CN103288779B - Method for oxidizing allyl alcohol - Google Patents
Method for oxidizing allyl alcohol Download PDFInfo
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- CN103288779B CN103288779B CN201210050626.4A CN201210050626A CN103288779B CN 103288779 B CN103288779 B CN 103288779B CN 201210050626 A CN201210050626 A CN 201210050626A CN 103288779 B CN103288779 B CN 103288779B
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Abstract
The invention discloses a method for oxidizing allyl alcohol. The method comprises the following step: in a condition of an oxidizing reaction, contacting allyl alcohol with an oxidant. The method is characterized in that the oxidant is a gas containing ozone. The method is good in selectivity of epoxy propanol, and the selectivity of the product epoxy propanol and the ozone effective utilization ratio are further improved in the presence of a titaniferous catalyst.
Description
Technical field
The invention relates to a kind of method that allylic alcohol prepares R-GLYCIDOL.
Background technology
R-GLYCIDOL, also known as Racemic glycidol, is colourless and is bordering on the liquid of odorless.Miscible with water, low-carbon alcohol, ether, benzene, toluene, chloroform etc., be partially soluble in dimethylbenzene, zellon, trichloroethane, be dissolved in aliphatics and alicyclic hydro carbons hardly.Be a kind of important fine chemical material, be used for doing the stablizer of natural oil and vinyl polymer, emulsion splitter, dyeing layering agent, be also used for the intermediate of synthetic glycerine, glycidyl ether (amine etc.).Can be used for topcoating, chemosynthesis, medicine, medication chemistry, sterilant and solid-fuelled gelifying agent.
Industrial production R-GLYCIDOL mainly contains following two kinds of methods: 1, glycerine chlorohydrination, is reacted in the presence of a base and obtain by propylene glycol of chlorine.Reaction is carried out at about 0 DEG C usually, refines, obtain pure Racemic glycidol after reaction product isolates salt with underpressure distillation.2, alcohol propylene method, can obtain Racemic glycidol with hydrogen peroxide or peracetic acid to allyl alcohol epoxidation.When adopting peracetic acid to be epoxidizing agent, speed of response is very fast, in product, Racemic glycidol very easily generates Racemic glycidol acetic ester with acetic acidreaction, make fractionation by distillation difficulty, and the mixture of Racemic glycidol and acetic acid at room temperature can occur very exothermic reaction set off an explosion, therefore industrially application difficult is very large for this method.Sexavalence tungstate can also be adopted to be that vinyl carbinol and oxygenant (as hypochlorous acid or perchloric acid) are carried out epoxidation reaction and obtain by catalyzer, but this process is big for environment pollution, and used catalyst activity is low, non-renewable.
Summary of the invention
The object of this invention is to provide a kind of technique simple, allylic alcohol method with low cost, R-GLYCIDOL selectivity is good.
The problems referred to above of R-GLYCIDOL method existence are prepared in order to overcome prior art, the present inventor conducts in-depth research, find to adopt ozone to carry out oxyalkylene propyl alcohol as oxygenant, can overcome on the one hand that the operational condition that prior art exists is harsh, equipment corrosion is serious and the defect of contaminate environment, and gratifying R-GLYCIDOL selectivity can be obtained, this completes the present invention.
The invention provides a kind of method of allylic alcohol, the method comprises, and under oxidation reaction condition, by vinyl carbinol and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
The method of allylic alcohol provided by the invention, oxygenant is made with ozone, high R-GLYCIDOL selectivity and comparatively high ozone effective rate of utilization can be obtained in unstripped gas without the need to adding any initiator, and in the presence of a titanium-containing catalyst, R-GLYCIDOL selectivity and ozone effective rate of utilization can be improved further.The method process is simple and easy to control, is beneficial to suitability for industrialized production and application.
Embodiment
The method of allylic alcohol provided by the invention, the method comprises, and under oxidation reaction condition, by vinyl carbinol and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
According to method of the present invention, adopt the gas containing ozone as oxygenant.(molecular formula is O to ozone
3, have another name called three atomic oxygens, be commonly called as " good fortune oxygen, super oxygen, oxygen of living ") at normal temperatures and pressures, for being nattier blue gas.The present inventor finds in research process, and adopt the gas containing ozone to carry out oxyalkylene propyl alcohol as oxygenant, have higher selectivity for R-GLYCIDOL, its simple process is easy, and operational condition is gentle.Further, ozone can disintegrate be oxygen at normal temperatures, can not produce and such as use hydrogen peroxide to carry out the shortcoming such as processing to the solution containing hydrogen peroxide as the needs faced during oxygenant.Therefore, according to the inventive method environmental friendliness.
According to method of the present invention, the described gas containing ozone can be ozone, can also be the mixed gas of ozone and diluent gas.According to method of the present invention, the described gas containing ozone is preferably the mixed gas of ozone and diluent gas, can regulate easily like this, thus control speed of reaction better to the concentration of ozone.
In the present invention, when the described gas containing ozone is the mixed gas of ozone and diluent gas, in described mixed gas, the concentration of ozone can carry out appropriate selection according to concrete oxidation reaction condition.Preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %.More preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %.Usually, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone can be 5-80 volume %, is preferably 5-50 volume %, is more preferably 5-20 volume %.
The present invention is not particularly limited for the kind of described diluent gas, and described diluent gas can be such as at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.Preferably, described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.According to the present invention, ozone can be mixed with above-mentioned diluent gas, thus the described mixed gas containing ozone of preparation; Because air contains oxygen, carbonic acid gas and nitrogen, also by ozone and air mixed, thus the mixed gas of ozone described in preparation, can be contained.According to method of the present invention, when adopting the on-the-spot generation ozone of ozonizer, oxygen can be adopted as the source of oxygen of described ozonizer, air also can be adopted to provide oxygen to described ozonizer.The smelly oxygen purity adopting oxygen to obtain as the source of oxygen of described ozonizer is higher, can obtain higher vinyl carbinol transformation efficiency and R-GLYCIDOL selectivity; Adopt air as the source of oxygen of described ozonizer, then can reduce running cost further.
According to method of the present invention, at the mixed gas that described oxygenant is ozone and diluent gas, and described diluent gas is when being two or more, the present invention is not particularly limited for the content of each diluent gas, as long as final contains in the gas of ozone, the content of ozone can by allylic alcohol, such as: the content of described ozone can be ozone content mentioned above.
One according to the present invention preferred embodiment in, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.One according to the present invention more preferred embodiment in, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
Method according to the present invention is by adopting the gas containing ozone to realize preparing R-GLYCIDOL with the operational condition of gentleness and higher selectivity as oxygenant, also can not produce the object of serious corrosion to equipment simultaneously.The present invention without particular requirement, can carry out appropriate selection according to concrete application scenario for the mol ratio of the ozone in vinyl carbinol and oxygenant.Under the optionally condition of the transformation efficiency and R-GLYCIDOL of guaranteeing vinyl carbinol, from the consumption reducing ozone further, and then reduction is set out according to the angle of the cost of method of the present invention further, the mol ratio of the ozone in described vinyl carbinol and oxygenant is preferably 1: 0.1-10, be more preferably 1: 0.1-5, more preferably 1: 0.5-5.
According to method of the present invention, the contact of vinyl carbinol and oxygenant is preferably carried out in the presence of a titanium-containing catalyst.The present inventor finds in research process, when carrying out under existence at titanium-containing catalyst of the contact of vinyl carbinol and oxygenant, the transformation efficiency of the vinyl carbinol of the inventive method can be improved, particularly can increase substantially the effective rate of utilization of ozone and the selectivity of R-GLYCIDOL.
According to method of the present invention, the consumption of described titanium-containing catalyst can carry out appropriate selection according to concrete application scenario.Preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and vinyl carbinol is 1: 0.1-100.More preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and vinyl carbinol is 1: 1-50.
According to method of the present invention, described titanium-containing catalyst can be various forms of titanium-containing catalyst.Preferably, described titanium-containing catalyst is at least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide.More preferably, described titanium-containing catalyst is at least one in 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 (as Ti-MCM-41, Ti-SBA-15) of hexagonal structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS (as Ti-ZSM-48) of other structures and titanium dioxide.More preferably, described titanium-containing catalyst is the HTS (as TS-1) of MFI structure.Above-mentioned molecular sieve can be commercially available, or adopts method well known in the art to synthesize, and repeats no more herein.
According to method of the present invention, described titanium-containing catalyst most preferably is the HTS of the MFI structure of hollow structure crystal grain, and 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.Hereinafter, the HTS of the type is called hollow HTS.
According to method of the present invention, the contact of vinyl carbinol and oxygenant is preferably carried out in the presence of solvent, the contact of vinyl carbinol and oxygenant can be made so more even, thus better control speed of response.The present invention is not particularly limited for the kind of described solvent, all kinds of SOLVENTS that described solvent can be commonly used for this area.Preferably, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone, C
2-C
8nitrile and C
1-C
6carboxylic acid at least one.Such as, described solvent can be at least one in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile and acetic acid.The present inventor finds unexpectedly in research process, is water, C at described solvent
1-C
4alcohol and/or C
3-C
8ketone time, the transformation efficiency of vinyl carbinol and the selectivity of R-GLYCIDOL can be improved further.Further preferably, described solvent is water, methyl alcohol and/or acetone.
According to method of the present invention, the amount of described solvent can be the routine selection of this area.From the angle of cost reducing further method of the present invention, the mol ratio of described vinyl carbinol and solvent is preferably 1: 1-150, is more preferably 1: 1-100, and more preferably 1: 1-50.
According to method of the present invention, for described oxidation reaction condition without particular requirement, it can be conventional oxidation reaction condition.Under preferable case, described oxidation reaction condition comprises: temperature can be 0-180 DEG C, is preferably 20-160 DEG C, more preferably 20-120 DEG C; Pressure can be 0.1-3MPa, is preferably 0.1-2.5MPa, more preferably 0.1-2MPa.
According to method of the present invention, the duration of contact of vinyl carbinol and oxygenant can carry out appropriate selection.Usually, the time of described contact can be 0.1-10 hour, is preferably 1-5 hour.It should be noted that, when at said temperatures, when can produce required pressure, described pressure can be autogenous pressure, when at said temperatures, when the pressure that described temperature produces does not reach required pressure, described pressure can apply pressure to realize by the external world, this is technology well known in the art, no longer describes in detail herein.
According to method of the present invention, ordinary method can be adopted to be separated from the product of contact of vinyl carbinol and oxygenant by R-GLYCIDOL.Such as: by described product of contact is carried out fractionation, thus R-GLYCIDOL can be isolated.The method of described fractionation and condition are known in the field, repeat no more herein.
According to method of the present invention, can adopt periodical operation, also can adopt operate continuously etc., feed way also can be any suitable mode well known by persons skilled in the art, and the present invention, does not repeat at this all without particular requirement one by one to this.During operate continuously, in the presence of a titanium-containing catalyst, be 10-10000h in ozone air speed
-1react under condition, ozone air speed is preferably 10-5000h
-1.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In embodiment, if not otherwise specified, used reagent is commercially available analytical reagent, and used reactor is universal 250mL stainless steel autoclave formula reactor.
In embodiment, ozone used provides for the NLO-15 type ozonizer produced by Fujian New Continent Environmental Protection Technology Co., Ltd, and ozone concn is adjustable, and maximum volume concentration can reach 80%.In following examples if not otherwise specified, source of oxygen is all used to prepare ozone.
In embodiment, HTS (TS-1) catalyzer used is the TS-1 sieve sample prepared by the method described in document [Zeolites, 1992, Vol.12 943-950 page], and titanium oxide content is 2.4 % by weight.
In embodiment, (Hunan Jianchang Petrochemical Co., Ltd manufactures the Industrial products of HTS described in hollow HTS HTS system CN1301599A used, 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.
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 an embodiment:
Embodiment 1
Under temperature is 60 DEG C and pressure is 0.5MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), vinyl carbinol, ozone and solvent acetone are reacted according under the mol ratio of 1: 1: 1.The result of reacting 2 hours is as follows: vinyl carbinol transformation efficiency is 64%; Ozone effective rate of utilization is 41%; R-GLYCIDOL selectivity is 53%.
Embodiment 2
Under temperature is 20 DEG C and pressure is 1.5MPa, is oxygenant with ozone (30% volume ratio, all the other are air), vinyl carbinol, ozone and solvent acetic acid are reacted according under the mol ratio of 1: 1: 5.The result of reacting 5 hours is as follows: vinyl carbinol transformation efficiency is 25%; Ozone effective rate of utilization is 38%; R-GLYCIDOL selectivity is 69%.
Embodiment 3
Under temperature is 80 DEG C and pressure is 0.2MPa, is oxygenant with ozone (5% volume ratio, all the other are oxygen), vinyl carbinol, ozone and solvent acetonitrile are reacted according under the mol ratio of 1: 2: 10.The result of reacting 1 hour is as follows: vinyl carbinol transformation efficiency is 82%; Ozone effective rate of utilization is 43%; R-GLYCIDOL selectivity is 47%.
Embodiment 4
Under temperature is 40 DEG C and pressure is 0.1MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), vinyl carbinol, ozone and solvent acetone are reacted according under the mol ratio of 1: 4: 50.The result of reacting 2 hours is as follows: vinyl carbinol transformation efficiency is 47%; Ozone effective rate of utilization is 39%; R-GLYCIDOL selectivity is 52%.
Embodiment 5
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Take TS-1 as catalyzer, the molar ratio of catalyzer and vinyl carbinol is 1: 50, and ozone volume space velocity is 20h
-1, other reaction conditions is with embodiment 4.The result of reacting 2 hours is as follows: vinyl carbinol transformation efficiency is 61%; Ozone effective rate of utilization is 68%; R-GLYCIDOL selectivity is 61%.
Embodiment 6
The present embodiment illustrates reaction process in the presence of a catalyst and result.
React according to the reaction conditions of embodiment 5, unlike substituting TS-1 with HTS for catalyzer.The result of reacting 3 hours is as follows: vinyl carbinol transformation efficiency is 66%; Ozone effective rate of utilization is 74%; R-GLYCIDOL selectivity is 72%.
Embodiment 7
Under temperature is 50 DEG C and pressure is 1.0MPa, is oxygenant with ozone (10% volume ratio, all the other are air), vinyl carbinol, ozone and aqueous solvent are reacted according under the mol ratio of 1: 0.3: 3.The result of reacting 4 hours is as follows: vinyl carbinol transformation efficiency is 26%; Ozone effective rate of utilization is 72%; R-GLYCIDOL selectivity is 53%.
Embodiment 8
Under temperature is 120 DEG C and pressure is 1.0MPa, is oxygenant with ozone (10% volume ratio, all the other are isopyknic carbon dioxide and oxygen), vinyl carbinol, ozone and solvent acetone are reacted according under the mol ratio of 1: 0.7: 25.The result of reacting 3 hours is as follows: vinyl carbinol transformation efficiency is 31%; Ozone effective rate of utilization is 46%; R-GLYCIDOL selectivity is 56%.
Embodiment 9
The present embodiment illustrates reaction process in the presence of a catalyst and result.
With TiO
2for catalyzer (commercially available, Detitanium-ore-type), the molar ratio of catalyzer and vinyl carbinol is 1: 5, and ozone volume space velocity is 3000h
-1, other reaction conditions is with embodiment 8.
The result of reacting 3 hours is as follows: vinyl carbinol transformation efficiency is 52%; Ozone effective rate of utilization is 76%; R-GLYCIDOL selectivity is 67%.
Embodiment 10
Under be 100 DEG C and pressure being 2.0MPa in temperature, with ozone (10% volume ratio, all the other for volume ratio be helium and the oxygen of 7: 10) be oxygenant, vinyl carbinol, ozone and solvent acetonitrile are reacted according under the mol ratio of 1: 2: 60.The result of reacting 1 hour is as follows: vinyl carbinol transformation efficiency is 48%; Ozone effective rate of utilization is 42%; R-GLYCIDOL selectivity is 55%.
Embodiment 11
The present embodiment illustrates reaction process when solvent is methyl alcohol and result.
Reacting according to the reaction conditions of embodiment 10, substituting acetonitrile for solvent unlike utilizing methyl alcohol.The result of reacting 1 hour is as follows: vinyl carbinol transformation efficiency is 57%; Ozone effective rate of utilization is 64%; R-GLYCIDOL selectivity is 61%.
Embodiment 12
The present embodiment illustrates reaction process in the presence of a catalyst and result.
Take HTS as catalyzer, the molar ratio of catalyzer and vinyl carbinol is 1: 10, and ozone volume space velocity is 1000h
-1, other reaction conditions is with embodiment 11.The result of reacting 1 hour is as follows: vinyl carbinol transformation efficiency is 81%; Ozone effective rate of utilization is 76%; R-GLYCIDOL selectivity is 73%.
Claims (10)
1. the method for an allylic alcohol, the method comprises, under oxidation reaction condition, by vinyl carbinol and oxidising agent, it is characterized in that, described contact is carried out in the presence of a titanium-containing catalyst, and in titanium dioxide, the mol ratio of described titanium-containing catalyst and vinyl carbinol is 1:0.1-100, described titanium-containing catalyst is the HTS of MFI structure, the crystal grain of described HTS is hollow structure, and 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; Described oxygenant is the gas containing ozone, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.
2., according to the process of claim 1 wherein, the mol ratio of the ozone in described vinyl carbinol and oxygenant is 1:0.1-10.
3. according to the process of claim 1 wherein, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
4. according to the process of claim 1 wherein, described contact is carried out in the presence of solvent, and the mol ratio of described vinyl carbinol and solvent is 1:1-150.
5. according to the method for claim 4, wherein, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone, C
2-C
8nitrile and C
1-C
6carboxylic acid at least one.
6. according to the method for claim 5, wherein, described solvent is water, C
1-C
4alcohol and C
3-C
8ketone at least one.
7. according to the method for claim 6, wherein, described solvent is water, acetone and/or methyl alcohol.
8. according to the process of claim 1 wherein, described oxidation reaction condition comprises: temperature is 0-180 DEG C, and pressure is 0.1-3MPa, and the time is 0.1-10 hour.
9. according to the method for claim 8, wherein, described temperature is 20-160 DEG C, and pressure is 0.1-2.5MPa.
10., according to the method for claim 1, it is characterized in that the method is 10-10000h in ozone air speed
-1react under condition.
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| CN201210050626.4A CN103288779B (en) | 2012-02-29 | 2012-02-29 | Method for oxidizing allyl alcohol |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452615A (en) * | 2000-09-05 | 2003-10-29 | 对流层研究协会研究所 | Method for producing epoxides by oxidising olefins |
| CN1507438A (en) * | 2001-05-01 | 2004-06-23 | ����̼����ѧ�����ϼ�����˾ | Synthesis of lower alkylene oxdies and lower alkylene glycols from lower alkanes and/or lower alkenes |
| CN101184740A (en) * | 2005-04-19 | 2008-05-21 | 西班牙高等科研理事会 | Method and catalysts for the epoxidation of olefinic compounds in the presence of oxygen |
| CN101570523A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol |
| CN101704802A (en) * | 2009-11-19 | 2010-05-12 | 浙江大学 | Preparation method of epoxy compound |
-
2012
- 2012-02-29 CN CN201210050626.4A patent/CN103288779B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452615A (en) * | 2000-09-05 | 2003-10-29 | 对流层研究协会研究所 | Method for producing epoxides by oxidising olefins |
| CN1507438A (en) * | 2001-05-01 | 2004-06-23 | ����̼����ѧ�����ϼ�����˾ | Synthesis of lower alkylene oxdies and lower alkylene glycols from lower alkanes and/or lower alkenes |
| CN101184740A (en) * | 2005-04-19 | 2008-05-21 | 西班牙高等科研理事会 | Method and catalysts for the epoxidation of olefinic compounds in the presence of oxygen |
| CN101570523A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol |
| CN101704802A (en) * | 2009-11-19 | 2010-05-12 | 浙江大学 | Preparation method of epoxy compound |
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