CN110483244A - A kind of preparation method of the tert-butyl alcohol - Google Patents
A kind of preparation method of the tert-butyl alcohol Download PDFInfo
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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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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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
- B01J2531/84—Metals of the iron group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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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 kind of methods for preparing the tert-butyl alcohol, this method is using iso-butane, oxygen as reaction raw materials, a certain amount of radical initiator and solvent is added, controlling reaction temperature is 50 ~ 90 DEG C, reaction pressure is 0.5 ~ 1.5 MPa, and selective oxidation prepares the tert-butyl alcohol under the catalysis of hexa-atomic bimetallic porphyrin.Used catalyst activated centre is selected from one of iron, cobalt, nickel, copper or zinc.The advantage of the invention is that reaction condition is mild, raw material sources are abundant, simple process, and conversion ratio and selectivity are high.
Description
Technical field
The present invention relates to a kind of preparation methods of tert-butyl alcohol, specifically, it is different to be related to a kind of bimetallic porphyrin bionic catalysis
The method that Selective oxidation of butane prepares the tert-butyl alcohol.
Background technique
The tert-butyl alcohol is also known as -2 propyl alcohol of 2- methyl, is colourless transparent liquid or colourless crystallization under room temperature, has similar camphor gas
Taste, tool have been widely used.It can be used as fuel oil additive, the production alkylated raw material of tert-butyl compound, as organic synthesis
Intermediate is used for the synthesis of drug, fragrance, n-butanol can be replaced as the solvent of coating and medicine.It prepares the tert-butyl alcohol mainly and has and is different
Butylene hydration method and oxidation of isobutane method.
Isobutene hydration method prepares method of the tert-butyl alcohol with ion exchange resin, ionic liquid or solid acid etc. for catalyst
Occupy leading position.The shortcomings that direct hydration method is that the intersolubility of isobutene and water is poor, therefore conversion ratio is lower.Sulfuric acid hydration
Although method can get the tert-butyl alcohol of high yield, there is the problems such as big pollution, equipment seriously corroded, three industrial wastes are more, at present
It is gradually eliminated.
Iso-butane is one of the main component in oil gas C 4 fraction, abundance, the preparation of direct oxidation iso-butane
The tert-butyl alcohol is concerned.United States Patent (USP) US 2845461 discloses the side that a kind of no catalyzing liquid phase oxidation iso-butane prepares the tert-butyl alcohol
Method, under the reaction pressure, 100~150 DEG C of reaction temperature of 3.4~4.8MPa, molecular oxygen direct oxidation iso-butane conversion ratio
It can reach 20~35%, tertiary butanol selectivity has 15~20%.United States Patent (USP) US 4404406 disclose iso-butane 140 DEG C with
On, molecular oxygen non-catalyst oxidation iso-butane conversion ratio is 10~25%, and the selectivity of the tert-butyl alcohol is 10~60%.These methods are equal
It need to carry out at high temperature under high pressure, tertiary butanol selectivity is all relatively low.
Chinese patent CN 102391167 discloses one kind with n-Hydroxyphthalimide (NHPI) or derivatives thereof
The method that iso-butane prepares the tert-butyl alcohol is aoxidized for catalyst.Oxygen source is molecular oxygen, 65~85 DEG C of reaction temperature, the reaction time 5~
7h, iso-butane conversion ratio 4~42%, tertiary butanol selectivity highest only 60%.This method reaction condition is milder, but the tert-butyl alcohol selects
Selecting property is low, catalyst amount is big.Chinese patent CN 104402675 discloses the side that a kind of bionic catalysis oxidation prepares the tert-butyl alcohol
Method, this method iso-butane conversion ratio and tertiary butanol selectivity are all higher, and reaction condition is mild, but are used as and urge in metalloporphyrin
It also needs additionally to add metal salt under agent as co-catalyst, causes reaction system product complicated, it is insoluble in industrial processes
The easy coking of metal salt make pipeline blockage.
Therefore, the technique side that a kind of mild reaction condition, green, efficient catalysis oxidation iso-butane prepare the tert-butyl alcohol is developed
Method has important practical significance and application prospect.
Summary of the invention
In order to overcome defect present in the above-mentioned prior art, it is high that the purpose of the present invention is to provide a kind of bimetallic porphyrins
The method that effect catalysis oxidation iso-butane prepares the tert-butyl alcohol.
In order to realize goal of the invention, used technical solution is:
Radical initiator and solvent is added using iso-butane, oxygen as reaction raw materials in a kind of preparation method of the tert-butyl alcohol,
Controlling reaction temperature is 50~90 DEG C, and reaction pressure is 0.5~1.5MPa, under the catalysis of general formula (I) structure bimetallic porphyrin
Selective oxidation prepares the tert-butyl alcohol；
M in general formula (Ι) is metallic atom Fe, Co, Ni, Cu or Zn, R1、R2、R3、R4And R5It is selected from hydrogen, halogen, nitre
Base, alkyl, alkoxy, hydroxyl, carboxyl or sulfonic group.
Preferably, the radical initiator is N- hydroxyl neighbour benzene two in the preparation method of the above-mentioned tert-butyl alcohol
One of carboximide (NHPI) or derivatives thereof.
Preferably, the solvent is selected from methylene chloride, 1,2-, bis- chloroethene in the preparation method of the above-mentioned tert-butyl alcohol
One of alkane, ethyl acetate, acetonitrile, benzonitrile or acetic acid.
Preferably, the catalyst amount is 10~50ppm, free radical in the preparation method of the above-mentioned tert-butyl alcohol
Initiator amount is 0.5~4mol% of raw material, and reaction temperature is 50~90 DEG C, and reaction pressure is 0.5~1.5MPa.
Compared with prior art, the invention has the following beneficial effects:
1. reaction efficiency of the present invention is high, selectivity of product is high, reaction condition is mild, and low energy consumption.
2. the present invention uses dinuclear metalloporphyrin for catalyst, avoids acid catalyst corrosion in isobutene hydration method and set
The problems such as standby, pollution environment.
3. double-core porphyrin catalytic activity used in the present invention is higher than classical porphyrins, addition metal salt is not needed as co-catalysis
Agent.
4. catalyst uniform dissolution in a solvent, is added radical initiator, is urging iso-butane and oxygen by the present invention
Agent acts on lower catalysis oxidation and generates the tert-butyl alcohol.Under the various reaction systems of the present invention, tert-butyl alcohol yield and selectivity are all higher, produce
Object is easily separated, and catalyst, radical initiator dosage be few, simple process, green safe, has good prospects for commercial application.
Specific embodiment
The present invention will be further explained with reference to the examples below, but protection scope of the present invention is not limited to implement
The range that example indicates.
Embodiment 1
In 100ml autoclave, 25ml is added and contains 10ppm with the structural metal general formula (Ι) porphyrin (M=Co, R3
=Cl, R1=R2=R4=R5=H) 1,2- dichloroethanes, the radical initiator NHPI of 0.3mmol is added, is filled with 20mmol
Iso-butane and 1MPa O2, 6h is reacted under conditions of 60 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 50%, uncle
Butanol selectivity is 75%.
Embodiment 2
In 100ml autoclave, 25ml is added and contains 30ppm with the structural metal general formula (Ι) porphyrin (M=Co, R3
=F, R1=R2=R4=R5=H) methylene chloride, the radical initiator NHPI of 0.2mmol is added, is filled with the different of 20mmol
The O of butane and 1.5MPa2, 8h is reacted under conditions of 50 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 32%, tertiary fourth
Alcohol is selectively 81%.
Embodiment 3
In 100ml autoclave, 25ml is added and contains 25ppm with the structural metal general formula (Ι) porphyrin (M=Fe, R3
=F, R1=R2=R4=R5=H) ethyl acetate, the radical initiator NHPI of 0.4mmol is added, is filled with the different of 20mmol
The O of butane and 1MPa2, 7h is reacted under conditions of 65 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 41%, the tert-butyl alcohol
Selectivity is 79%.
Embodiment 4
In 100ml autoclave, 25ml is added and contains 30ppm with the structural metal general formula (Ι) porphyrin (M=Ni, R1
=R2=R3=R4=R5=F) acetonitrile, the radical initiator NHPI of 0.2mmol is added, be filled with 20mmol iso-butane and
The O of 0.7MPa2, 7h is reacted under conditions of 80 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 60%, tert-butyl alcohol selection
Property is 72%.
Embodiment 5
In 100ml autoclave, 25ml is added and contains 30ppm with the structural metal general formula (Ι) porphyrin (M=Ni, R3
=Cl, R1=R2=R4=R5=H) 1,2- dichloroethanes, the radical initiator NHPI of 0.2mmol is added, is filled with 20mmol
Iso-butane and 1MPa O2, 6h is reacted under conditions of 60 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 60%, uncle
Butanol selectivity is 84%.
Embodiment 6
In 100ml autoclave, 25ml is added and contains 35ppm with the structural metal general formula (Ι) porphyrin (M=Cu, R3
=F, R1=R2=R4=R5=H) benzonitrile, the radical initiator NHPI of 0.2mmol is added, is filled with the isobutyl of 20mmol
The O of alkane and 1Mpa2, 8h is reacted under conditions of 75 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 75%, tert-butyl alcohol choosing
Selecting property is 89%.
Embodiment 7
In 100ml autoclave, 25ml is added and contains 35ppm with the structural metal general formula (Ι) porphyrin (M=Cu, R1
=R2=R3=R4=R5=F) acetonitrile, the radical initiator NHPI of 0.2mmol is added, be filled with 20mmol iso-butane and
The O of 0.8Mpa2, 7h is reacted under conditions of 90 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 85%, tert-butyl alcohol selection
Property is 82%.
Embodiment 8
In 100ml autoclave, 25ml is added and contains 50ppm with the structural metal general formula (Ι) porphyrin (M=Cu, R3
=NO2, R1=R2=R4=R5=H) acetic acid, the radical initiator NHPI of 0.4mmol is added, is filled with the iso-butane of 20mmol
With the O of 1Mpa2, 10h is reacted under conditions of 70 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 51%, tert-butyl alcohol selection
Property is 72%.
Embodiment 9
In 100ml autoclave, 25ml is added and contains 40ppm with the structural metal general formula (Ι) porphyrin (M=Zn, R1
=R2=R3=R4=R5=F) 1,2- dichloroethanes, the radical initiator NHPI of 0.2mmol is added, is filled with 20mmol's
The O of iso-butane and 1.5Mpa2, 8h is reacted under conditions of 80 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 42%, uncle
Butanol selectivity is 76%.
Embodiment 10
In 100ml autoclave, 25ml is added and contains 35ppm with the structural metal general formula (Ι) porphyrin (M=Co, R1
=R2=R3=R4=R5=F) 1,2- dichloroethanes, the radical initiator NHPI of 0.2mmol is added, is filled with 20mmol's
The O of iso-butane and 1Mpa2, 7h is reacted under conditions of 70 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 58%, tertiary fourth
Alcohol is selectively 76%.
Embodiment 11
In 100ml autoclave, 25ml is added and contains 15ppm with the structural metal general formula (Ι) porphyrin (M=Cu, R1
=R5=F, R2=R3=R4=H) acetonitrile, the radical initiator NHPI of 0.2mmol is added, is filled with the iso-butane of 20mmol
With the O of 1.2Mpa2, 9h is reacted under conditions of 65 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 62%, tert-butyl alcohol choosing
Selecting property is 79%.
Embodiment 12
In 100ml autoclave, 25ml is added and contains 30ppm with the structural metal general formula (Ι) porphyrin (M=Co, R1
=R5=F, R2=R3=R4=H) 1,2- dichloroethanes, the radical initiator NHPI of 0.4mmol is added, is filled with 20mmol
Iso-butane and 1.2Mpa O2, 6h is reacted under conditions of 80 DEG C.Through gas chromatographic detection, iso-butane conversion ratio is 64%,
Tertiary butanol selectivity is 81%.
Claims (7)
1. a kind of preparation method of the tert-butyl alcohol, it is characterised in that using iso-butane, oxygen as reaction raw materials, radical initiator is added
And solvent, control reaction temperature are 50~90 DEG C, reaction pressure is 0.5~1.5MPa, in general formula (I) structure bimetallic porphyrin
It is catalyzed lower selective oxidation and prepares the tert-butyl alcohol；
M in general formula (Ι) is metallic atom Fe, Co, Ni, Cu or Zn, R1、R2、R3、R4And R5It is selected from hydrogen, halogen, nitro, alkane
Base, alkoxy, hydroxyl, carboxyl or sulfonic group.
2. preparation method according to claim 1, it is characterised in that the radical initiator is selected from N- hydroxyl neighbour's benzene
One kind of dicarboximide or derivatives thereof.
3. preparation method according to claim 1, it is characterised in that the solvent is selected from methylene chloride, 1,2-, bis- chloroethene
One of alkane, ethyl acetate, acetonitrile, benzonitrile or acetic acid.
4. preparation method according to claim 1, it is characterised in that the bimetallic porphyrin catalyst amount be 10~
50ppm。
5. preparation method according to claim 1, it is characterised in that the radical initiator dosage is the 0.5 of raw material
~4mol%.
6. preparation method according to claim 1, it is characterised in that the reaction temperature is 50~90 DEG C.
7. preparation method according to claim 1, it is characterised in that the reaction pressure is 0.5~1.5MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536859A (en) * | 2022-11-30 | 2022-12-30 | 中山大学 | Porphyrin metal-organic framework material based on bimetallic oxygen chain and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536859A (en) * | 2022-11-30 | 2022-12-30 | 中山大学 | Porphyrin metal-organic framework material based on bimetallic oxygen chain and preparation method and application thereof |
| CN115536859B (en) * | 2022-11-30 | 2023-03-14 | 中山大学 | Porphyrin metal-organic framework material based on bimetallic oxygen chain and preparation method and application thereof |
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