CN103012119B - Method for oxidizing benzyl methyl ether - Google Patents
Method for oxidizing benzyl methyl ether Download PDFInfo
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- CN103012119B CN103012119B CN201110290099.XA CN201110290099A CN103012119B CN 103012119 B CN103012119 B CN 103012119B CN 201110290099 A CN201110290099 A CN 201110290099A CN 103012119 B CN103012119 B CN 103012119B
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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 the method for a kind of methyl benzyl ether oxidation.
Background technology
Phenylformic acid is also known as M-nitro benzoic acid, and be the simplest aromatic acid that carboxyl is directly connected with carbon atoms on a benzene ring, a hydrogen namely on phenyl ring is replaced the compound formed by carboxyl (-COOH).Phenylformic acid is colourless, tasteless tabular crystal, fusing point 122.13 DEG C, boiling point 249 DEG C, relative density 1.2659 (15/4 DEG C).Distil rapidly 100 DEG C time, its steam has very strong pungency, easily causes cough after suction.Phenylformic acid is weak acid, 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 is extensively 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 have the effect of Antifungi, bacterium, mould-growth, also can be used for the mordant of dyeing and red ink paste used for seals.
Initial phenylformic acid is obtained by loban destructive distillation or buck hydrolysis, also can be hydrolyzed obtained by urobenzoic acid.Industrially phenylformic acid obtains with atmospheric oxidation toluene under the catalyzer such as cobalt, manganese exists, or obtained by Tetra hydro Phthalic anhydride hydrolysis decarboxylation.
Last century early eighties, Italy Taramasso is in USP4410501, disclose the new catalytic oxidation material that one is called as HTS (TS-1), it has good selective oxidation (EP0230949 to hydrocarbon, alcohol, phenol etc., USP4480135, USP4396783).Document also have with HTS be catalyzer carry out methyl benzyl ether oxidation prepare phenylformic acid aspect research report [as Sasidharan M etc., Tetrahedron Lett., 1995,36:9071].
Summary of the invention
The object of this invention is to provide the method for a kind of methyl benzyl ether oxidation.
The present inventor finds in long-term research practice, prepare in phenylformic acid process in methyl benzyl ether oxidation and introduce multiple-metal oxygen-containing acid and/or Polyoxometalate bonding titanium si molecular sieves can improve methyl benzyl ether transformation efficiency in methyl benzyl ether oxidising process and phenylformic acid selectivity greatly as catalyzer, and complete the present invention based on this.
The method of methyl benzyl ether provided by the invention oxidation is under oxidation reaction condition, by methyl benzyl ether, hydrogen peroxide and catalyst exposure, 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, and production process is simple, easily controls, without special producing equipment requirements, is beneficial to suitability for industrialized production.Object good product selectivity, particularly under relative low temperature condition, compared with the single titanium-silicon molecular sieve catalyst of routine or multiple-metal oxygen-containing acid and salt thereof, under the prerequisite that selectivity improves, transformation efficiency also significantly improves.
Embodiment
The invention provides the method for a kind of methyl benzyl ether oxidation, the method comprises: under oxidation reaction condition, by methyl benzyl ether, hydrogen peroxide and catalyst exposure, it is characterized in that said catalyzer contains multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS.
According to method of the present invention, in catalyzer, the range of choices of the weight ratio of HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate is wider, in order to obtain higher methyl benzyl ether transformation efficiency and phenylformic acid selectivity, under 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 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 in 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.
According to method of the present invention, the acid of multiple-metal oxygen-containing described in the present invention can for conventional various multiple-metal oxygen-containing acid (comprising the acid of reduction-state multiple-metal oxygen-containing), described Polyoxometalate can for conventional various Polyoxometalates (comprising reduction-state Polyoxometalate), such as 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 the class acid be made up of identical acid anhydrides, also can think the acid of two or more simple oxygen acid molecule of the same race condensations.What in transition metal, easily form isopoly-acid has the elements such as Mo, W, V, Cr.Hydrogen ion in isopoly-acid is replaced by metal ion can generate corresponding isopoly-acid salt.
The concept of described heteropolyacid is also well known to those skilled in the art, and generally refers to that the class consisted of oxygen atom ligand bridging by certain structure heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.) contains oxygen polyacid.Hydrogen ion in heteropolyacid is replaced by metal ion can generate corresponding heteropolyacid salt.
In 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 usually reduced by heteropolyacid or heteropolyacid salt and obtains, and such as phosphato-molybdic heteropolyacid Reduction with Stannous Chloride obtains blue P-Mo blue, again such as [SiW
11o
39]
8-reducible is [SiW
12o
40]
6-blue compound, tungsten is wherein the mixed valence of+5 and+6 valencys, P
3+, Fe
3+and Cr
3+also can replace the position of a tungsten atom.Other heteropoly blue also can be obtained by its corresponding acid of reduction or salt, and this is no longer going to repeat them.
In research process, the present inventor finds, when the metallic element in described multiple-metal oxygen-containing acid and/or metal oxyacid salts is selected from one or more in IVB race, VB race, group vib and VIIB race metallic element, reaction-ure conversion-age can improve further; Under further preferable case, the metallic element in the acid of described multiple-metal oxygen-containing and/or metal oxyacid salts be selected from VB race, group vib metallic element one or more; Particularly, the metallic element in the acid of described multiple-metal oxygen-containing and/or metal oxyacid salts is one or more in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, is preferably one or more in molybdenum, tungsten, vanadium, chromium, tantalum and niobium; Particularly preferably, described multiple-metal oxygen-containing acid be phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, substituted complexes, metallic element molybdenum formed isopoly-acid, metallic element tungsten formed isopoly-acid and metallic element vanadium formed isopoly-acid in 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 corresponding with the acid of above-mentioned multiple-metal oxygen-containing, the salt that hydrogen ion is replaced by metal ion and reduzate thereof, such as, described Polyoxometalate can be one or more in ammonium corresponding to above-mentioned multiple-metal oxygen-containing acid, basic metal, alkaline earth salt, as ammonium salt, sodium salt, sylvite, calcium salt, magnesium salts etc., this is no longer going to repeat them.In addition, also comprise reduced form, heteropoly blue corresponding with described multiple-metal oxygen-containing acid (salt), as one or more in phosphorus tungsten heteropoly blue, phosphorus molybdenum heteropoly blue, phosphorus vanadium heteropoly blue, molybdenum vanadium heteropoly blue, molybdenum tungsten heteropoly blue and tungsten silicon heteropoly blue.The present invention without particular requirement, can be various structure, as being the structures such as Keggin, Dawson, Silverton, Waugh, Anderson to the structure of the acid of described multiple-metal oxygen-containing and/or Polyoxometalate.
According to method of the present invention, HTS described in the present invention can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structures.
Under preferable case, described HTS is one or more in the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, be more preferably the HTS of MFI structure, more preferably, described HTS is the MFI structure HTS of hollow structure crystal grain, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and 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, as the method described in document (Zeolites, 1992, Vol.12 943-950 page).
According to method of the present invention, and in order to make reaction system homogeneous, described contact is generally carried out in a 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 catalytic oxidation system, the effect of solvent is mainly 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 ensure that reaction is carried out efficiently like this, 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 the solvent meeting aforementioned claim, all can realize the present invention, but methyl benzyl ether transformation efficiency is still limited.The present inventor finds further, and during using one or more in water, alcohol, ketone, acid and nitrile as solvent, reaction effect is better, one or more in the nitrile of the more preferably alcohol of water, C1-C6, the ketone of C3-C8, the acid of C1-C3 and C2-C8; Wherein, the alcohol of described C1-C6 can be one or more in the organic alcohol solvent such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol and isopropylcarbinol; The ketone of described C3-C8 can be one or more in the organic ketone solvent such as acetone and butanone; The acid of C1-C3 can be one or more in the organic acid solvents such as formic acid, acetic acid, propionic acid; The nitrile of described C2-C8 can be one or more in the nitrile solvents such as acetonitrile, propionitrile, vinyl cyanide and benzyl cyanide.More preferably, described solvent is one or more in acetonitrile, acetic acid, acetone, methyl alcohol, the trimethyl carbinol and water.
The present invention to the condition of described oxidizing reaction without particular requirement, it can be the reaction conditions of the conventional oxidation system using HTS as catalyzer, owing to easily exploding when hydrogen peroxide exists in a gaseous form, therefore described in the present invention, hydrogen peroxide preferably provides with aqueous hydrogen peroxide solution.
In the present invention when described hydrogen peroxide provides with aqueous hydrogen peroxide solution, now the amount of described solvent also comprises the amount of the water in aqueous hydrogen peroxide solution.
The present invention without particular requirement, can be the hydrogen peroxide of 20-80 % by weight to the concentration of hydrogen peroxide in described aqueous hydrogen peroxide solution (hydrogen peroxide), such as, can be the hydrogen peroxide of commercially available 30 % 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, after solvent, catalyzer can being added reactor, adds methyl benzyl ether continuously, hydrogen peroxide reacts; When carrying out rhythmic reaction in closed tank reactor, catalyzer, solvent, methyl benzyl ether and hydrogen peroxide can be added hybrid reaction in still simultaneously.Can adopt the reactor that fixed-bed reactor, slurry bed reactor etc. are conventional when continuous mode carries out, when carrying out in fixed-bed reactor, solvent, methyl benzyl ether and hydrogen peroxide can add continuously by feed way after loading catalyzer; When carrying out in slurry bed reactor, add methyl benzyl ether continuously after catalysts and solvents can being pulled an oar, hydrogen peroxide reacts; The present invention, does not repeat at this all without particular requirement one by one to this.
In method provided by the invention, be preferred embodiment under temperature is 20-180 DEG C and pressure is the condition of 0.1-2.0MPa, be 1: 0.1-10 by methyl benzyl ether, hydrogen peroxide, solvent and catalyzer according to the mol ratio of methyl benzyl ether and hydrogen peroxide, the mass ratio of solvent and catalyzer is 1-1000: 1, the mass ratio of methyl benzyl ether and catalyzer be 1-100: 1 ratio react, wherein ratio 0.1-100: 1 of HTS and multiple-metal oxygen-containing acid or its salt in catalyzer.
In method provided by the invention, in further preferred embodiment, temperature of reaction is 50-150 DEG C, reaction pressure is 0.1-1.5MPa, proportioning raw materials is 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 method provided by the invention, in said catalyzer, HTS and multiple-metal oxygen-containing acid or the mass ratio of its salt are preferably 0.05-100: 1, and more preferably 0.1-50: 1.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and comparative example, if no special instructions, reaction is carried out in the universal autoclave of 250mL, and used reagent is commercially available analytical reagent, and the hydrogen peroxide wherein used is the aqueous solution, and its concentration is 30 % by weight.
The method preparation described in document (Zeolites, 1992, Vol.12 943-950 page) pressed by HTS (TS-1) catalyzer used, and titanium oxide content is 2.5 % by weight.
The Industrial products of HTS described in hollow HTS HTS system Chinese patent CN1301599A used (build feldspathization stock company and manufacture by Hunan, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
Multiple-metal oxygen-containing acid used and Polyoxometalate are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant and the selectivity of product on this basis.
In comparative example and embodiment:
Comparative example 1
Be 1: 2 by methyl benzyl ether, hydrogen peroxide and solvent methanol according to the mol ratio of methyl benzyl ether and hydrogen peroxide, react under be 80 DEG C of pressure being 1.5MPa in temperature.React after 2 hours, the transformation efficiency of methyl benzyl ether is 0.4%; Phenylformic acid selectivity is 5%.
Comparative example 2
Be 1: 2 by 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 catalyst quality ratio, the mass ratio of methyl benzyl ether and catalyzer is 20: 1, reacts under be 80 DEG C of pressure being 1.5MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 23%; Phenylformic acid selectivity is 81%.
Comparative example 3
By 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 catalyst quality ratio, and the mass ratio of methyl benzyl ether and catalyzer is 20: 1, reacts under be 100 DEG C of pressure being 0.5MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 15%; Phenylformic acid selectivity is 36%.
Embodiment 1
By 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 catalyst quality ratio, and the mass ratio of methyl benzyl ether and catalyzer is 20: 1, reacts under be 80 DEG C of pressure being 1.5MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 54%; Phenylformic acid selectivity is 93%.
Embodiment 2
By 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, and the mass ratio of sulfide and catalyzer is 40: 1, reacts under be 50 DEG C of pressure being 1.0MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 39%; Phenylformic acid selectivity is 94%.
Embodiment 3
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 80: 1, reacts under be 60 DEG C of pressure being 1.0MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 74%; Phenylformic acid selectivity is 98%.
Embodiment 4
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 2: 1, reacts under be 140 DEG C of pressure being 0.5MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 77%; Phenylformic acid selectivity is 96%.
Embodiment 5
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 5: 1, reacts under be 90 DEG C of pressure being 1.0MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 68%; Phenylformic acid selectivity is 95%.
Embodiment 6
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 10: 1, reacts under be 80 DEG C of pressure being 0.2MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 17%; Phenylformic acid selectivity is 93%.
Embodiment 7
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 100: 1, reacts under be 60 DEG C of pressure being 0.1MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 29%; Phenylformic acid selectivity is 97%.
Embodiment 8
By 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, and the mass ratio of methyl benzyl ether and catalyzer is 60: 1, reacts under be 130 DEG C of pressure being 1.5MPa in temperature.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 44%; Phenylformic acid selectivity is 93%.
Embodiment 9
Identical with the method for embodiment 1, unlike, TS-1 by etc. the HTS of weight replace.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 67%; Phenylformic acid selectivity is 95%.
Embodiment 10
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-MCM-41 (for by prior art: Corma etc., Chem.Commun., the method preparation described in 1994,147-148, titanium oxide content is 3%) of weight replace.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 45%; Phenylformic acid selectivity is 89%.
Embodiment 11
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-Beta of weight (for by prior art: Takashi Tatsumi etc., J.Chem.Soc., method preparation described in Chem.Commun.1997,677-678, titanium oxide content is 2.6%) replace.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 51%; Phenylformic acid selectivity is 91%.
Embodiment 12
Identical with the method for embodiment 1, unlike, 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 of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 28%; Phenylformic acid selectivity is 83%.
Embodiment 13
Identical with the method for embodiment 1, unlike, the acetic acid of the weight such as use replaces methyl alcohol as solvent.
The result of reacting 2 hours is as follows: methyl benzyl ether transformation efficiency is 73%; Phenylformic acid selectivity is 95%.
As can be seen from embodiment and comparative example: the inventive method methyl benzyl ether transformation efficiency is high, phenylformic acid selectivity is good.
Claims (10)
1. the method for a methyl benzyl ether oxidation, the method comprises: under oxidation reaction condition, by methyl benzyl ether, hydrogen peroxide contacts with catalyst mix, it is characterized in that said catalyzer contains multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 1: 0.05-100, wherein, described multiple-metal oxygen-containing acid is phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, substituted complexes, the isopoly-acid that metallic element molybdenum is formed, metallic element tungsten formed isopoly-acid and metallic element vanadium formed isopoly-acid in one or more, described Polyoxometalate is corresponding with the acid of above-mentioned multiple-metal oxygen-containing, the salt that hydrogen ion is replaced by metal ion and reduzate thereof.
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: 0.1-50.
3. according to the method for claim 1 or 2, wherein, described HTS is at least one in the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure and two-dimentional hexagonal structure.
4. according to the method for claim 3, wherein, described HTS is the HTS of MFI structure, and described HTS crystal grain is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
5. according to the process of claim 1 wherein, described reaction is carried out in a solvent, and the mass ratio of solvent and catalyzer is 1-1000: 1.
6. according to the process of claim 1 wherein, wherein, described solvent is one or more in the nitrile of water, the alcohol of C1-C6, the ketone of C3-C8, the acid of C1-C3 and C2-C8.
7. according to the method for claim 6, wherein, described solvent is one or more in acetic acid, acetonitrile, acetone, methyl alcohol, the trimethyl carbinol and water.
8. according to the method for claim 1, wherein, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, described oxidation reaction condition comprises, Contact Temperature is 20-180 DEG C and pressure is 0.1-2.0MPa, the mol ratio of methyl benzyl ether and hydrogen peroxide is 1: 0.1-10, and the mass ratio of methyl benzyl ether and catalyzer is 1-100: 1.
9. according to the process of claim 1 wherein, Contact Temperature is 50-150 DEG C, and reaction pressure is 0.1-1.5MPa, and the mol ratio of methyl benzyl ether and hydrogen peroxide is 1: 0.2-5.0, and the mass ratio of solvent and catalyzer is 1-1000: 1.
10. according to the method for claim 1, it is characterized in that under temperature is 50-150 DEG C and pressure is the condition of 0.1-1.5MPa, methyl benzyl ether, hydrogen peroxide, solvent and catalyst exposure are reacted, wherein, 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, ratio 0.1-50: 1 of HTS and multiple-metal oxygen-containing acid or its salt in catalyzer.
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