CN102757302A - Method for oxidizing isobutane - Google Patents
Method for oxidizing isobutane Download PDFInfo
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- CN102757302A CN102757302A CN2011101138284A CN201110113828A CN102757302A CN 102757302 A CN102757302 A CN 102757302A CN 2011101138284 A CN2011101138284 A CN 2011101138284A CN 201110113828 A CN201110113828 A CN 201110113828A CN 102757302 A CN102757302 A CN 102757302A
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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 is 2-methyl-2-propyl alcohol, is the simplest tertiary alcohol, is one of four kinds of isomer of butanols.The trimethyl carbinol can be used as solvent, also can be used in the production of Denatured alcohol, paint clean-out system, gasoline dope and other daily necessities such as spices and perfume.
In the industry; The trimethyl carbinol can be generated by oxidation of isobutane, and oxidation of isobutane mainly adopts air autoxidation technology, makes Trimethylmethane superoxide (Trimethylmethane hydrogen peroxide); This peroxide oxidation third rare propylene oxide that makes then, superoxide is converted into trimethyl carbinol sub product simultaneously.Propylene oxide in the industry that Here it is and trimethyl carbinol joint process are a kind of of conjugated oxidation, also are one of main production of propylene oxide (account for propylene oxide production capacity about 20%).
But during the conventional oxidation Trimethylmethane, oxidization time is long, efficient is low, causes oxidation furnaces huge, and cost of investment heightens.And when requiring must scale to acquire a certain degree, just have an economic benefit, thereby limited further developing of this technology.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, the method for the oxidation of isobutane that a kind of Trimethylmethane transformation efficiency is high, technology is simple, with low cost is provided.
Contriver of the present invention finds under study for action, uses ozone to come the oxidation Trimethylmethane can access higher Trimethylmethane transformation efficiency as oxygenant.And accomplished the present invention based on this.
The present invention provides a kind of method of oxidation of isobutane, and this method comprises, under oxidation reaction condition, Trimethylmethane is contacted with oxygenant, it is characterized in that, said oxygenant is the gas that contains ozone.
Method of the present invention promptly can be effectively with oxidation of isobutane through adopting ozone to need not to add catalyzer as oxygenant; And this method technological process is simple, but need not in reaction system to introduce the just degree of good control reaction of extra initiator or suppressor factor.Simultaneously, in system, introduce the transformation efficiency that catalyzer can improve reactant; Under special preferable case, adopt preferred catalyst of the present invention and preferred solvent, the transformation efficiency of reactant can further improve.
Than traditional method, method of the present invention has that technology is easy, with low cost, Trimethylmethane transformation efficiency advantages of higher.In addition, method of the present invention does not receive production-scale restriction, therefore, has the industrial applications prospect.
Embodiment
The present invention provides a kind of method of oxidation of isobutane, and this method comprises, under oxidation reaction condition, Trimethylmethane is contacted with oxygenant, it is characterized in that, said oxygenant is the gas that contains ozone.
In the method for oxidation of the present invention, the usage quantity of ozone can change in more wide in range scope in the oxygenant, and preferably, the mol ratio of the ozone in said Trimethylmethane and the oxygenant is 1: 0.1-10 further is preferably 1: 0.2-5.
Ozone has another name called three atomic oxygens, is commonly called as " good fortune oxygen, ultra oxygen, the oxygen of living ", and molecular formula is O
3, under the normal temperature and pressure, ozone is to be nattier blue gas.Among the present invention; The said gas that contains ozone can be the mixed gas of purified ozone or ozone and diluents; According to the method for the invention; The said gas that contains ozone is preferably the mixed gas of ozone and diluents, can regulate the concentration of ozone easily like this, thereby control the severe of reaction better.The effect of said diluents is that ozone is diluted, and therefore, any gas 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, said diluents is for being selected from oxygen, carbonic acid gas, nitrogen, helium, neon, argon gas and airborne at least a, further preferably; Said diluents most preferably is oxygen and/or air for being selected from oxygen, helium, carbonic acid gas and airborne at least a.
Among the present invention; The content of ozone in said mixed gas can in very large range change; And can adjust accordingly according to the difference of diluents; TV with mixed gas is a benchmark, and the content of ozone is preferably more than the 1 volume % in the said mixed gas, further is preferably more than the 5 volume %.
Contriver of the present invention finds that under study for action when Trimethylmethane carried out in the presence of titanium-containing catalyst with contacting of oxygenant, the Trimethylmethane transformation efficiency can improve further; The consumption of said titanium-containing catalyst can be catalyst consumption in the oxidation of isobutane technology of routine; Preferably, in titanium oxide, the mol ratio of said titanium-containing catalyst and Trimethylmethane is 1: 0.1-100; Further be preferably 1: 1-50 most preferably is 1: 5-50.
Can be used for the of a great variety of titanium-containing catalyst of the present invention; For example; Said titanium-containing catalyst can be in the preformed catalyst, amorphous silicon titanium and the titanium oxide that are selected from molecular sieve containing titanium, molecular sieve containing titanium at least a; Preferably, said titanium-containing catalyst is to be selected from least a in preformed catalyst and the titanium oxide of molecular sieve containing titanium, molecular sieve containing titanium.
According to the method for the invention; In order further to improve the transformation efficiency of Trimethylmethane; Molecular sieve containing titanium is preferably HTS described in the present invention, and what said HTS can be in the HTS (like Ti-ZSM-48) of the HTS (like Ti-TUN) of the HTS (like Ti-MOR) of the HTS (like Ti-MCM-41, Ti-SBA-15) of the HTS (like TS-1) of MFI structure, the HTS (like TS-2) of MEL structure, the HTS (like Ti-Beta) of BEA structure, the HTS (like Ti-MCM-22) of MWW structure, two-dimentional hexagonal structure, MOR structure, TUN structure and other structures is at least a.
Under the preferable case; Said HTS is the HTS of MFI structure; Further preferably; Said HTS is that MFI structure, crystal grain are the HTS of hollow structure, and the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and said HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 a milligrams/gram, has hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this HTS and the desorption isotherm.
In the present invention, said HTS can be commercially available, and also can prepare, and the method for preparing said HTS is for conventionally known to one of skill in the art, like document (Zeolites, 1992, Vol.12, the method described in 943-950).
According to the method for the invention, in order to make the reaction system homogeneous, said contact is preferably carried out in the presence of solvent, and the mol ratio of said Trimethylmethane and solvent can be 1: 1-150 is preferably 1: 1-100 further is preferably 1: 1-60.
As everyone knows; In the chemical reaction system; The effect of solvent mainly is in order to make reaction solution be homogeneous phase; Reaction can steadily be carried out, and contriver of the present invention finds, reaction effect is better during as solvent with in the organic acid of the nitrile of the ketone of the alcohol of water, C1-C6, C3-C8, C2-C8 and C1-C6 one or more; Wherein, the alcohol of said C1-C6 can be in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol and the isopropylcarbinol one or more; The ketone of said C3-C8 can be in acetone, butanone and the methyl phenyl ketone one or more; The nitrile of said C2-C8 can be in acetonitrile, propionitrile, vinyl cyanide and the benzyl cyanide one or more; The organic acid of said C1-C6 can be formic acid and/or acetate.
Contriver of the present invention finds unexpectedly, when said solvent is ketone and/or the water of C3-C8, further is preferably at least a in acetone, butanone, methyl phenyl ketone and the water, especially when acetone and/or water, can access very high Trimethylmethane transformation efficiency.
According to the present invention, said oxidation reaction condition comprises that the temperature of contact can be 0-180 ℃, is preferably 20-160 ℃, further is preferably 20-150 ℃; Pressure can be 0.1-3MPa, is preferably 0.3-2.5MPa, 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., feed way also can be any suitable way well known by persons skilled in the art, the present invention does not all have particular requirement to this, do not give unnecessary details one by one at this.
Following embodiment will do explanation further to the present invention, but therefore not limit content of the present invention.
Among the embodiment, as not specifying that agents useful for same is commercially available chemically pure reagent.Used ozone is provided by the NLO-15 type oxygen source ozone producer that Fujian New Continent Environmental Protection Technology Co., Ltd produces, and ozone concn is adjustable, and maximum volume concentration can reach 80%.Specify in following examples as not, all use source of oxygen to prepare ozone.
The sieve sample of used TS-1 catalyzer for preparing by prior art (Zeolites, 1992, the method described in the Vol.12,943-950), titanium oxide content is 2.4%.The sieve sample of used Ti-MCM-41 for preparing by prior art (methods described in the Corma etc., Chem.Commun.1994,147-148), titanium oxide content is 3%.The sieve sample of used Ti-Beta for preparing by prior art (methods described in the TakashiTatsumi etc., J.Chem.Soc.Chem.Commun.1997,677-678), titanium oxide content is 2.5 weight %.
(long manufactured is built in the Hunan to the Industrial products that used hollow HTS HTS is the said HTS of CN1301599A among the embodiment; Through the X-ray diffraction analysis is the HTS of MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption 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 a milligrams/gram), titanium oxide content is 2.5 weight %.
Among the present invention, adopt gc to carry out each analysis of forming in the system, carry out quantitatively all can carrying out, calculate the evaluation indexes such as yield and selectivity of transformation efficiency, the product of reactant on this basis with reference to prior art through proofreading and correct normalization method.
In an embodiment:
Embodiment 1
Being 60 ℃ in temperature is under the condition of 0.5MPa with pressure; With the mixed gas of ozone and oxygen (wherein; The mixed gas of 15 volume % is an ozone) for oxygenant, with Trimethylmethane, said mixed gas and solvent acetone according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of solvent acetone is the oxidizing reaction that 1: 1: 1 condition is carried out Trimethylmethane.
The result who reacts 2 hours is following: the Trimethylmethane transformation efficiency is 17%; Trimethylmethane superoxide selectivity is 94%, trimethyl carbinol selectivity 6%.
Embodiment 2
The oxygenant that uses in the present embodiment is the mixed gas that contains ozone; This mixed gas be through use air as the source of oxygen of ozonizer prepare (wherein; The mixed gas of 15 volume % is an ozone); Being 20 ℃ in temperature is under the condition of 1.5MPa with pressure, with Trimethylmethane, said mixed gas and solvent methanol according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of solvent methanol is the oxidizing reaction that 1: 1: 5 condition is carried out Trimethylmethane.
The result who reacts 5 hours is following: the Trimethylmethane transformation efficiency is 14%; Trimethylmethane superoxide selectivity is 97%, trimethyl carbinol selectivity 3%.
Embodiment 3
Being 80 ℃ in temperature is under the condition of 0.2MPa with pressure; With the mixed gas of ozone and oxygen (wherein; The mixed gas of 5 volume % is an ozone) for oxygenant, with Trimethylmethane, said mixed gas and solvent acetonitrile according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of solvent acetonitrile is the oxidizing reaction that 1: 2: 10 condition is carried out Trimethylmethane.
The result who reacts 2 hours is following: the Trimethylmethane transformation efficiency is 21%; Trimethylmethane superoxide selectivity is 92%, trimethyl carbinol selectivity 8%.
Embodiment 4
Being 40 ℃ in temperature is under the condition of 0.1MPa with pressure; With the mixed gas of ozone and oxygen (wherein; The mixed gas of 15 volume % is an ozone) for oxygenant, with Trimethylmethane, said mixed gas and solvent acetone according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of solvent acetone is the oxidizing reaction that 1: 4: 50 condition is carried out Trimethylmethane.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 18%; Trimethylmethane superoxide selectivity is 91%, trimethyl carbinol selectivity 9%.
Embodiment 5
Reaction process and the result of present embodiment explanation in the presence of catalyzer.
Carry out the oxidation of Trimethylmethane according to the method for embodiment 4, different is, adds TS-1 as catalyzer, and the molar ratio of TS-1 catalyzer and Trimethylmethane is 1|: 50.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 32%; Trimethylmethane superoxide selectivity is 86%, trimethyl carbinol selectivity 14%.
Embodiment 6
The oxygenant that uses in the present embodiment is the mixed gas that contains ozone; This mixed gas be through use air as the source of oxygen of ozonizer prepare (wherein; The mixed gas of 12 volume % is an ozone); Being 50 ℃ in temperature is under the condition of 1.0MPa with pressure, with Trimethylmethane, said mixed gas and aqueous solvent according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of aqueous solvent is the oxidizing reaction that 1: 0.3: 3 condition is carried out Trimethylmethane.
The result who reacts 4 hours is following: the Trimethylmethane transformation efficiency is 21%; Trimethylmethane superoxide selectivity is 89%, trimethyl carbinol selectivity 11%.
Embodiment 7
Being 120 ℃ in temperature is under the condition of 1.0MPa with pressure; With the mixed gas of ozone, carbonic acid gas and oxygen (wherein; The mixed gas of 8 volume % is an ozone; All the other are 7: 10 carbonic acid gas and oxygen for volume ratio) for oxygenant, with Trimethylmethane, mixed gas and solvent acetone according to Trimethylmethane: the ozone in the mixed gas: the mol ratio of solvent acetone is the oxidizing reaction that 1: 0.6: 25 condition is carried out Trimethylmethane.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 27%; Trimethylmethane superoxide selectivity is 83%, trimethyl carbinol selectivity 17%.
Embodiment 8
Carry out the oxidation of Trimethylmethane according to the method for embodiment 7, different is that solvent is an ethanol.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 22%; Trimethylmethane superoxide selectivity is 84%, and trimethyl carbinol selectivity is 16%.
Embodiment 9
Reaction process and the result of present embodiment explanation in the presence of catalyzer.
Carry out the oxidation of Trimethylmethane according to the method for embodiment 7, different is to 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 who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 36%; Trimethylmethane superoxide selectivity is 67%, trimethyl carbinol selectivity 33%.
Embodiment 10
Carry out the oxidation of Trimethylmethane according to the method for embodiment 9, different is that solvent is an ethanol.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 31%; Trimethylmethane superoxide selectivity is 69%, and trimethyl carbinol selectivity is 31%.
Embodiment 11
Carry out the oxidation of Trimethylmethane according to the method for embodiment 9, different is TiO
2By etc. the Ti-MCM-41 of weight replace.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 33%; Trimethylmethane superoxide selectivity is 67%, and trimethyl carbinol selectivity is 33%.
Embodiment 12
Carry out the oxidation of Trimethylmethane according to the method for embodiment 9, different is TiO
2By etc. the Ti-Beta of weight replace.
The result who reacts 2 hours is following: the Trimethylmethane transformation efficiency is 34%; Trimethylmethane superoxide selectivity is 68%, and trimethyl carbinol selectivity is 32%.
Embodiment 13
Carry out the oxidation of Trimethylmethane according to the method for embodiment 9, different is TiO
2By etc. the HTS of weight replace.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 65%; Trimethylmethane superoxide selectivity is 94%, and trimethyl carbinol selectivity is 6%.
Embodiment 14
Carry out the oxidation of Trimethylmethane according to the method for embodiment 13, different is that solvent is an acetonitrile.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 58%; Trimethylmethane superoxide selectivity is 75%, and trimethyl carbinol selectivity is 25%.
Embodiment 15
Carry out the oxidation of Trimethylmethane according to the method for embodiment 13, different is that solvent is an acetate.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 57%; Trimethylmethane superoxide selectivity is 68%, and trimethyl carbinol selectivity is 32%.
Embodiment 16
Carry out the oxidation of Trimethylmethane according to the method for embodiment 13, different is that solvent is an ethanol.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 55%; Trimethylmethane superoxide selectivity is 63%, and trimethyl carbinol selectivity is 37%.
Embodiment 17
Carry out the oxidation of Trimethylmethane according to the method for embodiment 13, different is that solvent is a water.
The result who reacts 3 hours is following: the Trimethylmethane transformation efficiency is 64%; Trimethylmethane superoxide selectivity is 92%, and trimethyl carbinol selectivity is 8%.
Embodiment 18
Being 100 ℃ in temperature is under the condition of 2.0MPa with pressure; With the mixed gas of ozone, helium and oxygen (wherein; The mixed gas of 10 volume % is an ozone; All the other are isopyknic helium and oxygen) for oxygenant, with Trimethylmethane, said mixed gas and solvent acetic acid according to Trimethylmethane: the ozone in the said mixed gas: the mol ratio of solvent acetic acid is the oxidizing reaction that 1: 2: 60 condition is carried out Trimethylmethane.
The result who reacts 1 hour is following: the Trimethylmethane transformation efficiency is 24%; Trimethylmethane superoxide selectivity is 85%, trimethyl carbinol selectivity 15%.
Claims (13)
1. the method for an oxidation of isobutane, this method comprises, under oxidation reaction condition, Trimethylmethane is contacted with oxygenant, it is characterized in that, said oxygenant is the gas that contains ozone.
2. method according to claim 1, wherein, the mol ratio of the ozone in said Trimethylmethane and the oxygenant is 1: 0.1-10.
3. method according to claim 1; Wherein, The said gas that contains ozone is the mixed gas of ozone or ozone and diluents; And the TV with mixed gas is a benchmark, and the content of ozone is more than the 1 volume % in the said mixed gas, and said diluents is for being selected from oxygen, carbonic acid gas, nitrogen, helium, neon, argon gas and airborne at least a.
4. method according to claim 3 wherein, is a benchmark with the TV of mixed gas, and the content of ozone is more than the 5 volume % in the said mixed gas, and said diluents is oxygen and/or air.
5. according to any described method among the claim 1-4, wherein, said contact is carried out in the presence of titanium-containing catalyst, and in titanium oxide, the mol ratio of said titanium-containing catalyst and Trimethylmethane is 1: 0.1-100.
6. method according to claim 5, wherein, said titanium-containing catalyst is at least a in preformed catalyst, amorphous silicon titanium and the titanium oxide that is selected from molecular sieve containing titanium, molecular sieve containing titanium.
7. method according to claim 6; Wherein, said molecular sieve containing titanium is at least a in the HTS of HTS and two-dimentional hexagonal structure 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.
8. method according to claim 7; Wherein, said HTS is the HTS of MFI structure, and said HTS crystal grain is hollow structure; The radical length of the cavity part of this hollow structure is the 5-300 nanometer, and said HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 a milligrams/gram, has hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this HTS and the desorption isotherm.
9. according to any described method among the claim 1-4, wherein, said contact is carried out in the presence of solvent, and the mol ratio of said Trimethylmethane and solvent is 1: 1-150.
10. method according to claim 9, wherein, said solvent is at least a in the organic acid of nitrile and C1-C6 of ketone, C2-C8 of alcohol, the C3-C8 of water, C1-C6.
11. method according to claim 10, wherein, said solvent is the ketone of water and/or C3-C8.
12. method according to claim 11, wherein, said solvent is at least a in water, acetone, butanone and the methyl phenyl ketone.
13. according to any described method among the claim 1-4, wherein, said oxidation reaction condition comprises that the temperature of contact is 0-180 ℃, 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022192866A1 (en) * | 2021-03-09 | 2022-09-15 | University Of Kansas | Hydroxylation of alkanes using ozone |
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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 |
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022192866A1 (en) * | 2021-03-09 | 2022-09-15 | University Of Kansas | Hydroxylation of alkanes using ozone |
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