CN102807469B - Method for preparing tertiary butanol by oxidizing iso-butane - Google Patents
Method for preparing tertiary butanol by oxidizing iso-butane Download PDFInfo
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- CN102807469B CN102807469B CN201210299643.1A CN201210299643A CN102807469B CN 102807469 B CN102807469 B CN 102807469B CN 201210299643 A CN201210299643 A CN 201210299643A CN 102807469 B CN102807469 B CN 102807469B
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- trimethylmethane
- butane
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Abstract
The invention relates to a method for preparing tertiary butanol by oxidizing iso-butane. According to the method, the tertiary butanol is prepared by performing catalytic oxidation on iso-butane or mixed butane of iso-butane and n-butane and an oxygen source which serve as reaction raw materials selectively in a liquid phase at reaction temperature of between 50 and 155 DEG C under the reaction pressure of 0.7 to 6.5 MPa for 1 to 10 hours under the catalytic action of a catalyst, wherein the partial pressure of oxygen is 0.05 to 1.0 MPa; the catalyst is mononuclear and multinuclear metal phthalocyanin or a mixture thereof; and active central metal is selected from one or more of aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin and platinum. According to the method, the high selectivity of the tertiary butanol can be kept under the high conversion rate of the iso-butane, the raw materials are abundant in sources, and a process is simple, mild in reaction condition and low in requirement on the purity of the iso-butane.
Description
Technical field
The present invention relates to a kind of method that oxidation of isobutane prepares the trimethyl carbinol.
Background technology
Mixed butanes or Trimethylmethane are mainly derived from the catalytic cracking unit of petrochemical enterprise or the by product of ethylene producing device, are the main components of " liquefied petroleum gas (LPG) ", are mainly used in industry or domestic gas at present.
The trimethyl carbinol is a kind of important Organic Chemicals and intermediates, and molecular formula is (CH
3)
3c-OH.The trimethyl carbinol is of many uses, can dewater and produce iso-butylene, methyl tertiary butyl ether, also oxidable production methyl methacrylate, is also widely used as the auxiliary agent that fine chemicals is produced.
The method of the current suitability for industrialized production trimethyl carbinol has three kinds: iso-butylene sulfuric acid hydration process, iso-butylene direct hydration method and Ha Kang propylene oxide co-production method.Iso-butylene sulfuric acid hydration process due to technical process long, equipment corrosion is serious and have a large amount of acid waste water to produce, and therefore this method is now eliminated substantially.Iso-butylene direct hydration method adopts strong acid ion exchange resin or the high density heteropolyacid aqueous solution to be catalyzer, processing condition are gentle, it is the main method of the current domestic production trimethyl carbinol, but by the restriction of raw material iso-butylene solubleness and chemical equilibrium in water, the per pass conversion of reaction is only 45 ~ 55%.It is reported, raw material iso-butylene is mainly for the production of the important Chemicals such as isoprene-isobutylene rubber, polyisobutene, methyl tertiary butyl ether, and iso-butylene resource is well sold and in short supply limits the scale that hydration method produces the trimethyl carbinol.Propylene oxide co-production method to be succeeded in developing by U.S. Ha Kang (Halcon) company in 1967 and with joint blue (Oxriane) company in Acker west that forms of Atlantic Richfield (Arco) company, this method is dropped into industrial production, first Trimethylmethane is generated the trimethyl carbinol and tertbutyl peroxide by molecular oxygen oxidation, tertbutyl peroxide generates propylene oxide and the trimethyl carbinol with propylene initial ring oxidizing reaction under soluble molybdenum catalyst action, this method abundant raw material source, pollute few, but investment is large and Technology is complicated.
US Patent No. 2845461 discloses the method that Trimethylmethane liquid phase non-catalytic oxidation prepares the trimethyl carbinol, under the condition of temperature of reaction 100 ~ 150 DEG C, reaction pressure 3.4 ~ 4.8MPa, 20 ~ 35% are about with the transformation efficiency of molecular oxygen direct oxidation Trimethylmethane, the selectivity of the trimethyl carbinol is only 15 ~ 50%, and primary product is tertbutyl peroxide.Under US Patent No. 4404406 discloses the supercritical state of Trimethylmethane more than 140 DEG C, be about 10 ~ 25% with the transformation efficiency of molecular oxygen direct oxidation Trimethylmethane, the selectivity of the trimethyl carbinol is only 10 ~ 60%.In addition, US Patent No. 4408081, US4401082, US5162593, US5399777, US5436375 etc. disclose the method for Trimethylmethane non-catalytic oxidation preparing tert-butanol, achieve certain effect, but react high to the purity requirement of raw material Trimethylmethane and all need to carry out at high temperature under high pressure, the selectivity of the trimethyl carbinol is lower.
Chinese patent CN 102391167A discloses a kind of method that oxidation of isobutane prepares tertbutyl peroxide and the trimethyl carbinol, take molecular oxygen as oxygen source, HP (NHPI) or derivatives thereof is catalyzer, under polar solvent exists, Trimethylmethane liquid phase catalytic oxidation prepares tertbutyl peroxide and the trimethyl carbinol, temperature of reaction 65 ~ 85 DEG C, reaction times 5 ~ 7h, Trimethylmethane transformation efficiency 4 ~ 42%, the overall selectivity of tertbutyl peroxide and the trimethyl carbinol can up to 99.8%, but reaction only has 60% to the selectivity of the trimethyl carbinol is the highest.The method temperature of reaction and pressure lower, but tertiary butanol selectivity is low, catalyst levels is large.
Summary of the invention
Based on above-mentioned technical problem, the invention provides a kind of method that oxidation of isobutane prepares the trimethyl carbinol.
Its technical solution is:
A kind of oxidation of isobutane prepares the method for the trimethyl carbinol, it is that the mixed butanes and oxygen source that form with Trimethylmethane or Trimethylmethane and normal butane are for reaction raw materials, under the katalysis of catalyzer, liquid phase selective catalyzed oxidation prepares the trimethyl carbinol, temperature of reaction is 50 ~ 155 DEG C, reaction pressure is 0.7 ~ 6.5MPa, and the dividing potential drop of oxygen is 0.05 ~ 1.0MPa, and the reaction times is 1 ~ 10h; Described catalyzer is the multi-nuclear metal phthalocyanine shown in the mononuclear phthalocyanine shown in logical formula I or general formula (II) or their mixture, and lead in formula I and general formula (II), M is the metal as active centre; X is peripheric substitution base; Y is non-circumferential substituting group; L is axial ligand; In general formula (II), n be more than or equal to 0 integer, when n >=1, i=2,3 ... (n+1);
（II）
The situation of n=0 or 1 in above-mentioned catalyzer preferred formula (II), i.e. binuclear metallo phthalocyanine or three core metal phthalocyanines.
In above-mentioned logical formula I, active centre metal M is the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum; In above-mentioned general formula (II), active centre metal M
1... M
i... M
n+2be respectively the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum, namely the active centre metal types of multi-nuclear metal phthalocyanine can be the same or different.
In above-mentioned logical formula I and general formula (II), X and the Y on phenyl ring be respectively in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amine (ammonia) base, sulfonic group or carboxyl one or both; Namely two substituent X on phenyl ring can be the same or different, as the substituent X of two on phenyl ring can be H, and now X=H, H; Also can a substituent X be H, another substituent X be alkoxyl group (X=H, OCH
3) etc., two substituting group Y on same phenyl ring can be identical, also can be different.
In above-mentioned logical formula I, axial coordination group L
1, L
2be respectively the one in oxygen, halogen, hydroxyl, methyl ethyl diketone, other acid radical anions and five yuan, imidazoles, pyridine, thiophene or furans etc. or 6-membered heterocyclic compound, or be nothing; Axial coordinating group in above-mentioned general formula (II), L
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)be respectively the one in oxygen, halogen, hydroxyl, methyl ethyl diketone, other acid radical anions and five yuan, imidazoles, pyridine, thiophene or furans etc. or 6-membered heterocyclic compound, or be nothing.
Above-mentioned catalyst levels is 0.001 ~ 10% of Trimethylmethane quality, and preferred catalyst consumption is 0.005 ~ 2% of Trimethylmethane quality.
Above-mentioned temperature of reaction preferably 90 ~ 130 DEG C, reaction pressure is 2.0 ~ 4.0MPa preferably, and the dividing potential drop preferably 0.1 ~ 0.5Mpa of oxygen, the reaction times is 5 ~ 7h preferably.
In above-mentioned mixed butanes, the massfraction of preferred Trimethylmethane is not less than 80%.
In above-mentioned oxygen source, the volume fraction of oxygen is 5% ~ 100%, and if oxygen source can be the one in oxygen-denuded air, air, oxygen-rich air or pure oxygen, in preferred oxygen source, the volume fraction of oxygen is 80% ~ 100%.
Now there are some researches show, the non-catalytic oxidation reaction of Trimethylmethane is a reaction process of carrying out according to free chain reaction mechanism, under high-temperature and high-pressure conditions there is fracture and produce tertiary butyl free radical in tertiary carbon hydrogen bond, and generate the trimethyl carbinol through the peroxide bridge homolysis of intermediate product tertbutyl peroxide or heterolytic fission and a series of free radical transmittance process under molecular oxygen exists.Intermediate product tertbutyl peroxide belongs to heat-labile organo-peroxide, temperature can higher than when 90 DEG C acutely be decomposed and discharge a large amount of heats, traditional Trimethylmethane non-catalytic oxidation is prepared trimethyl carbinol technique and is often needed higher temperature of reaction, and the selectivity of the trimethyl carbinol is low in product, the concentration of tertbutyl peroxide is high, there is potential safety hazard to a certain degree.In addition, the reaction of Trimethylmethane non-catalytic oxidation is higher to the purity requirement of raw material Trimethylmethane, and a small amount of impurity can significant prolongation decomposition induction time reduce Trimethylmethane transformation efficiency.
Contriver finds in research process, and metal phthalocyanine class material can accelerate oxidation of isobutane speed of reaction, promote that intermediate product tertbutyl peroxide decomposes, and reduces reaction to the requirement of raw material isobutane purity and significantly improves the selectivity of the trimethyl carbinol.On the one hand, the central active metal of metal phthalocyanine catalyst can activate molecular oxygen, thus the reaction of acceleration molecular oxygen and substrate Trimethylmethane, on the other hand, metal phthalocyanine catalyst significantly can promote that intermediate product tertbutyl peroxide decomposes, and decomposes the free radical produced and adds speed of response and improve the selectivity of the trimethyl carbinol.
In sum, compared with preparing trimethyl carbinol Technology with existing oxidation of isobutane, present method is while guarantee Trimethylmethane transformation efficiency is high, and in the oxidation products obtained, the selectivity of the trimethyl carbinol can reach about 80%; And the present invention one step can obtain the trimethyl carbinol, technique is simple, and preparation easily; Reaction conditions of the present invention is relatively gentle in addition, and security is good, and catalyst activity is high, consumption is few, can reuse and be easy to and product separation, the cheaper starting materials adopted is easy to get, require low to isobutane purity, do not need in reaction process to use other solvents, cost is low.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but therefore do not limit protection scope of the present invention.
Embodiment 1
The metal phthalocyanine that 19.7mg has logical formula I structure is added, wherein X=Y=H, H, M=Fe, L in 250ml autoclave
1=L
2=nothing, 47.3g Trimethylmethane, the oxygen passing into 2.5MPa is continued at 100 DEG C, cool after stirring reaction 6h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 10.3g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 17.6%, the selectivity of the trimethyl carbinol is 81.6%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Embodiment 2
The metal phthalocyanine that 8.5mg has general formula (II) structure is added, wherein X=Y=H, H, n=0, M in 250ml autoclave
1=Co, M
2=Cu, L
1~ L
4=nothing, 50.2g Trimethylmethane, the oxygen passing into 3.2MPa is continued at 115 DEG C, cool after stirring reaction 5h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 23.6g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 36.8%, the selectivity of the trimethyl carbinol is 80.5%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide, formic acid etc.
Embodiment 3
The metal phthalocyanine that 12.6mg has general formula (II) structure is added, wherein X=OCH in 250ml autoclave
3, H, Y=H, H, n=0, M
1=Cr, M
2=Mn, L
1~ L
4=Cl, 51.7g Trimethylmethane, the oxygen passing into 3.3MPa is continued at 120 DEG C, cool after stirring reaction 7h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 26.1g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 39.6%, the selectivity of the trimethyl carbinol is 78.9%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide, formic acid, CO
2deng.
Embodiment 4
The metal phthalocyanine that 12.6mg has general formula (II) structure is added, wherein X=Y=H, H, n=0, M in 250ml autoclave
1=M
2=Mo, L
1=L
3=O, L
2=L
4=nothing, 48.9g Trimethylmethane, the oxygen passing into 3.0MPa is continued at 115 DEG C, cool after stirring reaction 6h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 10.2g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 16.3%, the selectivity of the trimethyl carbinol is 80.2%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Embodiment 5
The metal phthalocyanine that 16.0mg has logical formula I structure is added, wherein X=Y=H, H, M=Co, L in 250ml autoclave
1=L
2=nothing, 48.4g Trimethylmethane, the air passing into 4.0MPa is continued at 125 DEG C, cool after stirring reaction 6h, the unreacted Trimethylmethane of slow releasing and remaining air, obtain product liquid 13.9g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 22.5%, the selectivity of the trimethyl carbinol is 76.7%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Embodiment 6
The metal phthalocyanine that 12.6mg has logical formula I structure is added, wherein X=Y=H, H, M=Co, L in 250ml autoclave
1=L
2=nothing, 47.6g Trimethylmethane, the oxygen passing into 4.0MPa is continued at 135 DEG C, cool after stirring reaction 2h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 16.8g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 27.6%, the selectivity of the trimethyl carbinol is 78.5%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Embodiment 7
The metal phthalocyanine that 11.4mg has general formula (II) structure is added, wherein X=Y=H, H, n=0, M in 250ml autoclave
1=Fe, M
2=Co, L
1~ L
4=nothing, 42.5g Trimethylmethane, 8.1g normal butane, at 120 DEG C, continue the oxygen passing into 3.2MPa, cool after stirring reaction 6h, slowly release unreacted butane and remaining oxygen, obtain product liquid 12.7g, the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 23.4%, and the selectivity of the trimethyl carbinol is 79.5%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol, sec-butyl alcohol, methylethylketone, acetic acid and ditertiary butyl peroxide etc.
Embodiment 8
In 250ml autoclave, add 0.05g imidazoles, 23.7mg has the metal phthalocyanine of logical formula I structure, wherein X=Y=H, H, M=Co, L
1=imidazoles, L
2=nothing, 52.1g Trimethylmethane, the oxygen passing into 2.8MPa is continued at 110 DEG C, cool after stirring reaction 8h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 15.3g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 23.2%, the selectivity of the trimethyl carbinol is 80.8%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Embodiment 9
The metal phthalocyanine that 5.0mg has general formula (II) structure is added, wherein X=Y=H, H, n=0, M in 250ml autoclave
1=Co, M
2=Cu, L
1~ L
4=nothing, 47.9g Trimethylmethane, 2.7g normal butane, at 120 DEG C, continue the oxygen passing into 3.2MPa, cool after stirring reaction 7h, slowly release unreacted butane and remaining oxygen, obtain product liquid 33.0g, the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 54.0%, and the selectivity of the trimethyl carbinol is 82.6%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol, ditertiary butyl peroxide, sec-butyl alcohol, methylethylketone etc.
Embodiment 10
The metal phthalocyanine that 7.3mg has general formula (II) structure is added, wherein X=Y=H, H, n=2, M in 250ml autoclave
1~ M
4=Fe, L
1~ L
8=nothing, 50.3g Trimethylmethane, 8.4g normal butane, at 130 DEG C, continue the oxygen passing into 3.6MPa, cool after stirring reaction 4h, slowly release unreacted butane and remaining oxygen, obtain product liquid 25.1g, the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 39.1%, and the selectivity of the trimethyl carbinol is 81.1%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol, ditertiary butyl peroxide, sec-butyl alcohol, methylethylketone etc.
Comparative example 1(non-catalytic oxidation)
51.7g Trimethylmethane is added in 250ml autoclave, the oxygen passing into 3.2MPa is continued at 120 DEG C, cool after stirring reaction 6h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 11.3g, the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 17.1%, and the selectivity of the trimethyl carbinol is 62.1%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Comparative example 2(non-catalytic oxidation)
48.8g Trimethylmethane is added in 250ml autoclave, 5.4g normal butane, the oxygen passing into 4.0MPa is continued at 130 DEG C, cool after stirring reaction 6h, the unreacted butane of slow releasing and remaining oxygen, obtain product liquid 8.2g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 13.2%, the selectivity of the trimethyl carbinol is 54.6%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
Comparative example 3(metal salt catalyst is oxidized)
5.2mg FeCl is added in 250ml autoclave
350.6g Trimethylmethane, the oxygen passing into 3.0MPa is continued at 110 DEG C, cool after stirring reaction 6h, the unreacted Trimethylmethane of slow releasing and remaining oxygen, obtain product liquid 9.1g, and the transformation efficiency that Trimethylmethane is measured in gas chromatographic analysis is 14.1%, the selectivity of the trimethyl carbinol is 62.6%, and Main By product is tertbutyl peroxide, acetone, methyl alcohol and ditertiary butyl peroxide etc.
As can be seen from comparing of embodiment and comparative example, the selectivity of the metal phthalocyanine catalyst gained trimethyl carbinol is adopted to be significantly improved compared with the selectivity of the gained trimethyl carbinol under non-catalytic oxidation or metal salt catalyst oxidizing condition.
Claims (2)
1. an oxidation of isobutane prepares the method for the trimethyl carbinol, it is characterized in that: the mixed butanes formed with Trimethylmethane or Trimethylmethane and normal butane and oxygen source are for reaction raw materials, under the katalysis of catalyzer, liquid phase selective catalyzed oxidation prepares the trimethyl carbinol, temperature of reaction is 90 ~ 130 DEG C, reaction pressure is 2.0 ~ 4.0MPa, and oxygen partial pressure is 0.1 ~ 0.5Mpa, and the reaction times is 5 ~ 7h; Described catalyzer is the multi-nuclear metal phthalocyanine shown in logical formula II, in logical formula II, and M
1... M
i... M
n+2be the metal as active centre, be respectively the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum; X, Y be respectively in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amino, sulfonic group or carboxyl one or both; L
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)be respectively the one in oxygen, halogen, hydroxyl, methyl ethyl diketone, acid radical anion, imidazoles, pyridine, thiophene or furans, or be nothing; In logical formula II, n be more than or equal to 0 integer, when n>=1, i=2,3 ... (n+1);
Described catalyst levels is 0.001 ~ 10% of Trimethylmethane quality;
In described mixed butanes, the massfraction of Trimethylmethane is not less than 80%;
In described oxygen source, the volume fraction of oxygen is 80% ~ 100%.
2. a kind of oxidation of isobutane according to claim 1 prepares the method for the trimethyl carbinol, it is characterized in that: described catalyst levels is 0.005 ~ 2% of Trimethylmethane quality.
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| CN104262222B (en) * | 2014-09-04 | 2016-08-17 | 中山大学惠州研究院 | A kind of method that bionic catalysis oxidation of isobutane prepares tert-butyl hydroperoxide |
| CN110483244B (en) * | 2019-08-21 | 2022-07-08 | 中山大学 | Preparation method of tert-butyl alcohol |
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| US4922036A (en) * | 1987-09-08 | 1990-05-01 | Texaco Inc. | Tertiary butyl hydroperoxide decomposition |
| CN101899022A (en) * | 2010-07-27 | 2010-12-01 | 中山大学 | Method for preparing epoxypropane by bionically catalyzing epoxidation of propylene |
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2012
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| US3816548A (en) * | 1971-04-27 | 1974-06-11 | Mobil Oil Corp | Catalytic oxidation process for isoparaffin hydrocarbons |
| US4296263A (en) * | 1980-09-19 | 1981-10-20 | Atlantic Richfield Company | Tertiary butyl alcohol production |
| US4922036A (en) * | 1987-09-08 | 1990-05-01 | Texaco Inc. | Tertiary butyl hydroperoxide decomposition |
| CN101899022A (en) * | 2010-07-27 | 2010-12-01 | 中山大学 | Method for preparing epoxypropane by bionically catalyzing epoxidation of propylene |
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Effective date of registration: 20191105 Address after: 266590 No. 579, Bay Road, Huangdao District, Shandong, Qingdao Co-patentee after: CNNOOC TAIZHOU PETROCHEMICAL CO.,LTD. Patentee after: SHANDONG University OF SCIENCE AND TECHNOLOGY Address before: 266590 Qingdao economic and Technological Development Zone, Shandong, former Bay Road, No. 579 Co-patentee before: TAIZHOU DONGLIAN CHEMICAL Co.,Ltd. Patentee before: Shandong University of Science and Technology |
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Granted publication date: 20150204 |