CN102863368A - Method for oxidizing tertiary butanol - Google Patents
Method for oxidizing tertiary butanol Download PDFInfo
- Publication number
- CN102863368A CN102863368A CN2011101888115A CN201110188811A CN102863368A CN 102863368 A CN102863368 A CN 102863368A CN 2011101888115 A CN2011101888115 A CN 2011101888115A CN 201110188811 A CN201110188811 A CN 201110188811A CN 102863368 A CN102863368 A CN 102863368A
- Authority
- CN
- China
- Prior art keywords
- hts
- trimethyl carbinol
- acid
- metal oxygen
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for oxidizing tertiary butanol. The method comprises the following steps of: enabling tertiary butanol, hydrogen peroxide and a catalyzer to be contacted under an oxidizing reaction condition, wherein the catalyzer contains titanosincalite molecular sieves and multi-metal oxyacid and/or multi-metal oxysalt. The method is environment-friendly, high in conversion rate of tertiary butanol and high in yield coefficient of a target product-tert-butyl hydroperoxide.
Description
Technical field
The present invention relates to a kind of method of Oxidation of t-Butanol.
Background technology
Tertbutyl peroxide is water white transparency or yellow liquid, can with the immiscible organic solvents such as ethanol, ether, be widely used in dyeing and the stamp of the fibers such as cotton, viscose glue, silk, continuous synthetic fibre and fabric thereof, also be used for washing/gluing blended fabric dyeing, can also be as the catalyzer of polyreaction, the siccative of unsaturated melamine resin coating, polymerization starter and organic synthesis intermediate.
The method for preparing at present tertbutyl peroxide mainly contains following several: a kind of is by with after the p-Nitroaniline ortho-sulfonic acid diazotization, with sour coupling, then the nitroreduction in the conjugates is become amino, again with the phosgene condensation, finally by saltouing, filter and dry and make; Another is to make with hydroperoxidation after generating the hydrogen sulfate tert-butyl ester by the trimethyl carbinol and sulfuric acid reaction; Also have a kind of method, by the trimethyl carbinol is under agitation mixed with hydrogen peroxide, then be warming up to 50 ℃, add sulfuric acid, reaction 5h, temperature remains on 55-60 ℃, and standing demix is got the top oil reservoir with anhydrous sodium sulfate drying, filtration, obtains tertbutyl peroxide.This shows that existing various preparation technologies all need use acidic substance, therefore have the problems such as equipment corrosion is serious, hazardous emission, this utmost point does not meet eco-friendly developing direction.
Disclose a kind of method for preparing tertbutyl peroxide among the CN1699339A, the method makes tertbutyl peroxide take hydrogen peroxide as oxygenant take HTS as the catalyst oxidation trimethyl carbinol.The problems such as the prior art equipment corrosion is serious although the method efficiently solves, hazardous emission, however the yield of tertbutyl peroxide still remains to be improved in this process.
Summary of the invention
The method that the purpose of this invention is to provide the Oxidation of t-Butanol that a kind of eco-friendly, trimethyl carbinol transformation efficiency is high, target product tertbutyl peroxide yield is high.
The present inventor further studies with the trimethyl carbinol as raw material on the basis of CN1699339A, prepare take HTS as catalyzer in the process of tertbutyl peroxide and find, in any case by further optimizing various processing parameters in this process (as selecting suitable solvent, optimize the condition of oxidizing reaction etc.), the yield of the transformation efficiency of the trimethyl carbinol and target product tertbutyl peroxide all can't further significantly improve.Through long-term endeavour, by multiple imagination is put into practice, the present inventor finds finally, introducing multiple-metal oxygen-containing acid and/or Polyoxometalate can improve the transformation efficiency of the trimethyl carbinol in the oxidising process and the yield of target product tertbutyl peroxide greatly in this process, have finished the present invention based on this discovery.
The invention provides a kind of method of Oxidation of t-Butanol, the method comprises: under oxidation reaction condition, the trimethyl carbinol, hydrogen peroxide are contacted with catalyzer, wherein, described catalyzer contains HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate.
Method environmental friendliness of the present invention, the transformation efficiency of the trimethyl carbinol is high, and the yield of target product tertbutyl peroxide is high.Contrast embodiments of the invention and Comparative Examples can find that the transformation efficiency of the trimethyl carbinol that the method reaction of embodiments of the invention 1 obtained after 2 hours is 1.2 times of Comparative Examples 2, and the yield of tertbutyl peroxide is 1.3 times of Comparative Examples 2; The transformation efficiency of the trimethyl carbinol that the method reaction of embodiments of the invention 1 obtained after 2 hours is 1.1 times of Comparative Examples 3, and the yield of tertbutyl peroxide is 2.8 times of Comparative Examples 3.
Embodiment
The method of Oxidation of t-Butanol of the present invention comprises: under oxidation reaction condition, the trimethyl carbinol, hydrogen peroxide are contacted with catalyzer, wherein, described catalyzer contains HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate.
Among the present invention, multiple-metal oxygen-containing acid and/or Polyoxometalate refer to multiple-metal oxygen-containing acid, Polyoxometalate or their mixture.
The method according to this invention, in the catalyzer, the optional a wider range of the weight ratio of HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate, but in order to make method of the present invention obtain higher trimethyl carbinol transformation efficiency and the yield of target product, under the preferable case, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS can be 0.01-20: 1, more preferably in the situation, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 0.01-10: 1.
Among the present invention, described multiple-metal oxygen-containing acid (that is, polyacid) refers to the oxygen acid cluster compound that a plurality of metal oxygen-containing acid molecules form by dehydrating condensation.The method according to this invention, described multiple-metal oxygen-containing acid can be various multiple-metal oxygen-containing acid commonly used, and Polyoxometalate can replace the Polyoxometalate that forms with the one or more hydrogen ions in the described multiple-metal oxygen-containing acid with ammonium radical ion or metal ion for various passing through commonly used.Among the present invention, described multiple-metal oxygen-containing acid can be heteropolyacid and/or isopoly-acid, and described Polyoxometalate can be the salt of heteropolyacid and/or the salt of isopoly-acid.Among the present invention, the salt of described heteropolyacid comprises various one or more hydrogen ions in the heteropolyacid are replaced with metal ion or ammonium radical ion and the salt that forms, can also comprise the heteropoly blue that heteropolyacid or heteropolyacid salt is reduced and obtain.Among the present invention, described heteropolyacid is well known to those skilled in the art, and generally contains 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 many atoms metals (such as Mo, W, V, Nb, Ta etc.).Described heteropoly blue can be obtained by heteropolyacid or heteropolyacid salt reduction usually, for example phospho-molybdic acid can access blue phosphorus molybdenum blue with Reduction with Stannous Chloride, other heteropolyacid indigo plant also can obtain by reducing its corresponding heteropolyacid or heteropolyacid salt, gives unnecessary details no longer one by one at this.The present invention without particular requirement, can be heteropolyacid or the heteropolyacid salt of various structures to the structure of described heteropolyacid and heteropolyacid salt, for example can be Keggin structure, Dawson structure, Silverton structure, Waugh structure or Anderson structure.Described isopoly-acid is also for those skilled in the art know, and the hydrogen ion in the isopoly-acid is replaced the salt that can generate corresponding isopoly-acid by metal ion.
The present inventor finds in research process, when the metallic element in the salt of the acid of described multiple-metal oxygen-containing and/or described multiple-metal oxygen-containing acid is in IVB family metallic element, VB family metallic element, group vib metallic element and the VIIB family metallic element one or more, can further improve the activity of catalyst according to the invention, thereby further improve the selectivity of transformation efficiency and the tertbutyl peroxide of the trimethyl carbinol.Metallic element in the salt of the acid of described multiple-metal oxygen-containing and/or described multiple-metal oxygen-containing acid for example can be in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium and the rhenium one or more.Preferably, the metallic element in the salt of described multiple-metal oxygen-containing acid and/or described multiple-metal oxygen-containing acid is one or more in VB family metallic element and the group vib metallic element.More preferably, the metallic element in the salt of described multiple-metal oxygen-containing acid and/or described multiple-metal oxygen-containing acid is one or more in molybdenum, tungsten, vanadium, chromium, tantalum and the niobium.Further preferably, described multiple-metal oxygen-containing acid be phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, in the isopoly-acid that formed by molybdenum, the isopoly-acid that is formed by tungsten and the isopoly-acid that formed by vanadium one or more; In the salt of the salt of the salt of the isopoly-acid that the salt of described multiple-metal oxygen-containing acid is the salt of salt, the molybdenum vanadium heteropolyacid of salt, the phosphorus vanadium heteropolyacid of salt, the phosphato-molybdic heteropolyacid of phosphorus heteropoly tungstic acid, formed by molybdenum, the isopoly-acid that formed by tungsten and the isopoly-acid that formed by vanadium one or more.Among the present invention, the specific examples of described isopoly-acid can for but be not limited to: H
4V
2O
7, H
6V
4O
13, H
7V
5O
16, H
6V
10O
2, H
6Mo
7O
24, H
4Mo
8O
26And H
10Mo
12O
41In one or more.The salt of described multiple-metal oxygen-containing acid can be the ammonium salt of above-mentioned multiple-metal oxygen-containing acid, an alkali metal salt or alkaline earth salt, for example: the ammonium salt of phosphorus heteropoly tungstic acid, the an alkali metal salt of phosphorus heteropoly tungstic acid, the alkaline earth salt of phosphorus heteropoly tungstic acid, the ammonium salt of phosphato-molybdic heteropolyacid, the an alkali metal salt of phosphato-molybdic heteropolyacid, the alkaline earth salt of phosphato-molybdic heteropolyacid, the ammonium salt of phosphorus vanadium heteropolyacid, the an alkali metal salt of phosphorus vanadium heteropolyacid, the alkaline earth salt of phosphorus vanadium heteropolyacid, the ammonium salt of molybdenum vanadium heteropolyacid, the an alkali metal salt of molybdenum vanadium heteropolyacid, the alkaline earth salt of molybdenum vanadium heteropolyacid, the ammonium salt of the isopoly-acid that is formed by molybdenum, the an alkali metal salt of the isopoly-acid that is formed by molybdenum, the alkaline earth salt of the isopoly-acid that is formed by molybdenum, the ammonium salt of the isopoly-acid that is formed by tungsten, the an alkali metal salt of the isopoly-acid that is formed by tungsten, the alkaline earth salt of the isopoly-acid that is formed by tungsten, the ammonium salt of the isopoly-acid that is formed by vanadium, the alkaline earth salt of an alkali metal salt of the isopoly-acid that is formed by vanadium and the isopoly-acid that formed by vanadium.
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, 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.
In the present invention, described HTS can be commercially available, and also can prepare, and prepares the method for described HTS for conventionally known to one of skill in the art, does not repeat them here.
The method according to this invention, in order to make the reaction system homogeneous, under the preferable case, described contact is generally carried out in solvent, and the mass ratio of solvent and catalyzer is 2-200: 1,2-100 more preferably: 1.
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, described hydrogen peroxide is because explode easily when existing with gaseous form, therefore generally provide with aqueous hydrogen peroxide solution, at this moment, the mol ratio that the condition of described oxidizing reaction generally comprises the trimethyl carbinol and hydrogen peroxide is 1: 0.1-20 is preferably 1: 0.5-5; The mass ratio of the trimethyl carbinol and catalyzer is 1-200: 1, be preferably 10-200: 1; The temperature of contact is 10-160 ℃, is preferably 30-90 ℃; Pressure is 0.1-2MPa, is preferably 0.5-1.5MPa.Under these conditions, can select as required the time of required contact, be generally 0.1-20h, be preferably 0.1-15h.
When described hydrogen peroxide provided with aqueous hydrogen peroxide solution, the amount of solvent generally 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, for example can be the hydrogen peroxide of 30 commercially available % by weight, 50 % by weight and 70 % by weight.
As everyone knows, with HTS/H
2O
2Catalytic oxidation system, the effect of solvent mainly are 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 the scope of selecting can not be confined to above-mentioned requirements, specifically must select according to concrete oxidizing reaction system.The present inventor finds, in the Oxidation of t-Butanol system, at the solvent system that satisfies on the basis of aforementioned requirement, the trimethyl carbinol all can be converted into target product, but the yield of its transformation efficiency and target product is still limited.And the present inventor further finds, reaction effect is better during as solvent with in water, ketone and the nitrile one or more, more preferably one or more in the nitrile solvent of the ketone solvent of water, C3-C8 and C2-C8, more preferably one or more in the nitrile solvent of the ketone solvent of C3-C6 and C2-C7; Wherein, described ketone can be in organic ketone solvents such as acetone and butanone one or more, and described nitrile can be in the nitrile solvents such as acetonitrile, propionitrile and benzyl cyanide one or more.More preferably described solvent is one or more in acetone, propionitrile, butanone and the water.
Method provided by the invention can adopt periodical operation, also can operate continuously etc., 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 the trimethyl carbinol continuously, hydrogen peroxide reacts; When in closed tank reactor, carrying out rhythmic reaction, catalyzer, solvent, the trimethyl carbinol 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, the trimethyl carbinol and hydrogen peroxide behind the catalyzer of packing into continuously; When in slurry bed reactor, carrying out, can be with the adding trimethyl carbinol, 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.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent.
Used HTS (TS-1) catalyzer is (TS-1) sieve sample of preparing by the method 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 long company and made for the Industrial products of the described HTS of CN1301599A among the embodiment, be the HTS of MFI structure through 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.
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 transformation efficiency of reactant, the evaluation indexes such as selectivity of product.
In Comparative Examples and embodiment:
Embodiment 1
With the trimethyl carbinol, hydrogen peroxide, solvent propionitrile and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 100: 1) (phosphorus heteropoly tungstic acid H
3PW
12O
40) be that (hydrogen peroxide provided with the aqueous hydrogen peroxide solution of 30 % by weight in 1: 2 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, following examples roughly the same), propionitrile, the trimethyl carbinol are 20: 20: 1 with the catalyst quality ratio, are 30 ℃ in temperature, and pressure is to react under the 1.5MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 55%, the tertbutyl peroxide selectivity is 98%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 53%, the tertbutyl peroxide selectivity is 97%.
Embodiment 2
With the trimethyl carbinol, hydrogen peroxide, solvent propionitrile and catalyzer (mass ratio of TS-1 and phosphorus vanadium heteropolyacid is 0.1) (phosphorus vanadium heteropolyacid H
3PV
12O
40) be 1: 2 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of propionitrile, the trimethyl carbinol and catalyzer is 120: 40: 1, is 30 ℃ in temperature, pressure is to react under the 1.5MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 68%, the tertbutyl peroxide selectivity is 98%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 65%, the tertbutyl peroxide selectivity is 98%.
Embodiment 3
With the trimethyl carbinol, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and molybdenum vanadium heteropolyacid is 50) (molybdenum vanadium heteropolyacid H
3VMo
12O
40) be 1: 5 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of acetone, the trimethyl carbinol and catalyzer is 200: 80: 1, is 60 ℃ in temperature, pressure is to react under the 1.0MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 97%, the tertbutyl peroxide selectivity is 98%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 96%, the tertbutyl peroxide selectivity is 96%.
Embodiment 4
With the trimethyl carbinol, hydrogen peroxide, solvent butanone and catalyzer (mass ratio of TS-1 and phosphato-molybdic heteropolyacid is 10) (phosphato-molybdic heteropolyacid H
3PMo
12O
40) be 1: 4 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of the trimethyl carbinol, butanone and catalyzer is 80: 2: 1, is 40 ℃ in temperature, pressure is to react under the 0.5MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 78%, the tertbutyl peroxide selectivity is 99%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 76%, the tertbutyl peroxide selectivity is 97%.
Embodiment 5
With the trimethyl carbinol, hydrogen peroxide, aqueous solvent and catalyzer (mass ratio of TS-1 and phosphorus tungsten heteropoly blue is 20) (phosphorus tungsten heteropoly blue H
5PW
12O
40) be 1: 3 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of water, the trimethyl carbinol and catalyzer is 180: 5: 1, is 90 ℃ in temperature, pressure is to react under the 1.0MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 98%, the tertbutyl peroxide selectivity is 97%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 94%, the tertbutyl peroxide selectivity is 98%.
Embodiment 6
With the trimethyl carbinol, hydrogen peroxide, solvent propionitrile and catalyzer (mass ratio of TS-1 and ammonium phosphomolybdate is 20) (ammonium phosphomolybdate (NH
3)
3PMo
12O
40) be 5: 1 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of propionitrile, the trimethyl carbinol and catalyzer is 10: 10: 1, is 40 ℃ in temperature, pressure is to react under the 0.5MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 16%, the tertbutyl peroxide selectivity is 96%.Reacted 15 hours: trimethyl carbinol transformation efficiency is 13%, the tertbutyl peroxide selectivity is 95%.
Embodiment 7
With the trimethyl carbinol, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and tungsten sila multi-acid salt is 15) (tungsten sila multi-acid salt K
3SiW
12O
40) be 3: 1 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of acetone, the trimethyl carbinol and catalyzer is 80: 100: 1, is 40 ℃ in temperature, pressure is to react under the 0.5MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 31%, the tertbutyl peroxide selectivity is 99%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 28%, the tertbutyl peroxide selectivity is 98%.
Embodiment 8
With the trimethyl carbinol, hydrogen peroxide, solvent propionitrile and catalyzer (TS-1 and H
4V
2O
7Mass ratio be 50) be 2: 1 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of propionitrile, the trimethyl carbinol and catalyzer is 40: 60: 1, is 30 ℃ in temperature, pressure is to react under the 1.SMPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 47%, the tertbutyl peroxide selectivity is 95%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 44%, the tertbutyl peroxide selectivity is 96%.
Embodiment 9
With the trimethyl carbinol, hydrogen peroxide, solvent propionitrile and catalyzer (TS-1 and H
4Mo
8O
26Mass ratio be 0.3) be 1: 1 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, propionitrile, the trimethyl carbinol with the catalyst quality ratio be 60: 1: 1, be 60 ℃ in temperature, pressure is to react under the 1.0MPa.Reacted 2 hours: trimethyl carbinol transformation efficiency is 91%, the tertbutyl peroxide selectivity is 98%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 87%, the tertbutyl peroxide selectivity is 95%.
Embodiment 10
Identical with the method for embodiment 1, different is that TS-1 is replaced by HTS, reacts 2 hours: trimethyl carbinol transformation efficiency is 99%, the tertbutyl peroxide selectivity is 99%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 98%, the tertbutyl peroxide selectivity is 100%.
Embodiment 11
Identical with the method for embodiment 1, different is, TS-1 by Ti-MCM-41 (according to prior art Corma etc. at Chem.Commun., 1994, method preparation described in the 147-148, titanium oxide content is 3 % by weight) replace, reacted 2 hours: trimethyl carbinol transformation efficiency is 42%, the tertbutyl peroxide selectivity is 91%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 30%, the tertbutyl peroxide selectivity is 85%.
Embodiment 12
Identical with the method for embodiment 1, different is, TS-1 by Ti-Beta (according to prior art Takashi Tatsumi etc. at J.Chem.Soc., Chem.Commun.1997, method preparation described in the 677-678, titanium oxide content is 2.6 % by weight) replace, reacted 2 hours: trimethyl carbinol transformation efficiency is 44%, the tertbutyl peroxide selectivity is 89%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 36%, the tertbutyl peroxide selectivity is 81%.
Embodiment 13
Identical with the method for embodiment 1, different is that the mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 1000: 1, reacts 2 hours: trimethyl carbinol transformation efficiency is 51%, the tertbutyl peroxide selectivity is 92%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 43%, the tertbutyl peroxide selectivity is 89%.
Embodiment 14
Identical with the method for embodiment 1, different is that solvent is acetic acid, reacts 2 hours: trimethyl carbinol transformation efficiency is 59%, the tertbutyl peroxide selectivity is 76%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 47%, the tertbutyl peroxide selectivity is 81%.
Comparative Examples 1
Identical with the method for embodiment 1, different is does not react in the presence of the catalyzer having.Reacted 2 hours: trimethyl carbinol transformation efficiency is 0.8%, the tertbutyl peroxide selectivity is 48%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 0.7%, the tertbutyl peroxide selectivity is 50%.
Comparative Examples 2
Identical with the method for embodiment 1, different is that catalyzer all is TS-1.Reacted 2 hours: trimethyl carbinol transformation efficiency is 43%, the tertbutyl peroxide selectivity is 91%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 41%, the tertbutyl peroxide selectivity is 88%.
Comparative Examples 3
Identical with the method for embodiment 1, different is that catalyzer all is H
3PW
12O
40Reacted 2 hours: trimethyl carbinol transformation efficiency is 46%, the tertbutyl peroxide selectivity is 39%; Reacted 15 hours: trimethyl carbinol transformation efficiency is 23%, the tertbutyl peroxide selectivity is 28%.
The result of comparative example and Comparative Examples can obviously find out: method catalytic activity of the present invention is high, and selectivity is good, and activity does not obviously reduce yet after the long-time reaction of catalyzer of the present invention, illustrates that catalyst activity stability of the present invention might as well.
Claims (14)
1. the method for an Oxidation of t-Butanol, the method comprises: under oxidation reaction condition, the trimethyl carbinol, hydrogen peroxide are contacted with catalyzer, it is characterized in that, described catalyzer contains HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate.
2. method according to claim 1, wherein, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 0.01-20: 1.
3. method according to claim 2, wherein, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 0.01-10: 1.
4. the described method of any one according to claim 1-3, wherein, described multiple-metal oxygen-containing acid is heteropolyacid and/or isopoly-acid.
5. method according to claim 4, wherein, the metallic element in the described multiple-metal oxygen-containing acid is selected from one or more in IV B family, V B family, group VIB and the VII B family metallic element.
6. method according to claim 5, wherein, the metallic element in the described multiple-metal oxygen-containing acid is selected from one or more in V B family, the group VIB metallic element.
7. method according to claim 6, wherein, the metallic element in the described multiple-metal oxygen-containing acid is selected from one or more in metallic element molybdenum, tungsten, vanadium, chromium, tantalum and the niobium.
8. method according to claim 7, wherein, described multiple-metal oxygen-containing acid is one or more in phosphorus heteropoly tungstic acid, molybdenum phospha polyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid and the isopoly-acid that formed by metallic element molybdenum, tungsten or vanadium.
9. the described method of any one according to 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. method according to claim 9, wherein, described HTS is the MFI structure, and HTS crystal grain is hollow structure, and 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. method according to claim 1, wherein, described contact is carried out in solvent, and the mass ratio of solvent and catalyzer is 2-200: 1.
12. method according to claim 11, wherein, described solvent is one or more in water, ketone and the nitrile.
13. method according to claim 12, wherein, described solvent is one or more in acetone, propionitrile, butanone and the water.
14. according to claim 1 or 11 described methods, wherein, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, the condition of described oxidizing reaction comprises that the mol ratio of the trimethyl carbinol and hydrogen peroxide is 1: 0.1-20, the mass ratio of the trimethyl carbinol and catalyzer is 1-200: 1, and the temperature of contact is that 10-160 ℃, pressure are 0.1-2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110188811.5A CN102863368B (en) | 2011-07-05 | 2011-07-05 | Method for oxidizing tertiary butanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110188811.5A CN102863368B (en) | 2011-07-05 | 2011-07-05 | Method for oxidizing tertiary butanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102863368A true CN102863368A (en) | 2013-01-09 |
| CN102863368B CN102863368B (en) | 2014-08-20 |
Family
ID=47442533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110188811.5A Active CN102863368B (en) | 2011-07-05 | 2011-07-05 | Method for oxidizing tertiary butanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102863368B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480416A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method for Pd-V-polyoxometalate one-component three-active-center catalyst and application |
| CN103480415A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method and application of Pd complex-phosphomolybdic acid one-component dual-active-center catalyst |
| CN103480417A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method and application of Pb complex-vanadate substituted phosphomolybdic acid one-component dual-active-center catalyst |
| CN114621124A (en) * | 2022-04-19 | 2022-06-14 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB682424A (en) * | 1949-07-01 | 1952-11-12 | Bataafsche Petroleum | A process for the production of organic hydroperoxides and the organic hydroperoxides so produced |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN1699339A (en) * | 2004-05-19 | 2005-11-23 | 中国石油化工股份有限公司 | Process for preparing tert-butyl hydroperoxide |
-
2011
- 2011-07-05 CN CN201110188811.5A patent/CN102863368B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB682424A (en) * | 1949-07-01 | 1952-11-12 | Bataafsche Petroleum | A process for the production of organic hydroperoxides and the organic hydroperoxides so produced |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN1699339A (en) * | 2004-05-19 | 2005-11-23 | 中国石油化工股份有限公司 | Process for preparing tert-butyl hydroperoxide |
Non-Patent Citations (3)
| Title |
|---|
| LUIS C. PASSONI ET AL.: "Niobium peroxo compounds as catalysts for liquid-phase oxidation with hydrogen peroxide", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 赵忠奎等: "杂多酸催化剂及其在精细化学品合成中的应用", 《化学进展》 * |
| 郎贤军等: "多金属氧酸盐催化的液相氧化反应", 《化学进展》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480416A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method for Pd-V-polyoxometalate one-component three-active-center catalyst and application |
| CN103480415A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method and application of Pd complex-phosphomolybdic acid one-component dual-active-center catalyst |
| CN103480417A (en) * | 2013-09-24 | 2014-01-01 | 北京理工大学 | Preparation method and application of Pb complex-vanadate substituted phosphomolybdic acid one-component dual-active-center catalyst |
| CN114621124A (en) * | 2022-04-19 | 2022-06-14 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
| CN114621124B (en) * | 2022-04-19 | 2024-02-13 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102863368B (en) | 2014-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102757301B (en) | Method for oxidizing phenol | |
| CN102863368B (en) | Method for oxidizing tertiary butanol | |
| CN103012063A (en) | Preparation method of propylene glycol | |
| Hua et al. | A Ti-substituted polyoxometalate as a heterogeneous catalyst for olefin epoxidation with aqueous hydrogen peroxide | |
| CN103012077B (en) | Method for preparing propylene glycol monomethyl ether by catalyzing alcoholysis of propylene epoxide | |
| CN103012366B (en) | A kind of method of thiophene-type sulfide oxidation | |
| CN103012078B (en) | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide | |
| CN102850188B (en) | Method for simultaneously producing hydroquinone and catechol | |
| CN104707646B (en) | A kind of dimethyl ether oxidative dehydrogenation prepares catalyst of toluene and its preparation method and application | |
| CN102757408B (en) | Method for oxidizing chloropropene | |
| CN102850198B (en) | Cyclohexanol oxidation method | |
| CN103012064B (en) | Method for preparing propylene glycol from propylene | |
| CN111974455A (en) | Catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@PC | |
| CN102757374B (en) | Oxidation method for tert-butyl alcohol | |
| CN102850205B (en) | Method for producing 1,2-cyclohexanediol and adipic acid | |
| CN103012133B (en) | Method for catalytically oxidizing acetophenone | |
| CN102766037B (en) | Method for preparing adipic acid from cyclohexene | |
| CN103204769B (en) | Method for production of cyclohexanone from cyclohexanol | |
| CN103012127B (en) | A kind of phenol and dimethyl ester carry out the method for transesterify | |
| CN103012119B (en) | Method for oxidizing benzyl methyl ether | |
| CN103977839A (en) | Ionic organic metal tungstate epoxidation catalyst and preparation method thereof | |
| CN102850207A (en) | Method for oxidizing styrene | |
| CN103204809B (en) | A kind of method of producing hexanolactam | |
| CN102757333B (en) | Method for preparing hexanedioic acid by oxidizing cyclohexanol | |
| CN103204835B (en) | A kind of preparation method of butyrolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |