CN110483244B - Preparation method of tert-butyl alcohol - Google Patents
Preparation method of tert-butyl alcohol Download PDFInfo
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- CN110483244B CN110483244B CN201910774810.5A CN201910774810A CN110483244B CN 110483244 B CN110483244 B CN 110483244B CN 201910774810 A CN201910774810 A CN 201910774810A CN 110483244 B CN110483244 B CN 110483244B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for preparing tert-butyl alcohol, which comprises the steps of taking isobutane and oxygen as reaction raw materials, adding a certain amount of free radical initiator and solvent, controlling the reaction temperature to be 50-90 ℃, controlling the reaction pressure to be 0.5-1.5 MPa, and selectively oxidizing under the catalysis of hexatomic bimetallic porphyrin to prepare the tert-butyl alcohol. The active center of the catalyst is selected from one of iron, cobalt, nickel, copper or zinc. The invention has the advantages of mild reaction conditions, rich raw material sources, simple process and high conversion rate and selectivity.
Description
Technical Field
The invention relates to a preparation method of tertiary butanol, in particular to a method for preparing tertiary butanol by performing biomimetic catalysis on isobutane and selective oxidation by using bimetallic porphyrin.
Background
The tert-butyl alcohol is also called as 2-methyl-2 propanol, is colorless transparent liquid or colorless crystals at normal temperature, has the smell similar to camphor and has wide application. Can be used as fuel oil additive, raw material for producing alkylation of tert-butyl compound, organic synthesis intermediate for synthesizing medicine and perfume, and can replace n-butanol as solvent for paint and medicine. The production of tert-butanol is mainly carried out by the isobutylene hydration method and the isobutane oxidation method.
The method for preparing tert-butyl alcohol by isobutene hydration method takes ion exchange resin, ionic liquid or solid acid as catalyst. The direct hydration process has the disadvantage of relatively poor miscibility of isobutylene with water and, therefore, relatively low conversion. Although the sulfuric acid hydration method can obtain high-yield tertiary butanol, the method has the problems of large pollution, serious equipment corrosion, more industrial three wastes and the like, and is gradually eliminated at present.
Isobutane is one of the main components in the C4 fraction of cracked petroleum gas, and is abundant in source, and it is very interesting to directly oxidize isobutane to prepare tert-butanol. U.S. Pat. No. 4, 2845461 discloses a method for preparing tert-butyl alcohol by catalytic liquid phase oxidation of isobutane, wherein the conversion rate of isobutane by direct oxidation of molecular oxygen can reach 20-35% and the tert-butyl alcohol selectivity is 15-20% under the reaction pressure of 3.4-4.8 MPa and the reaction temperature of 100-150 ℃. The US patent US 4404406 discloses that when the temperature of isobutane is over 140 ℃, the conversion rate of molecular oxygen non-catalytic oxidation isobutane is 10-25%, and the selectivity of tertiary butanol is 10-60%. These processes are carried out at high temperature and high pressure, and the selectivity of tert-butanol is low.
Chinese patent CN 102391167 discloses a method for preparing tert-butanol by oxidizing isobutane with N-hydroxyphthalimide (NHPI) or its derivatives as catalyst. The oxygen source is molecular oxygen, the reaction temperature is 65-85 ℃, the reaction time is 5-7 h, the isobutane conversion rate is 4-42%, and the tertiary butanol selectivity is only 60% at most. The method has mild reaction conditions, but low tert-butyl alcohol selectivity and large catalyst consumption. Chinese patent CN 104402675 discloses a method for preparing tert-butyl alcohol by biomimetic catalytic oxidation, wherein isobutane conversion rate and tert-butyl alcohol selectivity are high, reaction conditions are mild, but metal salt is additionally added as a cocatalyst under the condition that metalloporphyrin is used as a catalyst, so that a reaction system product is complex, and insoluble metal salt is easy to coke in an industrial production process to block a pipeline.
Therefore, the development of the process method for preparing the tert-butyl alcohol by catalytic oxidation of isobutane under mild, green and efficient reaction conditions has important practical significance and application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing tert-butyl alcohol by efficiently catalyzing and oxidizing isobutane with bimetallic porphyrin.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
the preparation method of the tertiary butanol comprises the steps of taking isobutane and oxygen as reaction raw materials, adding a free radical initiator and a solvent, controlling the reaction temperature to be 50-90 ℃, controlling the reaction pressure to be 0.5-1.5 MPa, and preparing the tertiary butanol through selective oxidation under the catalysis of bimetallic porphyrin with a structure shown in a general formula (I);
m in the general formula (I) is a metal atom Fe, Co, Ni, Cu or Zn, R1、R2、R3、R4And R5Are all selected from hydrogen, halogen, nitro, alkyl, alkoxy, hydroxyl, carboxyl or sulfonic group.
Preferably, in the above method for preparing tert-butanol, the radical initiator is N-hydroxyphthalimide (NHPI) or one of its derivatives.
Preferably, in the above method for producing t-butanol, the solvent is one selected from dichloromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, benzonitrile and acetic acid.
Preferably, in the preparation method of the tert-butyl alcohol, the dosage of the catalyst is 10-50 ppm, the dosage of the free radical initiator is 0.5-4 mol% of the raw materials, the reaction temperature is 50-90 ℃, and the reaction pressure is 0.5-1.5 MPa.
Compared with the prior art, the invention has the following beneficial effects:
1. the method has the advantages of high reaction efficiency, high product selectivity, mild reaction conditions and low energy consumption.
2. The invention adopts the binuclear metalloporphyrin as the catalyst, thereby avoiding the problems of equipment corrosion, environmental pollution and the like caused by acid catalyst in the isobutene hydration method.
3. The catalytic activity of the dinuclear porphyrin used in the invention is higher than that of the traditional porphyrin, and metal salt is not required to be added as a cocatalyst.
4. The catalyst is uniformly dissolved in the solvent, and the free radical initiator is added to cause isobutane and oxygen to be catalytically oxidized under the action of the catalyst to generate the tert-butyl alcohol. The invention has the advantages of high yield and selectivity of the tert-butyl alcohol, easy separation of products, low consumption of the catalyst and the free radical initiator, simple process, environmental protection and safety and good industrial application prospect in various reaction systems.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the scope of the examples.
Example 1
A100 ml autoclave was charged with 25ml of a solution containing 10ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Co, R)3＝Cl，R1＝R2＝R4＝R5H) 1, 2-dichloroethane, 0.3mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1MPa of O were charged2And reacting for 6 hours at the temperature of 60 ℃. The gas chromatography detection shows that the isobutane conversion rate is 50% and the tert-butyl alcohol selectivity is 75%.
Example 2
A100 ml autoclave was charged with 25ml of a solution containing 30ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Co, R)3＝F，R1＝R2＝R4＝R5H) was added 0.2mmol of the radical initiator NHPI, charged with 20mmol of isobutane and 1.5MPa of O2And reacting for 8h at 50 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 32% and the tertiary butanol selectivity is 81%.
Example 3
A100 ml autoclave was charged with 25ml of a solution containing 25ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Fe, R)3＝F，R1＝R2＝R4＝R5H) was added 0.4mmol of the radical initiator NHPI, charged with 20mmol of isobutane and 1MPa of O2And reacting for 7 hours at 65 ℃. The gas chromatography detection shows that the isobutane conversion rate is 41% and the tert-butyl alcohol selectivity is 79%.
Example 4
A100 ml autoclave was charged with 25ml of a solution containing 30ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Ni, R)1＝R2＝R3＝R4＝R5F) acetonitrile, 0.2mmol of a radical initiator NHPI was added and charged20mmol of isobutane and 0.7MPa of O2And reacting for 7 hours at the temperature of 80 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 60% and the tertiary butanol selectivity is 72%.
Example 5
In a 100ml high pressure reaction kettle, 25ml metal porphyrin (M ═ Ni, R) containing 30ppm structure with general formula (I) is added3＝Cl，R1＝R2＝R4＝R5H) 1, 2-dichloroethane, 0.2mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1MPa of O were charged2And reacting for 6 hours at the temperature of 60 ℃. The gas chromatography detection shows that the isobutane conversion rate is 60% and the tert-butyl alcohol selectivity is 84%.
Example 6
A100 ml autoclave was charged with 25ml of a solution containing 35ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Cu, R)3＝F，R1＝R2＝R4＝R5H) benzonitrile, 0.2mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1Mpa of O were charged2And reacting for 8 hours at the temperature of 75 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 75% and the tert-butyl alcohol selectivity is 89%.
Example 7
A100 ml autoclave was charged with 25ml of a solution containing 35ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Cu, R)1＝R2＝R3＝R4＝R5= F) acetonitrile, 0.2mmol of the radical initiator NHPI, 20mmol of isobutane and 0.8Mpa of O2And reacting for 7h at 90 ℃. Through gas chromatography detection, the isobutane conversion rate is 85%, and the tert-butyl alcohol selectivity is 82%.
Example 8
In a 100ml autoclave, 25ml metalloporphyrin (M ═ Cu, R) containing 50ppm metalloporphyrin with structure of general formula (I) was added3＝NO2，R1＝R2＝R4＝R5H) acetic acid, 0.4mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1Mpa of O were charged2And reacting for 10 hours at 70 ℃. Detection by gas chromatography of isobutaneThe conversion was 51% and the tert-butanol selectivity was 72%.
Example 9
In a 100ml high pressure reaction kettle, 25ml metalloporphyrin (M ═ Zn, R) containing 40ppm metalloporphyrin with structure of general formula (I) is added1＝R2＝R3＝R4＝R5F) of 1, 2-dichloroethane, 0.2mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1.5Mpa of O were charged2And reacting for 8 hours at the temperature of 80 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 42% and the tert-butyl alcohol selectivity is 76%.
Example 10
A100 ml autoclave was charged with 25ml of a solution containing 35ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Co, R)1＝R2＝R3＝R4＝R5F) of 1, 2-dichloroethane, 0.2mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1Mpa of O were charged2And reacting for 7 hours at the temperature of 70 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 58% and the tert-butyl alcohol selectivity is 76%.
Example 11
A100 ml autoclave was charged with 25ml of a solution containing 15ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Cu, R)1＝R5＝F，R2＝R3＝R4H) acetonitrile, 0.2mmol of the radical initiator NHPI, 20mmol of isobutane and 1.2Mpa of O2And reacting for 9 hours at 65 ℃. The gas chromatography detection shows that the isobutane conversion rate is 62% and the tert-butyl alcohol selectivity is 79%.
Example 12
A100 ml autoclave was charged with 25ml of a solution containing 30ppm of a metalloporphyrin having a structure of the general formula (I) (M ═ Co, R)1＝R5＝F，R2＝R3＝R4H) 1, 2-dichloroethane, 0.4mmol of the radical initiator NHPI was added, 20mmol of isobutane and 1.2Mpa of O were charged2And reacting for 6 hours at 80 ℃. The detection of gas chromatography shows that the isobutane conversion rate is 64% and the tertiary butanol selectivity is 81%.
Claims (6)
1. The preparation method of the tertiary butanol is characterized in that isobutane and oxygen are used as reaction raw materials, a free radical initiator and a solvent are added, the reaction temperature is controlled to be 50-90 ℃, the reaction pressure is 0.5-1.5 MPa, and the tertiary butanol is prepared by selective oxidation under the catalysis of bimetallic porphyrin with a structure shown in a general formula (I);
m in the general formula (I) is a metal atom Fe, Co, Ni, Cu or Zn, R1、R2、R3、R4And R5Are all selected from hydrogen and halogen;
the free radical initiator is selected from N-hydroxyphthalimide or one of derivatives thereof.
2. The method according to claim 1, wherein the solvent is one selected from the group consisting of dichloromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, benzonitrile and acetic acid.
3. The preparation method of claim 1, wherein the amount of the bimetallic porphyrin catalyst is 10-50 ppm.
4. The method according to claim 1, wherein the amount of the radical initiator is 0.5 to 4 mol% based on the raw material.
5. The method according to claim 1, wherein the reaction temperature is 50 to 90 ℃.
6. The method according to claim 1, wherein the reaction pressure is 0.5 to 1.5 MPa.
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