CN103772152A - Preparation method of terephthalyl alcohol - Google Patents
Preparation method of terephthalyl alcohol Download PDFInfo
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- CN103772152A CN103772152A CN201210412579.3A CN201210412579A CN103772152A CN 103772152 A CN103772152 A CN 103772152A CN 201210412579 A CN201210412579 A CN 201210412579A CN 103772152 A CN103772152 A CN 103772152A
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- terephthalyl alcohol
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of terephthalyl alcohol, which mainly solves the problems of long reaction path and serious pollution in the prior art. The method employs the technical scheme that terephthalyl alcohol is prepared through liquid phase oxidation of paraxylene with an oxidant by taking water-soluble Cu salt and water-soluble Fe salt as a catalyst, and taking water as a solvent under the conditions of reaction temperature of 70-120 DEG C, reaction pressure of 0.8-1.5MPa, and reaction time of 3-7h, wherein the catalyst takes quaternary ammonium salt and at least one nitride oxide shown as general formulae I, II, III and IV as shown in the specification as a promoter, R1 and R2 are the same or different and indicate a hydrogen atom, a halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl or acyl respectively, and R3 and R4 are the same or different and indicate the hydrogen atom or acyl, so that the problems are better solved, and the method can be used for industrial production of terephthalyl alcohol.
Description
Technical field
The present invention relates to a kind of method of being prepared terephthalyl alcohol by p-Xylol liquid-phase oxidation.
Background technology
Terephthalyl alcohol is a kind of important organic polymer intermediate, because it structurally has two active hydroxyls, can react and generate multiple polymers with the compound that has hydroxyl, aldehyde radical, carboxyl etc. and have α-reactive hydrogen, they be main raw materials of producing the products such as softening agent, synthon, synthetic resins and binding agent.The production of terephthalyl alcohol is mainly take p-Xylol as raw material at present, after chlorination, be hydrolyzed and make, mainly contain U.S. Pat 3546301(title and be: Process for the preparation of aromatic glycols) and US3993699(title be: Process for producing xylylene glycols).The shortcoming of these methods is that reaction scheme is long, chlorination reaction causes and corrodes and produce pollution equipment.In addition, the disclosed Chinese patent CN101096333(of the people such as Zhu Zhiqing title is: a kind of method of preparing terephthalyl alcohol), CN100584813(title is: by preparing terephthalyl alcohol by hydrogenation of terephthalic acid) and CN100556879(title be: the method for preparing terephthalyl alcohol by hydrogenation of terephthalic acid) take Ru-Sn/Al2O3 as catalyzer, by hydrogenation, terephthalic acid is reduced to terephthalyl alcohol, the yield of its terephthalyl alcohol reaches as high as 94.2%, but the price of raw material terephthalic acid compares dimethylbenzene and wants high a lot, and be to obtain by the oxidation of p-Xylol.Therefore, from an economic point of view, described technique is disadvantageous.
Summary of the invention
Technical problem to be solved by this invention is the long and with serious pollution problem of the reaction scheme that exists in prior art, and a kind of preparation method of terephthalyl alcohol is provided, the method have reaction scheme short, pollute less and the high feature of terephthalyl alcohol yield.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of terephthalyl alcohol, take water-soluble Cu salt and water-soluble Fe salt as catalyzer, water is solvent, it is 70～120 ℃ in temperature of reaction, reaction pressure is 0.8～1.5MPa, reaction times is under the condition of 3～7h, prepare terephthalyl alcohol with oxygenant liquid-phase oxidation p-Xylol, described catalyzer is take quaternary ammonium salt and select at least one oxynitrides that free general formula I, II, III or IV represent as promotor:
（I） （II）
（III） （IV）
Wherein, R
1and R
2for identical or different, represent separately hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group; R
3, R
4and R
5for identical or different, be expressed as hydrogen atom or acyl group.
In such scheme, the preferred Tetrabutyl amonium bromide of described quaternary ammonium salt, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, C
12-16any in alkyl trimethyl ammonium bromide and triethyl benzyl ammonia chloride; Described quaternary ammonium salt and the mol ratio of water are preferably 0.0001～0.01, and more preferably 0.003～0.0045; Described oxynitrides and the mol ratio of water are preferably 0.01～0.1, and more preferably 0.025～0.075; In described catalyzer, Cu salt is preferably from CuCl
2, CuBr
2, Cu (OAc)
2, Cu (acac)
2, Cu (NO
3)
2and CuSO
4in any, more preferably CuCl
2or CuBr
2; Fe salt is preferably from FeCl
3, FeBr
3, Fe (OAc)
3, Fe (acac)
3, Fe (NO
3)
3and Fe
2(SO
4) 3in any, more preferably FeCl
3or FeBr
3; The mol ratio that the mol ratio of the Cu in described catalyzer and the total amount of Fe and water is preferably 0.0045～0.009, Cu:Fe is preferably 1:(0.5～0.7); The mol ratio of described p-Xylol/water is preferably 0.001～0.005; Described oxygenant is preferably air or H
2o
2, the mol ratio of air and raw material p-Xylol is preferably 30～50, H
2o
2be preferably 3～10 with the mol ratio of raw material p-Xylol.
According to the custom of this area, unless otherwise noted, above described pressure all refer to gauge pressure.
The discovery that contriver is surprised, adopts after aforesaid method, and the generation alcohol that the oxidation of p-Xylol can highly selective, generates aldehyde and carboxylic acid and there is not deep oxidation.Experimental result shows, the terephthalyl alcohol yield that prior art (US3546301) obtains is 73%, and the inventive method can to make the yield of terephthalyl alcohol be 86.2%, obtained good technique effect.
Embodiment
[embodiment 1]
The preparation of terephthalyl alcohol: by 2.5mol water, 0.01molCuCl
2, 0.005mol FeCl
3, 0.0075mol Tetrabutyl amonium bromide, 0.0625molN-hydroxyphthalimide (NHPI) and 0.1mol p-Xylol add in titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with nitrogen, improve stirring velocity to 800rpm, supply with continuously pressurized air to reaction pressure 1.0MPa, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 100 ℃, reaction pressure 1.0MPa, the mol ratio of air and p-Xylol is 40, after sustained reaction 3h, and stopped reaction.
Product analysis: gas chromatographic analysis p-Xylol and terephthalyl alcohol wherein for the reaction mixture that above-mentioned reaction is obtained, the yield that obtains as calculated terephthalyl alcohol is 75.8%.
[embodiment 2]
The preparation of terephthalyl alcohol: by 2.5mol water, 0.01molCuCl
2, 0.005mol FeCl
3, 0.0075mol Tetrabutyl amonium bromide, 0.0625molN-hydroxyphthalimide (NHPI), 0.5molH
2o
2add in titanium material reactor with 0.1mol p-Xylol, improve stirring velocity to 800rpm, control reaction pressure 1.0MPa, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 100 ℃, after sustained reaction 3h, and stopped reaction.
Product analysis: gas chromatographic analysis p-Xylol and terephthalyl alcohol wherein for the reaction mixture that above-mentioned reaction is obtained must be 86.2% to the yield of terephthalyl alcohol as calculated.
[embodiment 3-7]
Change Cu, Fe salt kind, but do not change its input amount, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 2.
[embodiment 8-15]
Change CuCl
2and FeCl
3input amount, all the other operate with embodiment 2, the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 1.
[embodiment 16-20]
Change quaternary ammonium salt and oxynitrides kind, do not change it and drop into molar weight, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 1.
[embodiment 21-28]
Change the input amount of Tetrabutyl amonium bromide and HP (NHPI), do not change the input amount of all the other raw materials, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 2.
[embodiment 29-32]
Change the input amount of p-Xylol, do not change the input amount of all the other raw materials, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 2.
[embodiment 33-37]
Change H
2o
2input amount, do not change the input amount of all the other raw materials, all the other operate with embodiment 2, the yield of the terephthalyl alcohol of each embodiment gained is as shown in table 2.
[comparative example 1]
With the FeCl of same molar
3replace CuCl
2, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of comparative example 1 gained is as shown in table 1.
[comparative example 2]
With the CuCl of same molar
2replace FeCl
3, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of comparative example 2 gained is as shown in table 1.
[comparative example 3]
Do not add Tetrabutyl amonium bromide, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of comparative example 3 gained is as shown in table 1.
[comparative example 4]
Do not add HP, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of comparative example 4 gained is as shown in table 1.
[comparative example 5]
Do not add Tetrabutyl amonium bromide and HP, all the other operate with embodiment 2, and the yield of the terephthalyl alcohol of comparative example 5 gained is as shown in table 1.
Table 1
Continued 1
Table 2
Claims (10)
1. the preparation method of a terephthalyl alcohol, take water-soluble Cu salt and water-soluble Fe salt as catalyzer, water is solvent, it is 70～120 ℃ in temperature of reaction, reaction pressure is 0.8～1.5MPa, reaction times is under the condition of 3～7h, prepares terephthalyl alcohol with oxygenant liquid-phase oxidation p-Xylol, it is characterized in that described catalyzer take quaternary ammonium salt and selects at least one oxynitrides that free general formula I, II, III or IV represent as promotor:
（I） （II）
（III） （IV）
Wherein, R
1and R
2for identical or different, represent separately hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group; R
3, R
4and R
5for identical or different, be expressed as hydrogen atom or acyl group.
2. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that described quaternary ammonium salt is Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, C
12-16any in alkyl trimethyl ammonium bromide and triethyl benzyl ammonia chloride.
3. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that described quaternary ammonium salt and the mol ratio of water are 0.0001～0.01, and the mol ratio of oxynitrides and water is 0.01～0.1.
4.4 according to the preparation method of a kind of terephthalyl alcohol described in claim 1 or 3, it is characterized in that described quaternary ammonium salt and the mol ratio of water are 0.003～0.0045, and the mol ratio of oxynitrides and water is 0.025～0.075.
5. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that in described catalyzer, Cu salt can be selected from CuCl
2, CuBr
2, Cu (OAc)
2, Cu (acac)
2, Cu (NO
3)
2and CuSO
4in any, Fe salt can be selected from FeCl
3, FeBr
3, Fe (OAc)
3, Fe (acac)
3, Fe (NO
3)
3and Fe
2(SO
4)
3in any.
6. a kind of preparation method of terephthalyl alcohol according to claim 1 or 5, is characterized in that in described catalyzer, Cu is selected from CuCl
2or CuBr
2, Fe is selected from FeCl
3or FeBr
3.
7. the preparation method of a kind of terephthalyl alcohol according to claim 1, the mol ratio that the Cu in the catalyzer described in it is characterized in that and the total amount of Fe and the mol ratio of water are 0.0045～0.009, Cu:Fe is 1:(0.5～0.7).
8. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that the mol ratio of described p-Xylol/water is 0.001～0.005.
9. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that described oxygenant is air, and the mol ratio of air and raw material p-Xylol is 30～50.
10. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that described oxygenant is H
2o
2, H
2o
2with the mol ratio of raw material p-Xylol be 3～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412579.3A CN103772152B (en) | 2012-10-25 | 2012-10-25 | The preparation method of terephthalyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412579.3A CN103772152B (en) | 2012-10-25 | 2012-10-25 | The preparation method of terephthalyl alcohol |
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| CN103772152A true CN103772152A (en) | 2014-05-07 |
| CN103772152B CN103772152B (en) | 2015-10-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI634101B (en) * | 2016-08-24 | 2018-09-01 | 李長榮化學工業股份有限公司 | System and method for preparing aromatic derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485131A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
-
2012
- 2012-10-25 CN CN201210412579.3A patent/CN103772152B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485131A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YU LU ZHOU ET AL.: "PTCs promoted biphasic oxidation of ethylbenzene catalyzed by NHPI and CoSPc", 《CHINESE CHEMICAL LETTERS》 * |
| 姜瑞霞等: "对二甲苯氧化非溴催化体系研究新进展", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI634101B (en) * | 2016-08-24 | 2018-09-01 | 李長榮化學工業股份有限公司 | System and method for preparing aromatic derivative |
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| CN103772152B (en) | 2015-10-21 |
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