CN1417193A - Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid - Google Patents
Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid Download PDFInfo
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- CN1417193A CN1417193A CN 01133428 CN01133428A CN1417193A CN 1417193 A CN1417193 A CN 1417193A CN 01133428 CN01133428 CN 01133428 CN 01133428 A CN01133428 A CN 01133428A CN 1417193 A CN1417193 A CN 1417193A
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- acetic acid
- acid
- oxidation
- mesitylene
- tail gas
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Abstract
The liquid phase catalytic mesitylene oxidizing process of preparing benzenetricarboxylic acid has the features of low product cost, high product quality, mesitylene conversion of 98.5-99.0% and benzenetricarboxylic acid weight yield of 115-120 % in mesitylene. In the process mesitylene is used as raw material, air as oxidant, acetic acid as solvent, bromide as initiator, cobalt acetate as catalyst and manganese acetate as cocatalyst. The raw benzenetricarboxylic acid obtained through oxidation is re-crystallized in dilute acetic acid to obtain refined benzenetricarboxylic acid, with the dilute acetic acid being reused after distillation to eliminate organic carboxylic acid.
Description
The present invention be a kind of be raw material with the sym-trimethylbenzene, adopt the air liquid-phase oxidation to produce trimesic acid, belong to the fine chemical technology field.
With the sym-trimethylbenzene is that raw material is produced trimesic acid, generally adopts potassium permanganate oxidation method.This method disadvantage is that catalyzer potassium permanganate consumption is big, and catalyst levels is about 10 times of a raw material consumption, and price is expensive, therefore causes the product cost height, and has limited the application of this method.
The present invention seeks to disclose the method that a kind of mesitylene air liquid phase catalytic oxidation is produced trimesic acid, it is low to have product cost, characteristics such as good product quality.Its technological process is simple, technology maturation.Sym-trimethylbenzene transformation efficiency 98.5-990%o, for sym-trimethylbenzene, trimesic acid weight yield 115-120%.
Its technology of the present invention is: (is unit with the 300ml raw material) in stills for air blowing (material is the titanium material) adds sym-trimethylbenzene 300ml (content 99%) raw material, wherein: 1500ml acetic acid (99% acetic acid), 1.3g Cobaltous diacetate, 2.7g manganese acetate, 0,55ml tetrabromoethane.Reinforced back begins to feed pressurized air to the oxidation material heating when liquidus temperature reaches 170C in the stills for air blowing, the control air flow is 0.8-4.6M3/h, stirs 600-700 rev/min of revolution.Oxidizing reaction temperature maintains 220-250 ℃, pressure 2.2-2.5Mpa.Oxidizing reaction tail gas carries a small amount of sym-trimethylbenzene, acetic acid, and part is returned stills for air blowing after condensation.Remaining reaction tail gas through the acetic acid absorption tower to remove acetic acid wherein, again through the gac resorber to remove sym-trimethylbenzene wherein.After peroxyacetic acid and charcoal absorption, oxidized tail gas is just discharged.Be oxidizing to 100-120 minute, the tail gas oxygen level reaches 19-20% and is the oxidation terminal point.Oxidation rear oxidation liquid is put to crystallization kettle.Have stirring in the crystallization kettle, the still chuck feeds water of condensation.Through 4 hours, the trimesic acid crystallization in the oxidation products was complete approximately, and the crystallization outlet temperature is at 30-40 ℃.Material centrifugation after the crystallization.Mother liquor is acetic acid and is dissolved in wherein trimesic acid, pays and produce di-carboxylic acid, catalyzer.This material removes the acetic acid rectifying tower, 82-85% concentration acetic acid is carried dense to more than 98%.This acetic acid returns stills for air blowing and recycles.The centrifugal back of oxidation material is that filter cake is dissolved in dilute acetic acid in dissolution kettle.40% acetic acid that adds 10 times of filter cake weight in dissolution kettle, the gac of adding 5-10% filter cake weight is heated to boiling under agitation condition.Fully after the dissolving, take advantage of heat filtering, filtrate is removed the recrystallization still.Filter cake is gac and a spot of trimesic acid, di-carboxylic acid.For guaranteeing that quality product can repeat twice dissolving decolouring, recrystallization process.Obtain the white crystals trimesic acid like this.
The present invention is a raw material with the sym-trimethylbenzene, is that oxygenant, acetic acid are that solvent, bromide are that initiator, Cobaltous diacetate are that catalyst, manganese acetate are promotor with the air.The catalyst acetic acid cobalt is the acetate of generation 4 crystal water, and molecular formula is Co (CH
3COO)
2.4H
2O.Consumption is 0.1-1% (for a raw material sym-trimethylbenzene weight).Help the acetate of catalyst manganese acetate for generation 4 crystal water, molecular formula is M
nCH
3COO)
24H
20.Consumption is 0.1-1%.The initiator bromide is tetrabromoethane or Sodium Bromide or brometo de amonio.The tetrabromoethane consumption is 0.1-1.1% (for a raw material sym-trimethylbenzene weight).The thick trimesic acid acid number 780mgKOH/g that method oxidation of the present invention obtains, content 98% (gas chromatographic analysis) recrystallization in dilute acetic acid (10-60%) can make the elaboration trimesic acid.Dilute acetic acid is gone out after distillation and be can be recycled behind the organic carboxyl acid.For the organic pigment that removes in the trimesic acid can be decoloured with gac.Method according to above-mentioned introduction can obtain the trimesic acid elaboration, and product not only satisfies the demand that reverse osmosis membrane is handled in sea water desaltination, and satisfies the other industry requirement.
The present invention compares with potassium permanganate oxidation method that to have product cost low, advantages such as good product quality.
Claims (1)
1. a mesitylene air liquid phase catalytic oxidation is produced the method for trimesic acid, its technology is: (is unit with the 300ml raw material) in stills for air blowing (material is the titanium material) adds sym-trimethylbenzene 300ml (content 99%) raw material, wherein: 1500ml acetic acid (99% acetic acid), 1.3g Cobaltous diacetate, 2.7g manganese acetate, 0,55ml tetrabromoethane.Reinforced back begins to feed pressurized air to the oxidation material heating when liquidus temperature in the stills for air blowing reaches 170 ' C, the control air flow is 0.8-4.6M3/h, stirs 600-700 rev/min of revolution.Oxidizing reaction temperature maintains 220-250 ℃, pressure 2.2-2.5Mpa.Oxidizing reaction tail gas carries a small amount of sym-trimethylbenzene, acetic acid, and part tail gas returns stills for air blowing after condensation.Remaining reaction tail gas through the acetic acid absorption tower to remove acetic acid wherein, again through the gac resorber to remove sym-trimethylbenzene wherein.After peroxyacetic acid and charcoal absorption, oxidized tail gas is just discharged.Be oxidizing to 100-120 minute, the tail gas oxygen level reaches 19-20% and is the oxidation terminal point.Oxidation rear oxidation liquid is put to crystallization kettle.Have stirring in the crystallization kettle, the still chuck feeds water of condensation.Through 4 hours, the trimesic acid crystallization in the oxidation products was complete approximately, and the crystallization outlet temperature is at 30-40 ℃.Material centrifugation after the crystallization.Mother liquor is acetic acid and is dissolved in wherein trimesic acid, pays and produce di-carboxylic acid, catalyzer.This material removes the acetic acid rectifying tower, 82-85% concentration acetic acid is carried dense to 98% above acetic acid.This acetic acid returns stills for air blowing and recycles.The centrifugal back of oxidation material is that filter cake is dissolved in dilute acetic acid in dissolution kettle.40% acetic acid that adds 10 times of filter cake weight in dissolution kettle, the gac of adding 5-10% filter cake weight is heated to boiling under agitation condition.The dissolving after-filtration, filtrate is removed the recrystallization still, and filter cake is gac and a spot of trimesic acid, di-carboxylic acid.Can repeat twice dissolving decolouring.Recrystallization process.Obtain the white crystals trimesic acid like this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133428 CN1417193A (en) | 2001-11-06 | 2001-11-06 | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133428 CN1417193A (en) | 2001-11-06 | 2001-11-06 | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid |
Publications (1)
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|---|---|
| CN1417193A true CN1417193A (en) | 2003-05-14 |
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| CN 01133428 Pending CN1417193A (en) | 2001-11-06 | 2001-11-06 | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462144C (en) * | 2006-09-22 | 2009-02-18 | 曹善文 | Preparation method of composition |
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN103113219A (en) * | 2013-03-05 | 2013-05-22 | 黑龙江大学 | Synthetic method of 2-chlorine-4-trifluoromethyl benzoic acid |
| CN104513156A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | A purifying method for crude 1,3,5-benzenetricarboxylic acid |
-
2001
- 2001-11-06 CN CN 01133428 patent/CN1417193A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462144C (en) * | 2006-09-22 | 2009-02-18 | 曹善文 | Preparation method of composition |
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN103113219A (en) * | 2013-03-05 | 2013-05-22 | 黑龙江大学 | Synthetic method of 2-chlorine-4-trifluoromethyl benzoic acid |
| CN104513156A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | A purifying method for crude 1,3,5-benzenetricarboxylic acid |
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