CN103772152B - The preparation method of terephthalyl alcohol - Google Patents

The preparation method of terephthalyl alcohol Download PDF

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Publication number
CN103772152B
CN103772152B CN201210412579.3A CN201210412579A CN103772152B CN 103772152 B CN103772152 B CN 103772152B CN 201210412579 A CN201210412579 A CN 201210412579A CN 103772152 B CN103772152 B CN 103772152B
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terephthalyl alcohol
preparation
water
salt
mol ratio
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CN103772152A (en
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朱庆才
畅延青
陈大伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of preparation method of terephthalyl alcohol, mainly solve the reaction scheme length and with serious pollution problem that exist in prior art.The present invention is by adopting with water-soluble Cu salt and water-soluble Fe salt as catalyzer, water is solvent, it is 70 ~ 120 DEG C 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, at least one oxynitrides that described catalyzer is represented by general formula I, II, III or IV with quaternary ammonium salt and being selected from is for promotor: (I) (II) (III) (IV) wherein, R 1and R 2for identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group separately; R 3, R 4and R 5for identical or different, be expressed as the technical scheme of hydrogen atom or acyl group, solve this problem preferably, can be used in the industrial production of terephthalyl alcohol.

Description

The preparation method of terephthalyl alcohol
Technical field
The present invention relates to a kind of method 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 hydroxyl groups, can react with the compound having hydroxyl, aldehyde radical, carboxyl etc. and have α-reactive hydrogen and generate multiple polymers, they are the main raw materials producing the products such as softening agent, synthon, synthetic resins and binding agent.The production of current terephthalyl alcohol is mainly raw material with p-Xylol, after chlorination, hydrolysis is obtained, and mainly containing US Patent No. 3546301(title is: 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 equipment and corrodes and produce pollution.In addition, disclosed in the people such as Zhu Zhiqing, Chinese patent CN101096333(title is: a kind of method 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) be catalyzer with Ru-Sn/Al2O3, 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 obtained 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, provides a kind of preparation method of terephthalyl alcohol, 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, with water-soluble Cu salt and water-soluble Fe salt for catalyzer, water is solvent, it is 70 ~ 120 DEG C 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, at least one oxynitrides that described catalyzer is represented by general formula I, II, III or IV with quaternary ammonium salt and being selected from is for promotor:
（I） （II）
（III） （IV）
Wherein, R 1and R 2for identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxyl group or acyl group separately; 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 one 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, are more preferably 0.003 ~ 0.0045; Described oxynitrides and the mol ratio of water are preferably 0.01 ~ 0.1, are 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 one, 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 one, more preferably FeCl 3or FeBr 3; The mol ratio that the total amount of Cu and Fe in described catalyzer and the mol ratio of water are 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 23 ~ 10 are preferably with the mol ratio of raw material p-Xylol.
According to the custom of this area, unless otherwise noted, above, described pressure all refers to gauge pressure.
The discovery that contriver is surprised, adopts after aforesaid method, and the oxidation of p-Xylol can the generation alcohol of highly selective, and deep oxidation does not occur generates aldehyde and carboxylic acid.Experimental result shows, the terephthalyl alcohol yield that prior art (US3546301) obtains is 73%, and the inventive method can make the yield of terephthalyl alcohol be 86.2%, achieves 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 with nitrogen and be pressurized to 0.5MPa after air, improve stirring velocity to 800rpm, continuous supply pressurized air is to reaction pressure 1.0MPa, and stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 100 DEG C, reaction pressure 1.0MPa, the mol ratio of air and p-Xylol is 40, after sustained reaction 3h, stopped reaction.
Product analysis: by the above-mentioned reaction mixture gas chromatographic analysis be obtained by reacting p-Xylol wherein and terephthalyl alcohol, as calculated the yield of 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 DEG C, after sustained reaction 3h, stopped reaction.
Product analysis: by the above-mentioned reaction mixture gas chromatographic analysis be obtained by reacting p-Xylol wherein and terephthalyl alcohol, 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 operations are 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 operation 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 operations are 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 operations are 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 operations are 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 operation 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 operations are 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 operations are 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 operations are 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 operations are 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 operations are 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, with water-soluble Cu salt and water-soluble Fe salt for catalyzer, water is solvent, it is 70 ~ 120 DEG C 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 at least one oxynitrides that described catalyzer represents by general formula I, II, III or IV with quaternary ammonium salt and being selected from is for promotor:
Wherein, R 1and R 2for identical or different, represent hydrogen atom, halogen atom, alkyl, hydroxyl, alkoxyl group or acyl group separately; 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 one 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 the mol ratio of described quaternary ammonium salt and water is 0.0001 ~ 0.01, and the mol ratio of oxynitrides and water is 0.01 ~ 0.1.
4. the preparation method of a kind of terephthalyl alcohol according to claim 1 or 3, is characterized in that the mol ratio of described quaternary ammonium salt and water is 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 one, 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 one.
6. the preparation method of a kind of terephthalyl alcohol according to claim 1 or 5, is characterized in that, in described catalyzer, Cu salt is selected from CuCl 2or CuBr 2, Fe salt is selected from FeCl 3or FeBr 3.
7. the preparation method of a kind of terephthalyl alcohol according to claim 1, is characterized in that the total amount of Cu and Fe in described catalyzer and the mol ratio of water be the mol ratio of 0.0045 ~ 0.009, Cu:Fe are 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 2be 3 ~ 10 with the mol ratio of raw material p-Xylol.
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Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
PTCs promoted biphasic oxidation of ethylbenzene catalyzed by NHPI and CoSPc;Yu Lu Zhou et al.;《Chinese Chemical Letters》;20120704;第23卷;第896页scheme1，试验部分，Table1 *
对二甲苯氧化非溴催化体系研究新进展;姜瑞霞等;《石油化工》;20071231;第36卷(第1期);第100页摘要，第101页右栏-第103页左栏 *

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