CN102757302B - Method for oxidizing isobutane - Google Patents
Method for oxidizing isobutane Download PDFInfo
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- CN102757302B CN102757302B CN201110113828.4A CN201110113828A CN102757302B CN 102757302 B CN102757302 B CN 102757302B CN 201110113828 A CN201110113828 A CN 201110113828A CN 102757302 B CN102757302 B CN 102757302B
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- trimethylmethane
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Abstract
The invention provides a method for oxidizing isobutane. The method comprises the following step of: making isobutene contact with an oxidant under an oxidizing reaction condition, and is characterized in that: the oxidant is an ozone-containing gas. In the method, isobutene can be effectively oxidized by taking ozone as an oxidant without adding any catalyst; and moreover, the method has a simple process, and the reaction degree can be well controlled without adding an additional initiator or an inhibitor into a reaction system. Compared with the conventional method, the method provided by the invention has the advantages of simple and convenient process, low cost, high isobutene transformation rate and the like. Moreover, the method provided by the invention is not limited by the production scale, so that the method has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of method of oxidation of isobutane.
Background technology
The trimethyl carbinol and 2-methyl-2-propanol are the simplest tertiary alcohols, are one of butanols four kinds of isomer.The trimethyl carbinol can be used as solvent, also can be used for Denatured alcohol, paint clean-out system, gasoline dope and other daily necessities as in the production of spices and perfume.
Industrial, the trimethyl carbinol can be generated by oxidation of isobutane, and oxidation of isobutane mainly adopts air autoxidation technique, obtained Trimethylmethane superoxide (Trimethylmethane hydrogen peroxide), then the rare obtained propylene oxide of this peroxide oxidation third, peroxide conversion is trimethyl carbinol byproduct simultaneously.Here it is industrial propylene oxide and trimethyl carbinol joint process, being the one of conjugated oxidation, is also one of main production of propylene oxide (accounting for about 20% of propylene oxide production capacity).
But during conventional oxidation Trimethylmethane, oxidization time is long, efficiency is low, and cause oxidation furnaces huge, cost of investment increases.And require must scale when acquiring a certain degree, just have an economic benefit, thus limit further developing of this technique.
Summary of the invention
The object of the invention is the defect overcoming prior art, the method for the oxidation of isobutane that a kind of Trimethylmethane transformation efficiency is high, technique is simple, with low cost is provided.
The present inventor finds under study for action, uses ozone to be oxidized Trimethylmethane as oxygenant and can obtain higher Trimethylmethane transformation efficiency.And complete the present invention based on this.
The invention provides a kind of method of oxidation of isobutane, the method comprises, and under oxidation reaction condition, by Trimethylmethane and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
Method of the present invention namely can effectively by oxidation of isobutane without the need to adding catalyzer as oxygenant by employing ozone, and the method technological process is simple, just can the degree of good control reaction without the need to introducing extra initiator or inhibitor in reaction system.Meanwhile, in system, the transformation efficiency that catalyzer can improve reactant is introduced; In particularly preferably situation, adopt preferred catalyst of the present invention and preferred solvent, the transformation efficiency of reactant can improve further.
Compared to traditional method, method of the present invention has simple process, with low cost, Trimethylmethane transformation efficiency advantages of higher.In addition, method of the present invention by production-scale restriction, therefore, does not have industrial applications prospect.
Embodiment
The invention provides a kind of method of oxidation of isobutane, the method comprises, and under oxidation reaction condition, by Trimethylmethane and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone.
In method for oxidation of the present invention, in oxygenant, the usage quantity of ozone can change in more wide in range scope, and preferably, the mol ratio of the ozone in described Trimethylmethane and oxygenant is 1: 0.1-10, and more preferably 1: 0.2-5.
Ozone has another name called three atomic oxygens, and be commonly called as " good fortune oxygen, super oxygen, oxygen of living ", molecular formula is O
3, under normal temperature and pressure, ozone is in nattier blue gas.In the present invention, the described gas containing ozone can be the mixed gas of pure ozone or 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 the concentration of ozone easily like this, thus control the severe degree of reaction better.The effect of described diluent gas is diluted ozone, therefore, any gas that is inactive or that have an oxidisability all can be used for the present invention, preferably, take into account the requirement of cost, convenience and friendly process, described diluent gas is be selected from least one in oxygen, carbonic acid gas, nitrogen, helium, neon, argon gas and air, further preferably, described diluent gas is be selected from least one in oxygen, helium, carbonic acid gas and air, most preferably is oxygen and/or air.
In the present invention, the content of ozone in described mixed gas can in very large range change, and can adjust accordingly according to the difference of diluent gas, with the cumulative volume of mixed gas for benchmark, in described mixed gas, the content of ozone is preferably 1 more than volume %, more preferably 5 more than volume %.
The present inventor finds under study for action, when the contact of Trimethylmethane and oxygenant is carried out in the presence of a titanium-containing catalyst, Trimethylmethane transformation efficiency can improve further, the consumption of described titanium-containing catalyst can be the consumption of catalyzer in the oxidation of isobutane technique of routine, preferably, in titanium dioxide, the mol ratio of described titanium-containing catalyst and Trimethylmethane is 1: 0.1-100, more preferably 1: 1-50, most preferably be 1: 5-50.
Titanium-containing catalyst used in the present invention of a great variety, such as, described titanium-containing catalyst can for being selected from least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide, preferably, described titanium-containing catalyst is be selected from least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium and titanium dioxide.
According to method of the present invention, in order to improve the transformation efficiency of Trimethylmethane further, described in the present invention, molecular sieve containing titanium is preferably HTS, described HTS 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 the HTS of MFI structure, further preferably, described HTS is MFI structure, crystal grain is the HTS of 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.
In the present invention, described HTS can be commercially available, and also can prepare, the method preparing described HTS has been conventionally known to one of skill in the art, as document (Zeolites, 1992, Vol.12,943-950) described in method.
According to method of the present invention, in order to make reaction system homogeneous, described contact is preferably carried out in the presence of solvent, and the mol ratio of described Trimethylmethane and solvent can be 1: 1-150, is preferably 1: 1-100, more preferably 1: 1-60.
As everyone knows, in chemical reaction system, the effect of solvent is mainly in order to make reaction solution be homogeneous phase, reaction is steadily carried out, the present inventor finds, better as reaction effect during solvent using one or more in the organic acid of the nitrile of the ketone of the alcohol of water, C1-C6, C3-C8, C2-C8 and C1-C6; Wherein, the alcohol of described C1-C6 can be one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol and isopropylcarbinol; The ketone of described C3-C8 can be one or more in acetone, butanone and methyl phenyl ketone; The nitrile of described C2-C8 can be one or more in acetonitrile, propionitrile, vinyl cyanide and benzyl cyanide; The organic acid of described C1-C6 can be formic acid and/or acetic acid.
The present inventor finds unexpectedly, and when described solvent is ketone and/or the water of C3-C8, at least one more preferably in acetone, butanone, methyl phenyl ketone and water, especially when acetone and/or water, can obtain very high Trimethylmethane transformation efficiency.
According to the present invention, described oxidation reaction condition comprises, and the temperature of contact can be 0-180 DEG C, is preferably 20-160 DEG C, more preferably 20-150 DEG C; Pressure can be 0.1-3MPa, is preferably 0.3-2.5MPa, is more preferably 0.3-2MPa; Time can be 0.1-10 hour, is preferably 1-5 hour.
Method provided by the invention, can adopt periodical operation, also can operate continuously etc., and feed way also can be any suitable way 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.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment, if not otherwise specified, agents useful for same is commercially available chemically pure reagent.The NLO-15 type oxygen source ozone producer that ozone used is produced by Fujian New Continent Environmental Protection Technology Co., Ltd provides, 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.
TS-1 catalyzer used is the sieve sample prepared by prior art (Zeolites, the method described in 1992, Vol.12,943-950), and titanium oxide content is 2.4%.Ti-MCM-41 used is the sieve sample prepared by prior art (method described in Corma etc., Chem.Commun.1994,147-148), and titanium oxide content is 3%.Ti-Beta used is the sieve sample prepared by prior art (method described in TakashiTatsumi etc., J.Chem.Soc.Chem.Commun.1997,677-678), and titanium oxide content is 2.5 % by weight.
(Hunan Jian Chang company manufactures the Industrial products of HTS described in hollow HTS HTS system CN1301599A used in embodiment, 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 indexes such as the transformation efficiency of reactant, the yield of product and selectivity on this basis.
In an embodiment:
Embodiment 1
Under temperature is 60 DEG C and pressure is the condition of 0.5MPa, with the mixed gas of ozone and oxygen (wherein, the mixed gas of 15 volume % is ozone) be oxygenant, by Trimethylmethane, described mixed gas and solvent acetone according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of solvent acetone be 1: 1: 1 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 2 hours is as follows: Trimethylmethane transformation efficiency is 17%; Trimethylmethane superoxide selectivity is 94%, tertiary butanol selectivity 6%.
Embodiment 2
The oxygenant used in the present embodiment is the mixed gas containing ozone, this mixed gas is prepared (wherein by using air as the source of oxygen of ozonizer, the mixed gas of 15 volume % is ozone), under be 20 DEG C and pressure being the condition of 1.5MPa in temperature, by Trimethylmethane, described mixed gas and solvent methanol according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of solvent methanol be 1: 1: 5 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 5 hours is as follows: Trimethylmethane transformation efficiency is 14%; Trimethylmethane superoxide selectivity is 97%, tertiary butanol selectivity 3%.
Embodiment 3
Under temperature is 80 DEG C and pressure is the condition of 0.2MPa, with the mixed gas of ozone and oxygen (wherein, the mixed gas of 5 volume % is ozone) be oxygenant, by Trimethylmethane, described mixed gas and solvent acetonitrile according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of solvent acetonitrile be 1: 2: 10 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 2 hours is as follows: Trimethylmethane transformation efficiency is 21%; Trimethylmethane superoxide selectivity is 92%, tertiary butanol selectivity 8%.
Embodiment 4
Under temperature is 40 DEG C and pressure is the condition of 0.1MPa, with the mixed gas of ozone and oxygen (wherein, the mixed gas of 15 volume % is ozone) be oxygenant, by Trimethylmethane, described mixed gas and solvent acetone according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of solvent acetone be 1: 4: 50 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 18%; Trimethylmethane superoxide selectivity is 91%, tertiary butanol selectivity 9%.
Embodiment 5
The present embodiment illustrates reaction process in the presence of a catalyst and result.
The oxidation of Trimethylmethane is carried out according to the method for embodiment 4, unlike, add TS-1 as catalyzer, the molar ratio of TS-1 catalyzer and Trimethylmethane is 1|: 50.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 32%; Trimethylmethane superoxide selectivity is 86%, tertiary butanol selectivity 14%.
Embodiment 6
The oxygenant used in the present embodiment is the mixed gas containing ozone, this mixed gas is prepared (wherein by using air as the source of oxygen of ozonizer, the mixed gas of 12 volume % is ozone), under be 50 DEG C and pressure being the condition of 1.0MPa in temperature, by Trimethylmethane, described mixed gas and aqueous solvent according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of aqueous solvent be 1: 0.3: 3 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 4 hours is as follows: Trimethylmethane transformation efficiency is 21%; Trimethylmethane superoxide selectivity is 89%, tertiary butanol selectivity 11%.
Embodiment 7
Under temperature is 120 DEG C and pressure is the condition of 1.0MPa, with the mixed gas of ozone, carbon dioxide and oxygen (wherein, the mixed gas of 8 volume % is ozone, all the other for volume ratio be the carbon dioxide and oxygen of 7: 10) be oxygenant, by Trimethylmethane, mixed gas and solvent acetone according to Trimethylmethane: the ozone in mixed gas: the mol ratio of solvent acetone be 1: 0.6: 25 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 27%; Trimethylmethane superoxide selectivity is 83%, tertiary butanol selectivity 17%.
Embodiment 8
The oxidation of Trimethylmethane is carried out according to the method for embodiment 7, unlike, solvent is ethanol.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 22%; Trimethylmethane superoxide selectivity is 84%, and tertiary butanol selectivity is 16%.
Embodiment 9
The present embodiment illustrates reaction process in the presence of a catalyst and result.
The oxidation of Trimethylmethane is carried out according to the method for embodiment 7, unlike, add TiO
2as catalyzer (commercially available, Beijing chemical reagents corporation, Detitanium-ore-type), TiO
2the molar ratio of catalyzer and Trimethylmethane is 1: 5.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 36%; Trimethylmethane superoxide selectivity is 67%, tertiary butanol selectivity 33%.
Embodiment 10
The oxidation of Trimethylmethane is carried out according to the method for embodiment 9, unlike, solvent is ethanol.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 31%; Trimethylmethane superoxide selectivity is 69%, and tertiary butanol selectivity is 31%.
Embodiment 11
The oxidation of Trimethylmethane is carried out according to the method for embodiment 9, unlike, TiO
2by etc. weight Ti-MCM-41 replace.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 33%; Trimethylmethane superoxide selectivity is 67%, and tertiary butanol selectivity is 33%.
Embodiment 12
The oxidation of Trimethylmethane is carried out according to the method for embodiment 9, unlike, TiO
2by etc. weight Ti-Beta replace.
The result of reacting 2 hours is as follows: Trimethylmethane transformation efficiency is 34%; Trimethylmethane superoxide selectivity is 68%, and tertiary butanol selectivity is 32%.
Embodiment 13
The oxidation of Trimethylmethane is carried out according to the method for embodiment 9, unlike, TiO
2by etc. weight HTS replace.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 65%; Trimethylmethane superoxide selectivity is 94%, and tertiary butanol selectivity is 6%.
Embodiment 14
The oxidation of Trimethylmethane is carried out according to the method for embodiment 13, unlike, solvent is acetonitrile.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 58%; Trimethylmethane superoxide selectivity is 75%, and tertiary butanol selectivity is 25%.
Embodiment 15
The oxidation of Trimethylmethane is carried out according to the method for embodiment 13, unlike, solvent is acetic acid.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 57%; Trimethylmethane superoxide selectivity is 68%, and tertiary butanol selectivity is 32%.
Embodiment 16
The oxidation of Trimethylmethane is carried out according to the method for embodiment 13, unlike, solvent is ethanol.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 55%; Trimethylmethane superoxide selectivity is 63%, and tertiary butanol selectivity is 37%.
Embodiment 17
The oxidation of Trimethylmethane is carried out according to the method for embodiment 13, unlike, solvent is water.
The result of reacting 3 hours is as follows: Trimethylmethane transformation efficiency is 64%; Trimethylmethane superoxide selectivity is 92%, and tertiary butanol selectivity is 8%.
Embodiment 18
Under temperature is 100 DEG C and pressure is the condition of 2.0MPa, with the mixed gas of ozone, helium and oxygen (wherein, the mixed gas of 10 volume % is ozone, all the other are isopyknic helium and oxygen) be oxygenant, by Trimethylmethane, described mixed gas and solvent acetic acid according to Trimethylmethane: the ozone in described mixed gas: the mol ratio of solvent acetic acid be 1: 2: 60 condition carry out the oxidizing reaction of Trimethylmethane.
The result of reacting 1 hour is as follows: Trimethylmethane transformation efficiency is 24%; Trimethylmethane superoxide selectivity is 85%, tertiary butanol selectivity 15%.
Claims (8)
1. the method for an oxidation of isobutane, the method comprises, under oxidation reaction condition, by Trimethylmethane and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone, described contact is carried out under solvent and titanium-containing catalyst exist, described solvent is the ketone of water and/or C3-C8, described titanium-containing catalyst is molecular sieve containing titanium, described molecular sieve containing titanium is the HTS of HTS system, described HTS is MFI structure, hysteresis loop is there is between the adsorption isothermal line of the nitrogen absorption under low temperature of described HTS and desorption isotherm, described HTS crystal grain is hollow structure and the radical length of chamber portion is 15-180 nanometer, and described HTS is at 25 DEG C, P/P0=0.10, adsorption time is the benzene adsorptive capacity recorded under the condition of 1 hour is 78 milligrams/gram.
2. method according to claim 1, wherein, the mol ratio of the ozone in described Trimethylmethane and oxygenant is 1:0.1-10.
3. method according to claim 1, wherein, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is be selected from least one in oxygen, carbonic acid gas, nitrogen, helium, neon, argon gas and air.
4. method according to claim 3, wherein, with the cumulative volume of mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is oxygen and/or air.
5., according to the method in claim 1-4 described in any one, wherein, in titanium dioxide, the mol ratio of described titanium-containing catalyst and Trimethylmethane is 1:0.1-100.
6. according to the method in claim 1-4 described in any one, wherein, the mol ratio of described Trimethylmethane and solvent is 1:1-150.
7. method according to claim 1, wherein, described solvent is at least one in water, acetone, butanone and methyl phenyl ketone.
8. according to the method in claim 1-4 described in any one, wherein, described oxidation reaction condition comprises, and the temperature of contact is 0-180 DEG C, and pressure is 0.1-3MPa, and the time is 0.1-10 hour.
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| CN201110113828.4A CN102757302B (en) | 2011-04-29 | 2011-04-29 | Method for oxidizing isobutane |
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| CN201110113828.4A CN102757302B (en) | 2011-04-29 | 2011-04-29 | Method for oxidizing isobutane |
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Citations (4)
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|---|---|---|---|---|
| US4508923A (en) * | 1983-02-22 | 1985-04-02 | Atlantic Richfield Company | Oxidation of hydrocarbons |
| US5773634A (en) * | 1996-11-14 | 1998-06-30 | Huntsman Specialty Chemicals Corporation | Tertiary butyl alcohol absorption process for recovering propylene and isobutane |
| CN1328878A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Method for synthesizing titanium silicone molecular sieve |
| CN1359851A (en) * | 2001-12-07 | 2002-07-24 | 大连理工大学 | Gas-solid phase isomorphous replacement process for preparing Ti-Si zeolite |
-
2011
- 2011-04-29 CN CN201110113828.4A patent/CN102757302B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508923A (en) * | 1983-02-22 | 1985-04-02 | Atlantic Richfield Company | Oxidation of hydrocarbons |
| US5773634A (en) * | 1996-11-14 | 1998-06-30 | Huntsman Specialty Chemicals Corporation | Tertiary butyl alcohol absorption process for recovering propylene and isobutane |
| CN1328878A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Method for synthesizing titanium silicone molecular sieve |
| CN1359851A (en) * | 2001-12-07 | 2002-07-24 | 大连理工大学 | Gas-solid phase isomorphous replacement process for preparing Ti-Si zeolite |
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