CN103012119A - Method for oxidizing benzyl methyl ether - Google Patents
Method for oxidizing benzyl methyl ether Download PDFInfo
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- CN103012119A CN103012119A CN201110290099XA CN201110290099A CN103012119A CN 103012119 A CN103012119 A CN 103012119A CN 201110290099X A CN201110290099X A CN 201110290099XA CN 201110290099 A CN201110290099 A CN 201110290099A CN 103012119 A CN103012119 A CN 103012119A
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Abstract
The invention discloses a method for oxidizing benzyl methyl ether. The method comprises the step of mixing and contacting benzyl methyl ether, hydrogen peroxide, solvents and a catalyst under the condition of oxidation reaction. The method is characterized in that the catalyst contains multi-metal oxyacid and/or multi-metal oxysalt and titanium silicalite molecular sieves. The method is environment-friendly, is simple in production process and is beneficial to industrial production and application.
Description
Technical field
The invention relates to a kind of method of methyl benzyl ether oxidation.
Background technology
Phenylformic acid claims again M-nitro benzoic acid, is the simplest aromatic acid that carboxyl directly is connected with carbon atoms on a benzene ring, and namely a hydrogen on the phenyl ring (COOH) is replaced the compound that forms by carboxyl.Phenylformic acid is colourless, tasteless tabular crystal, 122.13 ℃ of fusing points, 249 ℃ of boiling points, relative density 1.2659 (15/4 ℃).Distil rapidly in the time of 100 ℃, its steam has very strong pungency, easily causes cough after the suction.Phenylformic acid is weak acid, and is stronger than lipid acid, is slightly soluble in water, is soluble in ethanol, ether, chloroform, benzene, toluene, dithiocarbonic anhydride, tetracol phenixin and turpentine wet goods organic solvent.Phenylformic acid extensively is present in occurring in nature with the form of free acid, ester or derivatives thereof.The general Chang Zuowei medicine of phenylformic acid or sanitas use, and the effect of Antifungi, bacterium, mould-growth is arranged, and also can be used for dyeing and the mordant of red ink paste used for seals.
Initial phenylformic acid is to make by loban destructive distillation or buck hydrolysis, also can be made by the urobenzoic acid hydrolysis.Be in the presence of the catalyzer such as cobalt, manganese, to make with atmospheric oxidation toluene at industrial phenylformic acid, or made by the Tetra hydro Phthalic anhydride hydrolysis decarboxylation.
Last century early eighties, Italy Taramasso is in USP4410501, a kind of new catalytic oxidation material that is called as HTS (TS-1) is disclosed, it has good selective oxidation (EP0230949 to hydrocarbon, alcohol, phenol etc., USP4480135, USP4396783).Document also has and carries out the research report [such as Sasidharan M etc., Tetrahedron Lett., 1995,36:9071] that the methyl benzyl ether oxidation prepares the phenylformic acid aspect take HTS as catalyzer.
Summary of the invention
The method that the purpose of this invention is to provide a kind of methyl benzyl ether oxidation.
The present inventor finds in long-term research practice, prepare in the phenylformic acid process in the methyl benzyl ether oxidation and to introduce multiple-metal oxygen-containing acid and/or Polyoxometalate bonding titanium si molecular sieves and can greatly improve methyl benzyl ether transformation efficiency and phenylformic acid selectivity in the methyl benzyl ether oxidising process as catalyzer, and finished the present invention based on this.
The method of methyl benzyl ether oxidation provided by the invention is under oxidation reaction condition, and methyl benzyl ether, hydrogen peroxide are contacted with catalyzer, it is characterized in that said catalyzer contains multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS.
Method of the present invention, reaction conditions is gentle, environmental friendliness, production process is simple, and easily control without the special producing equipment requirements, is beneficial to suitability for industrialized production.The purpose good product selectivity particularly under the relative low temperature condition, is compared with the single titanium-silicon molecular sieve catalyst of routine or multiple-metal oxygen-containing acid and salt thereof, and under the prerequisite that selectivity improves, transformation efficiency also significantly improves.
Embodiment
The invention provides a kind of method of methyl benzyl ether oxidation, the method comprises: under oxidation reaction condition, methyl benzyl ether, hydrogen peroxide are contacted with catalyzer, it is characterized in that said catalyzer contains multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS.
The method according to this invention, in the catalyzer, optional a wider range of the weight ratio of HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate, in order to obtain higher methyl benzyl ether transformation efficiency and phenylformic acid selectivity, under the preferable case, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS can be 1: 0.05-100, more preferably in the situation, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 1: 0.1-50.It should be explicitly made clear at this point, the multiple-metal oxygen-containing acid among the present invention and/or the weight of Polyoxometalate refer to: the weight sum of the multiple-metal oxygen-containing acid that may exist and the Polyoxometalate that may exist.
The method according to this invention, the acid of multiple-metal oxygen-containing described in the present invention can be various multiple-metal oxygen-containing acid (comprising the acid of reduction-state multiple-metal oxygen-containing) commonly used, described Polyoxometalate can be various Polyoxometalates (comprising the reduction-state Polyoxometalate) commonly used, for example described multiple-metal oxygen-containing acid can be heteropolyacid and/or isopoly-acid, and described Polyoxometalate can be heteropolyacid salt and/or isopoly-acid salt.
The concept of described isopoly-acid is well known to those skilled in the art, and refers to that a class that is comprised of identical acid anhydrides is sour, also can think the acid that two or more simple oxygen acid molecule of the same race condensations form.What easily form isopoly-acid in transition metal has elements such as Mo, W, V, Cr.Hydrogen ion in the isopoly-acid is replaced by metal ion can generate corresponding isopoly-acid salt.
The concept of described heteropolyacid also is well known to those skilled in the art, and generally refers to contain oxygen polyacid by certain structure by the class that the oxygen atom ligand bridging forms by heteroatoms (such as P, Si, Fe, Co etc.) and polyatom (such as Mo, W, V, Nb, Ta etc.).Hydrogen ion in the heteropolyacid is replaced by metal ion can generate corresponding heteropolyacid salt.
Among the present invention, described isopoly-acid (salt) comprises the isopoly-acid (salt) of reduced form, namely with how blue.Described heteropolyacid (salt) comprises the heteropolyacid (salt) of reduced form, i.e. heteropoly blue, and heteropoly blue is the general name of the transition metal heteropolyacid (salt) of a large class lower valency.Heteropoly blue is obtained by the reduction of heteropolyacid or heteropolyacid salt usually, and for example phosphato-molybdic heteropolyacid gets blue phosphorus molybdenum blue with Reduction with Stannous Chloride, again [SiW for example
11O
39]
8-Reducible is [SiW
12O
40]
6-Blue compound, tungsten wherein be+5 with the mixed valence of+6 valencys, P
3+, Fe
3+And Cr
3+The position that also can replace a tungsten atom.Other heteropoly blue also can obtain by reducing its corresponding acid or salt, gives unnecessary details no longer one by one at this.
In research process, the present inventor finds, when the metallic element in described multiple-metal oxygen-containing acid and/or the metal oxygen-containing hydrochlorate was selected from IVB family, VB family, group vib and the VIIB family metallic element one or more, reaction-ure conversion-age can further improve; Further under the preferable case, the metallic element in described multiple-metal oxygen-containing acid and/or the metal oxygen-containing hydrochlorate is selected from one or more in VB family, the group vib metallic element; Particularly, the metallic element in described multiple-metal oxygen-containing acid and/or the metal oxygen-containing hydrochlorate is one or more in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, the rhenium, is preferably in molybdenum, tungsten, vanadium, chromium, tantalum and the niobium one or more; Particularly preferably, in the isopoly-acid that the isopoly-acid that described multiple-metal oxygen-containing acid is the isopoly-acid that forms of phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, tungsten sila polyacid, metallic element molybdenum, metallic element tungsten forms and metallic element vanadium form one or more, described isopoly-acid is specifically as follows H
4V
2O
7, H
6V
4O
13, H
7V
5O
16, H
6V
10O
28, H
6Mo
7O
24, H
4Mo
8O
26And H
10Mo
12O
41In one or more.Described Polyoxometalate can be for corresponding with above-mentioned multiple-metal oxygen-containing acid, salt and reduzate thereof that hydrogen ion is replaced by metal ion, for example, described Polyoxometalate can be in ammonium corresponding to above-mentioned multiple-metal oxygen-containing acid, basic metal, the alkaline earth salt one or more, such as ammonium salt, sodium salt, sylvite, calcium salt, magnesium salts etc., give unnecessary details no longer one by one at this.In addition, also comprise reduced form, with the corresponding heteropoly blue of described multiple-metal oxygen-containing acid (salt), such as in phosphorus tungsten heteropoly blue, phosphorus molybdenum heteropoly blue, phosphorus vanadium heteropoly blue, molybdenum vanadium heteropoly blue, molybdenum tungsten heteropoly blue and the tungsten silicon heteropoly blue one or more.The present invention without particular requirement, can be various structures, as being the structures such as Keggin, Dawson, Silverton, Waugh, Anderson to the structure of described multiple-metal oxygen-containing acid and/or Polyoxometalate.
The method according to this invention, HTS described in the present invention can be the HTS (such as TS-1) of MFI structure, the HTS of MEL structure (such as TS-2), the HTS of BEA structure (such as Ti-Beta), the HTS of MWW structure (such as Ti-MCM-22), the HTS of two dimension hexagonal structure is (such as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (such as Ti-MOR), at least a in the HTS (such as Ti-ZSM-48) of the HTS of TUN structure (such as Ti-TUN) and other structures.
Under the preferable case, described HTS is one or more in the HTS of the HTS of HTS, MEL structure of MFI structure and BEA structure, the HTS of MFI structure more preferably, more preferably, described HTS is the MFI structure titanium silicon molecular sieve of hollow structure crystal grain, the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under 1 hour the condition at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and the desorption isotherm.
In the present invention, described HTS can be commercially available, and also can prepare, prepare the method for described HTS for conventionally known to one of skill in the art, such as the method described in the document (Zeolites, 1992, Vol.12 943-950 page or leaf).
The method according to this invention, and in order to make the reaction system homogeneous, described contact is generally carried out in solvent, and the consumption of described solvent can change in very wide in range scope, and preferably, the mass ratio of solvent and catalyzer is 1-1000: 1.
As everyone knows, at HTS/H
2O
2In the catalytic oxidation system, the effect of solvent mainly is in order to make reaction solution be homogeneous phase.Under this basic premise, the sterically hindered of solvent self can not be too large, can guarantee like this to react to carry out efficiently, and in the chosen process of solvent, those skilled in the art generally can select according to mentioned above principle.But can not be confined to above-mentioned requirements, concrete selection also needs to carry out according to concrete oxidizing reaction system.The present inventor finds, in the reaction system of methyl benzyl ether oxidation, in satisfying the solvent of aforementioned requirement, all can realize the present invention, but the methyl benzyl ether transformation efficiency is still limited.The present inventor further finds, reaction effect is better during as solvent with in water, alcohol, ketone, acid and the nitrile one or more, more preferably one or more in the nitrile of the acid of the ketone of the alcohol of water, C1-C6, C3-C8, C1-C3 and C2-C8; Wherein, the alcohol of described C1-C6 can be in the organic alcohol solvent such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol and isopropylcarbinol one or more; The ketone of described C3-C8 can be in organic ketone solvents such as acetone and butanone one or more; The acid of C1-C3 can be in the organic acid solvents such as formic acid, acetic acid, propionic acid one or more; The nitrile of described C2-C8 can be in the nitrile solvents such as acetonitrile, propionitrile, vinyl cyanide and benzyl cyanide one or more.More preferably, described solvent is one or more in acetonitrile, acetic acid, acetone, methyl alcohol, the trimethyl carbinol and the water.
The present invention to the condition of described oxidizing reaction without particular requirement, can for routine with the reaction conditions of HTS as the oxidation system of catalyzer, owing to easily explode when hydrogen peroxide exists with gaseous form, so hydrogen peroxide preferably providing with aqueous hydrogen peroxide solution described in the present invention.
When described hydrogen peroxide provided with aqueous hydrogen peroxide solution, the amount of described solvent also comprised the amount of the water in the aqueous hydrogen peroxide solution at this moment among the present invention.
The present invention without particular requirement, can be the hydrogen peroxide of 20-80 % by weight to the concentration of hydrogen peroxide in the described aqueous hydrogen peroxide solution (hydrogen peroxide), for example can be the hydrogen peroxide of 30 commercially available % by weight, 50 % by weight and 70 % by weight.
Method provided by the invention can adopt periodical operation, also can adopt operate continuously, the present invention to this without particular requirement.Feed way also can be any suitable way well known by persons skilled in the art, as when andnon-continuous operation manner is carried out, solvent, catalyzer can be added reactor after, add methyl benzyl ether continuously, hydrogen peroxide reacts; When in closed tank reactor, carrying out rhythmic reaction, catalyzer, solvent, methyl benzyl ether and hydrogen peroxide can be added hybrid reaction in the still simultaneously.Can adopt the reactor commonly used such as fixed-bed reactor, slurry bed reactor when continuous mode carries out, when carrying out in fixed-bed reactor, feed way can add solvent, methyl benzyl ether and hydrogen peroxide behind the catalyzer of packing into continuously; When in slurry bed reactor, carrying out, can be with adding methyl benzyl ether, hydrogen peroxide react continuously after the catalysts and solvents making beating; The present invention, does not give unnecessary details at this all without particular requirement one by one to this.
In method provided by the invention, be under the condition of 0.1-2.0MPa for being 20-180 ℃ with pressure in temperature preferred embodiment, be 1 with methyl benzyl ether, hydrogen peroxide, solvent and catalyzer according to the mol ratio of methyl benzyl ether and hydrogen peroxide: 0.1-10, the mass ratio of solvent and catalyzer is 1-1000: 1, the mass ratio of methyl benzyl ether and catalyzer is 1-100: the reaction of 1 ratio, wherein the ratio 0.1-100 of HTS and multiple-metal oxygen-containing acid or its salt in the catalyzer: 1.
In the method provided by the invention, in the further preferred embodiment, temperature of reaction is 50-150 ℃, reaction pressure is 0.1-1.5MPa, proportioning raw materials is that the mol ratio of methyl benzyl ether and hydrogen peroxide is 1: 0.2-5.0, the mass ratio of solvent and catalyzer is 5-200: 1, and the mass ratio of methyl benzyl ether and catalyzer is 5-80: 1.
In the method provided by the invention, the acid of HTS and multiple-metal oxygen-containing or the mass ratio of its salt are preferably 0.05-100 in the said catalyzer: 1, and 0.1-50 more preferably: 1.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and the Comparative Examples, if no special instructions, reaction is carried out in the universal autoclave of 250mL, and used reagent is commercially available analytical reagent, and use therein hydrogen peroxide is the aqueous solution, and its concentration is 30 % by weight.
Used HTS (TS-1) catalyzer is pressed the method preparation described in the document (Zeolites, 1992, Vol.12 943-950 page or leaf), and titanium oxide content is 2.5 % by weight.
Used hollow HTS HTS is that (Hunan is built feldspathization stock company and made for the Industrial products of the described HTS of Chinese patent CN1301599A, be the HTS of MFI structure through the X-ray diffraction analysis, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is the 15-180 nanometer; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
Used multiple-metal oxygen-containing acid and Polyoxometalate are all available from Chemical Reagent Co., Ltd., Sinopharm Group.
Among the present invention, adopt gas-chromatography to carry out each analysis that forms in the system, undertaken quantitatively all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the evaluation indexes such as selectivity of transformation efficiency and the product of reactant.
In Comparative Examples and embodiment:
Comparative Examples 1
Being 1: 2 with methyl benzyl ether, hydrogen peroxide and solvent methanol according to the mol ratio of methyl benzyl ether and hydrogen peroxide, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.React after 2 hours, the transformation efficiency of methyl benzyl ether is 0.4%; The phenylformic acid selectivity is 5%.
Comparative Examples 2
Be 1: 2 with methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1) according to the mol ratio of methyl benzyl ether and hydrogen peroxide, solvent methanol is 20: 1 with the catalyst quality ratio, the mass ratio of methyl benzyl ether and catalyzer is 20: 1, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 23%; The phenylformic acid selectivity is 81%.
Comparative Examples 3
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (phosphorus heteropoly tungstic acid H
3PW
12O
40) be 1: 5 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, solvent methanol is 20: 1 with the catalyst quality ratio, the mass ratio of methyl benzyl ether and catalyzer is 20: 1, is that 100 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 15%; The phenylformic acid selectivity is 36%.
Embodiment 1
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 and phosphorus heteropoly tungstic acid H
3PW
12O
40Mass ratio be 10: 1) be 1: 2 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, solvent methanol is 20: 1 with the catalyst quality ratio, the mass ratio of methyl benzyl ether and catalyzer is 20: 1, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 54%; The phenylformic acid selectivity is 93%.
Embodiment 2
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 and molybdenum tungsten heteropoly blue H
5MoW
12O
40Mass ratio be 0.1: 1) be 1: 4 according to the mol ratio of sulfide and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 120: 1, the mass ratio of sulfide and catalyzer is 40: 1, is that 50 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 39%; The phenylformic acid selectivity is 94%.
Embodiment 3
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 with vanadium polyacid H
4V
2O
7Mass ratio be 50: 1) be 1: 5 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 200: 1, the mass ratio of methyl benzyl ether and catalyzer is 80: 1, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 74%; The phenylformic acid selectivity is 98%.
Embodiment 4
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 and phosphato-molybdic heteropolyacid H
3PMo
12O
40Mass ratio be 10: 1) be 1: 3 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent tertiary butanol and catalyzer is 80: 1, the mass ratio of methyl benzyl ether and catalyzer is 2: 1, is that 140 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 77%; The phenylformic acid selectivity is 96%.
Embodiment 5
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 and phosphorus tungsten heteropoly blue H
5PW
12O
40Mass ratio be 20: 1) be 1: 3 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of aqueous solvent and catalyzer is 180: 1, the mass ratio of methyl benzyl ether and catalyzer is 5: 1, is that 90 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 68%; The phenylformic acid selectivity is 95%.
Embodiment 6
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 and ammonium phosphomolybdate (NH
4)
3PMo
12O
40Mass ratio be 20: 1) be 5: 1 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 10: 1, the mass ratio of methyl benzyl ether and catalyzer is 10: 1, is that 80 ℃ of pressure are to react under the 0.2MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 17%; The phenylformic acid selectivity is 93%.
Embodiment 7
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 with molybdenum polyacid H
4Mo
8O
26Mass ratio be 15: 1) be 3: 1 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 80: 1, the mass ratio of methyl benzyl ether and catalyzer is 100: 1, is that 60 ℃ of pressure are to react under the 0.1MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 29%; The phenylformic acid selectivity is 97%.
Embodiment 8
With methyl benzyl ether, hydrogen peroxide, solvent and catalyzer (TS-1 with tungsten polyacid ammonium (NH
4)
4W
8O
26Mass ratio be 50: 1) be 2: 1 according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 40: 1, the mass ratio of methyl benzyl ether and catalyzer is 60: 1, is that 130 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 44%; The phenylformic acid selectivity is 93%.
Embodiment 9
Identical with the method for embodiment 1, different is, TS-1 by etc. the HTS of weight replace.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 67%; The phenylformic acid selectivity is 95%.
Embodiment 10
Identical with the method for embodiment 1, different is, TS-1 by etc. the Ti-MCM-41 (for by prior art: Corma etc., the method preparation described in the Chem.Commun., 1994,147-148, titanium oxide content is 3%) of weight replace.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 45%; The phenylformic acid selectivity is 89%.
Embodiment 11
Identical with the method for embodiment 1, different is, TS-1 by etc. the Ti-Beta of weight (for by prior art: Takashi Tatsumi etc., J.Chem.Soc., method preparation described in the Chem.Commun.1997,677-678, titanium oxide content is 2.6%) replace.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 51%; The phenylformic acid selectivity is 91%.
Embodiment 12
Identical with the method for embodiment 1, different is, the add-on of phosphorus heteropoly tungstic acid is constant, and the weight ratio of TS-1 and phosphorus heteropoly tungstic acid is 1000: 1.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 28%; The phenylformic acid selectivity is 83%.
Embodiment 13
Identical with the method for embodiment 1, different is, the acetic acid of weight such as uses to replace methyl alcohol as solvent.
The result who reacts 2 hours is as follows: the methyl benzyl ether transformation efficiency is 73%; The phenylformic acid selectivity is 95%.
Can find out from embodiment and Comparative Examples: the inventive method methyl benzyl ether transformation efficiency is high, and the phenylformic acid selectivity is good.
Claims (16)
1. the method for a methyl benzyl ether oxidation, the method comprises: under oxidation reaction condition, methyl benzyl ether, hydrogen peroxide are contacted with catalyst mix, it is characterized in that said catalyzer contains multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS.
2. according to the process of claim 1 wherein, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 1: 0.05-100.
3. according to the method for claim 2, wherein, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 1: 0.1-50.
4. according to the method for any one among the claim 1-3, wherein, described multiple-metal oxygen-containing acid is heteropolyacid and/or isopoly-acid.
5. according to the method for claim 4, wherein, the metallic element in the described multiple-metal oxygen-containing acid is selected from one or more in IVB family, VB family, group vib and the VIIB family metallic element.
6. according to the method for claim 5, wherein, the metallic element in the described multiple-metal oxygen-containing acid is selected from one or more in VB family, the group vib metallic element.
7. according to the method for claim 6, wherein, the metallic element in the described multiple-metal oxygen-containing acid is one or more in molybdenum, tungsten, vanadium, chromium, tantalum and the niobium.
8. according to the method for claim 7, wherein, one or more in the isopoly-acid that the isopoly-acid that described multiple-metal oxygen-containing acid is the isopoly-acid that forms of phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, tungsten sila polyacid, metallic element molybdenum, metallic element tungsten forms and metallic element vanadium form.
9. according to the method for any one among the claim 1-3, wherein, described HTS is at least a in the HTS of the HTS of HTS, TUN structure of HTS, the MOR structure of HTS, the MWW structure of HTS, the BEA structure of HTS, the MEL structure of MFI structure and two-dimentional hexagonal structure.
10. according to the method for claim 9, wherein, described HTS is the HTS of MFI structure, and described HTS crystal grain is hollow structure, the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under 1 hour the condition at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and the desorption isotherm.
11. according to the process of claim 1 wherein, described reaction is carried out in solvent, the mass ratio of solvent and catalyzer is 1-1000: 1.
12. according to the process of claim 1 wherein, wherein, described solvent is one or more in the nitrile of the acid of ketone, C1-C3 of alcohol, the C3-C8 of water, C1-C6 and C2-C8.
13. according to the method for claim 12, wherein, described solvent is one or more in acetic acid, acetonitrile, acetone, methyl alcohol, the trimethyl carbinol and the water.
14. the method according to claim 1 or 11, wherein, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, described oxidation reaction condition comprises, it is 0.1-2.0MPa with pressure that Contact Temperature is 20-180 ℃, the mol ratio of methyl benzyl ether and hydrogen peroxide is 1: 0.1-10, the mass ratio of methyl benzyl ether and catalyzer are 1-100: 1.
15. according to the process of claim 1 wherein, Contact Temperature is 50-150 ℃, reaction pressure is 0.1-1.5MPa, and the mol ratio of methyl benzyl ether and hydrogen peroxide is 1: 0.2-5.0, the mass ratio of solvent and catalyzer are 1-1000: 1.
16. the method according to claim 1, it is characterized in that being 50-150 ℃ in temperature is under the condition of 0.1-1.5MPa with pressure, with methyl benzyl ether, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of methyl benzyl ether and hydrogen peroxide solvent is 1: 0.2-5.0, the mass ratio of solvent and catalyzer is 5-200: 1, and the mass ratio of methyl benzyl ether and catalyzer is 5-80: 1, the ratio 0.1-50 of the acid of HTS and multiple-metal oxygen-containing or its salt in the catalyzer: 1.
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| CN110655458A (en) * | 2018-06-29 | 2020-01-07 | 中国石油化工股份有限公司 | Method for simultaneously producing benzoic acid and acetone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655458A (en) * | 2018-06-29 | 2020-01-07 | 中国石油化工股份有限公司 | Method for simultaneously producing benzoic acid and acetone |
| CN110655458B (en) * | 2018-06-29 | 2022-07-12 | 中国石油化工股份有限公司 | Method for simultaneously producing benzoic acid and acetone |
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| CN103012119B (en) | 2015-02-25 |
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