWW structure.
Embodiment 1
Synthesizing of the first step boracic parent
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is a 0.033:1:0.67:1.4:19 preparation feedback mixture; Described titanium source is a tetrabutyl titanate, and described silicon source is a silicon sol, and described boron source is a boric acid; Described organic formwork agent is a piperidines; Described reaction mixture through filtration, washing, drying, obtains the boracic parent in 170 ℃ of hydrothermal crystallizings 7 days;
The second step aftertreatment
Boracic parent that the first step is obtained and fluorine-containing acidic solution are 1:30 preparation feedback mixture, wherein fluorine according to weight ratio: SiO in the boracic parent
2Mol ratio be 0.03:1, the acid concentration of acidic solution is 1mol/l, described fluorine source is that Neutral ammonium fluoride, described acid are nitric acid, handles 4 hours in 106 ℃, through filtration, washing, drying, obtains the boracic parent;
The 3rd one-step baking
Second after-treatment products that obtain of step in 550 ℃ of roastings 10 hours, is obtained product and promptly has the fluorine-containing HTS of MWW structure.
Present embodiment obtains has the fluorine-containing HTS of MWW structure; Its XRD spectra is shown in Fig. 1; As shown in the figure, this molecular sieve has characteristic peak 2 θ=7.22 °, 7.90 °, 9.54 °, 14.42 °, 16.14 °, 22.64 °, 23.72 °, 26.14 °, belongs to typical MWW structure;
19F MAS-NMR nuclear magnetic resonance spectrum is illustrated in Fig. 2, and is as shown in the figure, and this molecular sieve has chemical shift to be-characteristic peak of 152.8ppm and-140.6ppm, and mode and the framework of molecular sieve silicon atom bonding of fluorine atom with chemical bond is described, promptly fluorine is present in framework of molecular sieve.
Embodiment 2～6
Implementation process is except that following difference, and all the other are all with embodiment 1:
The first step boracic parent is synthetic
The mol ratio of reaction mixture is formed:
Embodiment 2 0.10TiO
2: SiO
2: 0.67B
2O
3: 3.5 organic formwork agents: 50H
2O;
Embodiment 3 0.05TiO
2: SiO
2: 0.67B
2O
3: 1.4 organic formwork agents: 25H
2O;
Embodiment 4 0.005TiO
2: SiO
2: 0.67B
2O
3: 1.4 organic formwork agents: 19H
2O;
Embodiment 6 0.033TiO
2: SiO
2: 0.67B
2O
3: 1.0 organic formwork agents: 10H
2O;
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 7
Implementation process is except that following difference, and all the other are all with embodiment 1:
The second step aftertreatment
Boracic parent that the first step is obtained and fluorine-containing acidic solution are 1:10 preparation feedback mixture, wherein fluorine according to weight ratio: SiO in the boracic parent
2Mol ratio be 0.25:1, the acid concentration of acidic solution is 3 mol/l, described fluorine source is a Sodium Fluoride, described acid is sulfuric acid.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 8
Implementation process is except that following difference, and all the other are all with embodiment 1:
The second step aftertreatment
Fluorine: SiO in the boracic parent
2Mol ratio be 0.01:1, the acid concentration of acidic solution is 0.5 mol/l, described fluorine source is a hydrofluoric acid, described acid is hydrochloric acid; Handled 8 hours in 100 ℃.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 9
Implementation process is except that following difference, and all the other are all with embodiment 1:
The second step aftertreatment
The acid concentration of acidic solution is 1.5 mol/l, and described fluorine source is a silicofluoric acid, handles 10 hours in 80 ℃.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Implementation process is except that following difference, and all the other are all with embodiment 1:
The second step aftertreatment
Described fluorine source is an ammonium silicofluoride.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 11
Implementation process is except that following difference, and all the other are all with embodiment 1:
The second step aftertreatment
In room temperature treatment 20 hours.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 12
Implementation process is except that following difference, and all the other are all with embodiment 1:
The silicon source is a silica gel in the first step, and the titanium source is a titanium tetrachloride, and the boron source is a Sodium Tetraborate, and organic formwork agent is a hexamethylene imine.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 13
Implementation process is except that following difference, and all the other are all with embodiment 1:
Organic formwork agent is the mixture of piperidines and hexamethylene imine, and weight ratio is 5:5.
What obtain has a fluorine-containing HTS of MWW structure, and its XRD spectra and Fig. 1 are similar,
19F MAS-NMR nmr spectrum and Fig. 2 are similar.
Embodiment 14～18 explanation has the fluorine-containing HTS of MWW structure, and to be used for the compound that contains carbon-to-carbon double bond and at least a other functional group as catalyzer be reactant, the method for the synthetic respective rings oxide compound of catalyzed oxidation.
Embodiment 14
The first step catalyzer has a fluorine-containing HTS of MWW structure for embodiment 1 preparation; Reactant is a n-hexylene, and solvent is an acetonitrile, and oxygenant is that concentration is 30.1% hydrogen peroxide; Successively catalyzer, solvent, reactant and oxygenant are added in the reactor drum; Stir, reactant: catalyzer: the weight ratio of solvent is 1:0.05:5, reactant: the mol ratio of oxygenant is 1:1.
Second step reacted after 2 hours when the temperature of reaction of the reaction system of the first step is raised to 60 ℃, isolated catalyzer by the conventional filtration method, pressed routine operation then, separate the epoxy hexane.
Analytical results shows that the n-hexylene transformation efficiency is 66.5%, and epoxy hexane selectivity is 99.9%.
Implementation process is except that following difference, and all the other are all with embodiment 14:
The first step reactant is a vinylcarbinol.
Second the step separate R-GLYCIDOL.
Analytical results shows that the vinylcarbinol transformation efficiency is 99.8%, and the R-GLYCIDOL selectivity is 99.9%.
Embodiment 16
Implementation process is except that following difference, and all the other are all with embodiment 14:
The first step reactant is a propenyl chloride.
Second the step separate epoxy chloropropionate alkene.
Analytical results shows that the propenyl chloride transformation efficiency is 88.5%, and epoxy chloropropionate alkene selectivity is 99.9%.
Embodiment 17
Implementation process is except that following difference, and all the other are all with embodiment 14:
The first step reactant is a diallyl ether.
Second the step separate glycidyl allyl ether.
Analytical results shows that the diallyl ether transformation efficiency is 48.5%, and the glycidyl allyl ether selectivity is 99.9%.
Embodiment 18
Implementation process is except that following difference, and all the other are all with embodiment 14:
The first step reactant is an allyl propyl ether.
Second the step separate the glycidyl propyl ether.
Analytical results shows that the allyl propyl ether transformation efficiency is 65.6%, and glycidyl propyl ether selectivity is 99.8%.
Embodiment 19～26 explanations have the fluorine-containing HTS of MWW structure is used for the synthetic oxime of catalysis as catalyzer method.
Embodiment 19
The first step catalyzer has a fluorine-containing HTS of MWW structure for embodiment 1 preparation, and ketone: catalyzer: the weight ratio of solvent is 1:0.02:5, ketone: the mol ratio of ammonia is 1:1.1, and ketone is pimelinketone, and ammonia is liquid ammonia, and concentration is 25%, and solvent is a water;
The second step temperature of reaction is 70 ℃, and ketone: the mol ratio of hydrogen peroxide is 1:1.05, and the concentration of hydrogen peroxide is 30.1%, and the dropping time is 1 hour, dropwises continued reaction 0.5 hour.
Analytical results shows that the pimelinketone transformation efficiency is 99.8%, and the OxiKhim-Styrol selectivity is 99.9%.
Implementation process is except that following difference, and all the other are all with embodiment 19:
The first step ketone: catalyzer: the weight ratio of solvent is 1:0.05:5, ketone: the mol ratio of ammonia is 1:1.7, and ketone is butanone;
The second step temperature of reaction is 65 ℃, and ketone: the mol ratio of hydrogen peroxide is 1:1.1.
Analytical results shows that the butanone transformation efficiency is 99.5%, and the Diacetylmonoxime selectivity is 99.7%.
Embodiment 21
Implementation process is except that following difference, and all the other are all with embodiment 19:
The first step ketone: catalyzer: the weight ratio of solvent is 1:0.03:10, ketone: the mol ratio of ammonia is 1:2, and ketone is acetone;
The second step temperature of reaction is 61 ℃, and ketone: the mol ratio of hydrogen peroxide is 1:1.15.
Analytical results shows that acetone conversion is 99.7%, and the acetoxime selectivity is 99.8%.
Embodiment 22
Implementation process is except that following difference, and all the other are all with embodiment 19:
In the first step, ketone: catalyzer: the weight ratio of solvent is 1:0.1:10, ketone: the mol ratio of ammonia is 1:1.3; In second step, temperature of reaction is 80 ℃, ketone: the mol ratio of hydrogen peroxide is 1:1.3, and the dropping time is 2 hours, dropwises continued reaction 1 hour.
Analytical results shows that the pimelinketone transformation efficiency is 99.9%, and the OxiKhim-Styrol selectivity is 99.9%.
Embodiment 23
Implementation process is except that following difference, and all the other are all with embodiment 19:
In the first step, solvent is a tertiary butanol aqueous solution, and wherein the content of water is 10% of total solution weight.
Analytical results shows that the pimelinketone transformation efficiency is 98.5%, and the OxiKhim-Styrol selectivity is 99.9%.
Embodiment 24
Implementation process is except that following difference, and all the other are all with embodiment 19:
In the first step, solvent is the aqueous solution of Virahol, and wherein the content of water is 50% of total solution weight.
Analytical results shows that the pimelinketone transformation efficiency is 99.0%, and the OxiKhim-Styrol selectivity is 99.5%.
Implementation process is except that following difference, and all the other are all with embodiment 19:
The first step aldehyde: catalyzer: the weight ratio of solvent is 1:0.2:5, aldehyde: the mol ratio of ammonia is 1:1.3, and aldehyde is acetaldehyde;
The second step temperature of reaction is 45 ℃.
Analytical results shows that the aldehyde transformation efficiency is 98.0%, and the aldoxime selectivity is 99.4%.
Embodiment 26
Implementation process is except that following difference, and all the other are all with embodiment 25:
The first step aldehyde is hexanal;
The second step temperature of reaction is 68 ℃.
Analytical results shows that the aldehyde transformation efficiency is 96.5%, and the aldoxime selectivity is 98.5%.
Claims (7)
1. one kind has the fluorine-containing HTS of MWW structure, it is characterized in that, fluorine atom links to each other with its framework silicon atom with the mode of chemical bond, and its XRD spectra contains the characteristic spectral line of MWW structure molecular screen, its
19The characteristic peak that occurs-150 ± 5ppm and-143 ± 5ppm in the F MAS-NMR nmr spectrum; This molecular sieve obtains through following steps:
Synthesizing of the first step boracic parent
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is (0.001～0.2): 1: (0.1～5): (0.1～5): (5～150) preparation feedback mixture, and described titanium source is tetralkyl titanate, halogenated titanium or titanium oxide; Described silicon source is silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester; Described boron source is boric acid or borate; Described organic formwork agent is piperidines, hexamethylene imine or both mixtures; Earlier the titanium source is joined in the aqueous solution of organic formwork agent, stir, add the boron source; Stir, add the silicon source, obtain reaction mixture; Described reaction mixture through filtration, washing, drying, obtains the boracic parent in 130～200 ℃ of hydrothermal crystallizings 5 hours～20 days;
The second step aftertreatment
Boracic parent that the first step is obtained and fluorine-containing acidic solution are 1 according to weight ratio: (5～50) preparation feedback mixture, wherein fluorine: SiO in the boracic parent
2Mol ratio be (0.01～0.3): 1; The acid concentration of acidic solution is 0.01～5 mol/l; Described fluorine source is Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid or silicofluoride, and described acid is mineral acid or organic acid, and ℃ processing is 10 minutes～20 hours in room temperature～120; Through filtration, washing, drying, obtain after-treatment products;
The 3rd one-step baking
Second product that obtain of step in 400～700 ℃ of roastings 3～20 hours, is obtained having the fluorine-containing HTS of MWW structure.
2. according to claim 1 have a fluorine-containing HTS of MWW structure, it is characterized in that said mineral acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and organic acid is formic acid, acetate, propionic acid or tartrate.
3. described preparation method with the fluorine-containing HTS of MWW structure of claim 1 is characterized in that this method comprises following concrete steps:
Synthesizing of the first step boracic parent
TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is (0.001～0.2): 1: (0.1～5): (0.1～5): (5～150) preparation feedback mixture, the perhaps TiO in the titanium source in molar ratio
2: the SiO in the silicon source
2: the B in the boron source
2O
3: organic formwork agent: H
2O is (0.005～0.1): 1: (0.15～2): (0.5～3): (15～50) preparation feedback mixture, and described titanium source is tetralkyl titanate, halogenated titanium or titanium oxide, described silicon source is silicic acid, silica gel, silicon sol or silicic acid tetraalkyl ester; Described boron source is boric acid or borate, and described organic formwork agent is piperidines, hexamethylene imine or both mixtures, earlier the titanium source is joined in the aqueous solution of organic formwork agent; Stir, add the boron source, stir; Add the silicon source, obtain reaction mixture, described reaction mixture was in 130～200 ℃ of hydrothermal crystallizings 5 hours～20 days; Through filtration, washing, drying, obtain the boracic parent;
The second step aftertreatment
Boracic parent that the first step is obtained and fluorine-containing acidic solution are 1 according to weight ratio: (5～50) preparation feedback mixture, wherein fluorine: SiO in the boracic parent
2Mol ratio be (0.01～0.3): 1, the acid concentration of acidic solution is 0.01～5 mol/l, handles 10 minutes～20 hours in room temperature～120 ℃, through filtration, washing, drying, obtains after-treatment products; Described fluorine source is Sodium Fluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid or silicofluoride, and described acid is mineral acid or organic acid;
The 3rd one-step baking
Second product that obtain of step in 400～700 ℃ of roastings 3～20 hours, is obtained having the fluorine-containing HTS of MWW structure.
4. the preparation method with the fluorine-containing HTS of MWW structure according to claim 3 is characterized in that said mineral acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and organic acid is formic acid, acetate, propionic acid or tartrate.
5. said application with the fluorine-containing HTS of MWW structure of claim 1 is characterized in that this molecular sieve is as the application of catalyzer in catalytic oxidation that contains carbon-to-carbon double bond and at least a other functional compounds and the synthetic oxime reaction of catalysis.
6. the application with the fluorine-containing HTS of MWW structure according to claim 5; It is characterized in that be reactant with the fluorine-containing HTS of MWW structure as catalyzer, with the compound that contains carbon-to-carbon double bond and at least a other functional group, the concrete operations step of the synthetic respective rings oxide compound of catalyzed oxidation:
The first step is added to catalyzer, solvent, reactant and oxygenant in the reactor drum successively, stirs; Reactant: catalyzer: the weight ratio of solvent is 1:0.03～0.15:1～10; Reactant: the mol ratio of oxygenant is 1:1～3; Described reactant is the compound that contains carbon-to-carbon double bond and at least a other functional group; Other functional group is at least a in alkyl, thiazolinyl, alkynyl, aryl, aryl, hydroxyl, ether, epoxy group(ing), halogeno-group, aldehyde radical, ketone group, carbonyl, ester group, carboxamido-group, cyanate ester based, NCO, thiocyanate groups, amido, diazo, nitro, itrile group, nitroso-group, sulfenyl, sulfoxide group, sulfuryl, thiol group, ortho acid ester group, imido grpup and the urea groups; Described oxygenant is at least a in hydrogen peroxide, tertbutyl peroxide, t-amyl peroxy hydrogen, cumyl hydroperoxide, ethylbenzene base hydrogen peroxide and the cyclohexyl hydroperoxide, and described solvent is alcohols, ketone, nitrile and water;
Second step reacted after 1～5 hour when the temperature of reaction of the reaction system of the first step is raised to 30～150 ℃, isolated catalyzer by the conventional filtration method, pressed routine operation then, separate with the corresponding epoxide of reactant.
7. the application with the fluorine-containing HTS of MWW structure according to claim 5 is characterized in that with the concrete operations step of the fluorine-containing HTS of MWW structure as the synthetic oxime of catalyst:
The first step is added to catalyzer, solvent, ketone or aldehyde, ammonia in the reactor drum successively, stirs; Ketone or aldehyde: catalyzer: the weight ratio of solvent is 1:0.03～0.15:1～10; Ketone or aldehyde: the mol ratio of ammonia is 1:1～3, and ketone is that carbonatoms is not more than 8 ketone, and aldehyde is that carbonatoms is not more than 6 aldehyde; Solvent can be the mixture of water or water and one of methyl alcohol, ethanol, the trimethyl carbinol, n-propyl alcohol, Virahol and sec-butyl alcohol; The content of water is at least 10% of total solution weight, and ammonia is gaseous ammonia or ammoniacal liquor, and the concentration of ammoniacal liquor is 1～50%;
Second step is when the temperature of reaction of the reaction system of the first step is raised to 30～150 ℃; In ketone or aldehyde: it is 1～50% hydrogen peroxide that the ratio of the mol ratio=1:1 of hydrogen peroxide～2 begins to drip concentration; The dropping time is 1～5 hour, dropwises continued reaction 0～3 hour;
After three-step reaction finishes, isolate catalyzer by the conventional filtration method, then by routine operation separate oxime.
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