CN100488936C - Method for preparing terephthalic acid - Google Patents
Method for preparing terephthalic acid Download PDFInfo
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- CN100488936C CN100488936C CNB200510032394XA CN200510032394A CN100488936C CN 100488936 C CN100488936 C CN 100488936C CN B200510032394X A CNB200510032394X A CN B200510032394XA CN 200510032394 A CN200510032394 A CN 200510032394A CN 100488936 C CN100488936 C CN 100488936C
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- Prior art keywords
- porphyrin
- terephthalic acid
- xylol
- general formula
- 30ppm
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Abstract
The invention discloses a method for preparing terephthalic acid, adding mun-oxygen monometallic porphyrin or bimetal porphyrin by 1-30ppm into a traditional system using acetic acid as solvent, cobalt acetate and manganese acetate as catalysts and bromide as accelerant, controlling reaction temperature at 150-250 deg.C, air pressure at 1.0-2.0MPa, and reaction time at 1-2 hours, and oxidizing para dimethyl benzene or dimethyl benzene mixtures in different proportions into corresponding terephatalic acid. And on the premise of not changing the existing production facility and process, adding in metal porphyrin by 2-30ppm can raise paradimethylbenzene conversion and terephthalic acid yield by 5%-10% and accelerate the reaction rate by 10%-35%. The invention uses less metal porphyrin, and has high catalyzing efficiency and high reaction rate and obvious production benefits.
Description
Technical field
The present invention relates to a kind of atmospheric oxidation p-Xylol and become method of terephthalic acid.
Background technology
Oxidation of p-xylene becomes method of terephthalic acid to mainly contain U.S. Amoco method, Britain ICI method and Mitsui method at present, they all are to be solvent with acetic acid, Cobaltous diacetate, manganese acetate are catalyzer, bromides etc. are promotor, under 180～200 ℃, 14～16MPa, use the atmospheric oxidation p-Xylol.As US 5,763,648 disclose in acetate solvate and to use Cobaltous diacetate or manganese and Potassium Bromide to make catalyzer, the atmospheric oxidation p-Xylol becomes method of terephthalic acid, US 6,175,038 discloses in acetic acid-water mixed solvent and to use composite metal salt and Potassium Bromide to make catalyzer, become method of terephthalic acid by the oxygen-rich air oxidation of p-xylene, US6,180,822 disclose in acetate solvate and to use metal-salt to make catalyzer, become method of terephthalic acid by carbonic acid gas with Air mixing gas oxidation of p-xylene.The oxidizing reaction rate of above method and reaction conversion ratio are all not high.CN1453259A discloses the method that is prepared phthalic acid by catalysis of metalloporphyrin atmospheric oxidation dimethylbenzene, but will change existing production unit and technology.
Summary of the invention
The object of the present invention is to provide a kind of is in the catalyst system at existing Cobaltous diacetate, manganese acetate and bromide, under the prerequisite that does not change existing production unit and technology, can obviously improve the preparation method of a kind of terephthalic acid of the oxidizing reaction rate of p-Xylol and reaction conversion ratio.
Technical scheme of the present invention is: be solvent with acetic acid, Cobaltous diacetate, manganese acetate are catalyzer, bromide is in the traditional system of promotor, add 1-30ppm by general formula (I) or μ (II)-oxygen monometallic porphyrin or bimetallic porphyrin, control reaction temperature 150-250 ℃, air pressure 1.0-2.0MPa reacted 1-2 hour, and the xylene mixture of p-Xylol or different ratios is oxidized to corresponding phthalic acid.
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2Can be Fe, Mn, Co, Cu, transition metal atoms such as Cr; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino; Dentate X can be an acetate, methyl ethyl diketone, halogen.
Described traditional system is to comprise following component and weight percent: raw material p-Xylol or xylene mixture 15-30; Solvent acetic acid 60-80, water 5-12; Catalyst acetic acid cobalt 200-400ppm, manganese acetate 200-400ppm; Promotor bromide 450-600ppm.
The mixture of described dimethylbenzene is p-Xylol and other dimethylbenzene mixture by various different ratioss.
Experiment shows that under the prerequisite that does not change existing production unit and technology, behind the adding 2-30ppm metalloporphyrin, the transformation efficiency of p-Xylol and terephthalic acid yield can improve 5-10%, and speed of response is accelerated 10-35%.The consumption that this technology adds metalloporphyrin is little, does not increase production cost, catalytic efficiency height basically, and speed of response is fast, and productivity effect is obvious.
Embodiment
Embodiment 1:
Containing p-Xylol 20%, acetic acid 71% in the system of water 9%, adds the 350ppm Cobaltous diacetate, and 350ppm manganese acetate, 500ppm Potassium Bromide and 10ppm have the μ-oxygen monometallic porphyrin of general formula (I), R
1=R
2=H, R
3=CH
3, M=Co, 180 ℃ of control reaction temperature, air pressure 1.2MPa, reactant 2 hours, the dimethylbenzene transformation efficiency is 88%, terephthalic acid yield 70% in the reaction product.
Embodiment 2:
Containing p-Xylol 15%, acetic acid 78% in the system of water 7%, adds the 200ppm Cobaltous diacetate, and 300ppm manganese acetate, 550ppm Sodium Bromide and 20ppm have the μ-oxygen monometallic porphyrin of general formula (I), R
1=R
2=OC
2H
5, R
3=Cl, M=Cu, 150 ℃ of control reaction temperature, air pressure 1.8MPa, reactant 2 hours, the p-Xylol transformation efficiency is 75%, terephthalic acid yield 54% in the reaction product.
Embodiment 3:
At p-Xylol 30%, acetic acid 65% in the system of water 5%, adds the 300ppm Cobaltous diacetate, and 400ppm manganese acetate, 500ppm Potassium Bromide and 2ppm have the μ-oxygen monometallic porphyrin of general formula (I), R
1=OH, R
2=R
3=C
2H
5, M=Mn, 220 ℃ of control reaction temperature, air pressure 1.0MPa, reactant 1 hour, the p-Xylol transformation efficiency is 90%, terephthalic acid yield 82% in the reaction product.
Embodiment 4:
At p-Xylol 25%, acetic acid 68% in the system of water 7%, adds the 280ppm Cobaltous diacetate, the 350ppm manganese acetate, and 600ppm Sodium Bromide and 30ppm have the bimetallic porphyrin of general formula (II), R
1=R
2=H, R
3=Br, M
1=M
2=Fe, 200 ℃ of control reaction temperature, air pressure 2.0MPa, reactant 1.5 hours, the p-Xylol transformation efficiency is 95%, terephthalic acid yield 86% in the reaction product.
Embodiment 5:
At p-Xylol 28%, acetic acid 62% in the system of water 10%, adds the 400ppm Cobaltous diacetate, and 200ppm manganese acetate, 450ppm Sodium Bromide and 5ppm have the μ-oxygen monometallic porphyrin of general formula (I), R
1=NH
2, R
2=R
3=F, M=Fe, 230 ℃ of control reaction temperature, air pressure 1.6MPa, reactant 1.0 hours, the p-Xylol transformation efficiency is 90%, terephthalic acid yield 76% in the reaction product.
Embodiment 6:
At the equivalent p-Xylol and the m-xylene that contain 23%, acetic acid 71% in the system of water 6%, adds the 350ppm Cobaltous diacetate, and 300ppm manganese acetate, 500ppm Sodium Bromide and 8ppm have the μ-oxygen bimetallic porphyrin of general formula (II), R
1=R
2=H, R
3=OCH
3, M=Mn, 190 ℃ of control reaction temperature, air pressure 1.4MPa, reactant 1.5 hours obtains pure mixed phthalic acid with 72%.
Embodiment 7:
At p-Xylol 21%, acetic acid 71% in the system of water 8%, adds the 380ppm Cobaltous diacetate, and 380ppm manganese acetate, 500ppm Potassium Bromide and 15ppm have the μ-oxygen monometallic porphyrin of general formula (I), R
1=N (CH
3)
2, R
2=R
3=H, M=Cr, 250 ℃ of control reaction temperature, air pressure 1.3MPa, reactant 1.5 hours, the p-Xylol transformation efficiency is 92%, terephthalic acid yield 83% in the reaction product.
Claims (1)
1. the preparation method of a terephthalic acid, it is characterized in that, it with acetic acid solvent, Cobaltous diacetate, manganese acetate are catalyzer, and bromide is in the traditional system of promotor, add 1-30ppm by general formula (I) or μ (II)-oxygen monometallic porphyrin or bimetallic porphyrin, control reaction temperature 150-250 ℃, air pressure 1.0-2.0MPa reacted 1-2 hour, and the xylene mixture of p-Xylol or different ratios is oxidized to corresponding phthalic acid; Described xylene mixture is meant p-Xylol and other dimethylbenzene mixture by various different ratioss;
General formula (I)
General formula (II)
Atoms metal M, M in the said structure
1, M
2Be transition metal atoms Fe, Mn, Co, Cu or Cr, substituent R on the phenyl ring
1, R
2, R
3Be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido or amino, according to the structure needs, dentate X is acetate, methyl ethyl diketone or halogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510032394XA CN100488936C (en) | 2005-11-18 | 2005-11-18 | Method for preparing terephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510032394XA CN100488936C (en) | 2005-11-18 | 2005-11-18 | Method for preparing terephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775725A CN1775725A (en) | 2006-05-24 |
| CN100488936C true CN100488936C (en) | 2009-05-20 |
Family
ID=36765466
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510032394XA Expired - Fee Related CN100488936C (en) | 2005-11-18 | 2005-11-18 | Method for preparing terephthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100488936C (en) |
-
2005
- 2005-11-18 CN CNB200510032394XA patent/CN100488936C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 实用有机化学辞典. 高鸿宾，783，高等教育出版社. 1997 |
| 实用有机化学辞典. 高鸿宾，783，高等教育出版社. 1997 * |
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| Publication number | Publication date |
|---|---|
| CN1775725A (en) | 2006-05-24 |
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Granted publication date: 20090520 Termination date: 20131118 |