CN107175128B - Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation - Google Patents

Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation Download PDF

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CN107175128B
CN107175128B CN201610139914.5A CN201610139914A CN107175128B CN 107175128 B CN107175128 B CN 107175128B CN 201610139914 A CN201610139914 A CN 201610139914A CN 107175128 B CN107175128 B CN 107175128B
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catalyst
hydroxyphthalimide
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bromine
acetate
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CN107175128A (en
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肖忠斌
朱小丽
孙广斌
王艳红
畅延青
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract

The invention relates to a catalyst for preparing aromatic polycarboxylic acid by liquid-phase oxidation, which mainly solves the problem of overhigh bromine consumption in the catalyst in the prior art. The catalyst comprises Co salt, Mn salt, IVB group metal salt, bromine-containing compound and 4-substituent-N-hydroxyphthalimide, wherein the weight ratio of Co to Mn to IVB group metal to Br to 4-substituent-N-hydroxyphthalimide is 500 (200-300) (10-50) (1000-2000) (50-100), the technical problem is better solved, and the catalyst can be used for producing terephthalic acid by liquid-phase oxidation of p-xylene.

Description

Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation
Technical Field
The present invention relates to a catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation.
Background
Purified terephthalic acid, commonly known as PTA, is a basic raw material for synthesizing polyethylene terephthalate (PET), and the demand thereof is continuously increasing, and it is expected that the global demand for PTA will reach 5000 ten thousand tons in 2015. At present, the PTA production technology is mainly a two-step process of p-xylene (PX) oxidation and hydrofining developed by Amoco-MC company, wherein a Co-Mn-Br catalyst system is adopted in the oxidation step, and acetic acid is used as a solvent; hydrogenation is mainly carried out by adding p-aldehyde benzoic acid (4-CBA) into p-methyl benzoic acid (p-TA), centrifuging and washing with water to remove.
In the development process of the PTA production process, four main patent technologies of Amoco, Mitsui, ICI and Eastman are formed. The four technologies have the common point that the four technologies all adopt an Amoco-MC liquid phase catalytic oxidation method, the catalyst is a cobalt-manganese-bromine system, the solvent is acetic acid, and the difference is that the oxidation reaction temperature of various technologies is different (from 160 ℃ to 225 ℃), and the corresponding process conditions, the reactor forms and the process design are also different. ICI and Amoco reaction temperature is highest, the three-well-Amoco temperature is intermediate, and Eastman is lowest, which are respectively called high temperature oxidation, medium temperature oxidation and low temperature oxidation process.
No matter which process is adopted, bromine is needed as a cocatalyst, the bromine has strong corrosivity, and particularly under the high-temperature condition, so all reactors adopt expensive titanium materials; at the same time, too much bromine causes side reactions to occur, resulting in loss of solvent and raw materials. Many scholars both at home and abroad are studying to reduce the bromine content or completely replace bromine. U.S. Pat. No. 4,7985875 (Process for preparing aromatic polycarboxylic acid by liquid alkylation) describes a Process in which a bromine-containing ionic liquid is used as a promoter to achieve the same effect as a conventional catalyst, but this does not substantially reduce the bromine content. U.S. Pat. No. 6,790 (Method to produced aromatic dicarboxylic acids using cobalt and zirconium catalysts) uses cobalt and zirconium in a molar ratio of 7:1 as catalysts, no bromine source is used, and the terephthalic acid yield is greater than 95%; however, the catalyst is used in an amount of more than 5 wt%.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of high bromine content in the catalyst in the prior art, and the invention provides the catalyst for preparing the aromatic polycarboxylic acid by liquid-phase oxidation, which has the characteristics of low bromine consumption, high yield of target products and low impurity content.
The second technical problem to be solved by the invention is a method for preparing terephthalic acid by the liquid-phase oxidation of paraxylene by using the catalyst described in the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for preparing the aromatic polycarboxylic acid by liquid-phase oxidation comprises Co salt, Mn salt, IVB group metal salt, a bromine-containing compound and 4-substituent-N-hydroxyphthalimide, wherein the weight ratio of Co to Mn to IVB group metal to Br to 4-substituent-N-hydroxyphthalimide is 500 (200-300) to 10-50 to 1000-2000 to 50-100.
In the above technical solution, the aromatic disulfonate is selected from 4-substituent-N-hydroxyphthalimide selected from at least one of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide, 4- (1, 4-naphthoquinon-2-yl) -N-hydroxyphthalimide, and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide, preferably, the 4-substituent-N-hydroxyphthalimide is at least one selected from the group consisting of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
In the above technical solution, the bromine-containing compound is preferably at least one selected from inorganic bromides and brominated hydrocarbons.
In the above technical solution, the Co salt is preferably cobalt acetate.
In the above technical solution, the Mn salt is preferably manganese acetate.
In the above technical scheme, the group IVB metal salt is at least one of zirconium acetate and hafnium acetate.
In the above technical solution, the inorganic bromide is preferably selected from hydrogen bromide or an alkali metal bromide.
In the above technical solution, the brominated hydrocarbon is preferably at least one selected from tetrabromoethane, tetrabromopropane and tetrabromobutane. Wherein the specific substitution position of the bromine in the brominated hydrocarbon is not particularly limited. The brominated hydrocarbon is at least one of 1,1,2, 2-tetrabromoethane, 1,1,1, 2-tetrabromoethane, 1,1,2, 2-tetrabromopropane and 2,2,3, 3-tetrabromobutane.
To solve the second technical problem, the technical solution of the present invention is as follows: a process for the liquid phase oxidation of p-xylene to terephthalic acid, said process comprising reacting p-xylene with an oxidizing agent in the presence of a catalyst as described in one of the above technical problems in the presence of acetic acid as solvent to obtain terephthalic acid.
In the above technical solution, the oxidizing agent is preferably a gas containing elemental oxygen. Such as, but not limited to, oxygen, air, oxygen nitrogen mixtures, oxygen air mixtures, oxygen nitrogen mixtures, and the like.
In the technical scheme, the reaction temperature is preferably 160-250 ℃.
In the technical scheme, the reaction pressure is preferably 0.8-2.0 MPa.
In the technical scheme, the reaction time is preferably 1-5 h.
In the technical scheme, the oxidant for the reaction is preferably air, and the mass space velocity is 2-5 h-1。
The mass space velocity of each gas in the present invention is the ratio of the mass flow rate of the gas to the mass of p-xylene in the initial reaction feed.
In the products of the examples and comparative examples of the present invention, the sample to be analyzed was first completely dissolved in dimethyl sulfoxide, PX was analyzed by gas chromatography, and other substances were analyzed by High Performance Liquid Chromatography (HPLC).
Figure BDA0000939222590000031
Figure BDA0000939222590000032
Compared with the traditional catalyst, the bromine content in the catalyst of the method for preparing the terephthalic acid by oxidizing the p-xylene is reduced by more than 30 percent (the bromine content in the BP-Mitsui process is 1500ppmw), and the yield of the terephthalic acid reaches more than 97 percent.
The technical key of the method is that the IVB group metal acetate and the 4-substituent-N-hydroxyphthalimide are added into the catalyst and are mutually synergistic, so that a good effect is achieved; experiments show that: meanwhile, zirconium acetate, hafnium acetate, zinc acetate, 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide catalysts are added, so that the oxidation effect is best, the PX conversion rate is 100%, and the yield of Terephthalic Acid (TA) is as high as over 99.0%.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, 1,2, 2-tetrabromoethane and 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide) are mixed uniformlyThen adding the mixture into a high-pressure kettle, and sealing the high-pressure kettle; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmw Zr4+1000ppmw of bromine and 80ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 2 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, hafnium acetate, 1,2, 2-tetrabromoethane and 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmwHf4+1000ppmw of bromine and 80ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 3 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, 1,2, 2-tetrabromoethane and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmw Zr4+1000ppmw bromine and 80ppmw4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 4 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, hafnium acetate, 1,2, 2-tetrabromoethane and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmw Hf4+1000ppmw bromine and 80ppmw4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 5 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, hafnium acetate, 1,2, 2-tetrabromoethane and 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmwHf4+1000ppmw of bromine and 80ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product is divided intoThe analysis results are shown in Table 2.
[ example 6 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, hafnium acetate, 1,2, 2-tetrabromoethane and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmw Hf4+1000ppmw bromine and 80ppmw4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 7 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, 1,2, 2-tetrabromoethane, 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmw Zr4+1000ppmw of bromine and 40ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide, 40ppmw of 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 8 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, hafnium acetate, 1,2, 2-tetrabromoethane and 4- (tetrabromoethane)1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide) are evenly mixed and then added into an autoclave for sealing; wherein the Co content is 500ppmw based on the weight of the mixture2+、250ppmw Mn2+、25ppmw Hf4+1000ppmw of bromine and 40ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide, 40ppmw of 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
[ example 9 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
6) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate, zirconium acetate, hafnium acetate, 1,2, 2-tetrabromoethane, 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide), adding into an autoclave, and sealing; wherein the mixture contains 500ppmw Co based on the weight of the mixture2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmw Hf4+1000ppmw of bromine and 40ppmw of 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide, 40ppmw of 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide.
7) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
8) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
9) Switching with air at 186 ℃, air mass space velocity is 4h-1The reaction was carried out for 180min while maintaining the temperature.
10) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
Comparative example 1
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate and 1,1,2, 2-tetrabromoethane), adding into an autoclave, and sealing; contains 500ppmw Co based on the weight of the mixture2+、250ppmwMn2+And 1000ppmw bromine.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And start stirringThe stirrer was heated to 186 ℃ at a stirring speed of 400rpm while maintaining a pressure of 1.0 MPa.
4) Switching with air at 186 ℃ and a mass space velocity of 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6%, and CO is generated2The content is controlled to be 1.0-1.5%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
Comparative example 2
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing 80g of p-xylene, 400g of acetic acid and 20g of catalyst acetic acid solution (containing cobalt acetate, manganese acetate and 1,1,2, 2-tetrabromoethane), adding into an autoclave, and sealing; contains 500ppmw Co based on the weight of the mixture2+、250ppmwMn2+And 1500ppmw bromine.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen gas, the mass space velocity is 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and a mass space velocity of 4h-1The reaction was carried out for 180min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the product analysis result is shown in table 2.
TABLE 1
Figure BDA0000939222590000111
TABLE 2
PX(wt％) HMBA(ppmw％) 4-CBA(ppmv％) p-TA(ppmv％) TA(wt％)
Example 1 0 1213 1674 1698 99.49
Example 2 0 1105 1523 1712 99.50
Example 3 0 1120 1599 1615 99.48
Example 4 0 998 1608 1422 99.52
Example 5 0 1011 1510 1311 99.58
Example 6 0 915 1450 1250 99.68
Example 7 0 857 1438 1051 99.65
Example 8 0 900 1425 1000 99.70
Example 9 0 680 1025 758 99.88
Comparative example 1 0.08 1586 4568 3845 98.02
Comparative example 2 0.05 1656 3838 2111 98.50

Claims (8)

1. A catalyst for preparing aromatic polycarboxylic acid by liquid-phase oxidation comprises Co salt, Mn salt, IVB group metal salt, a bromine-containing compound and 4-substituent-N-hydroxyphthalimide, wherein the weight ratio of Co, Mn, IVB group metal, Br and 4-substituent-N-hydroxyphthalimide is 500 (200-300), 10-50, 1000-2000 and 50-100;
the 4-substituent-N-hydroxyphthalimide is selected from 4- (1, 4-benzoquinonyl) -N-hydroxyphthalimide and 4- (9, 10-anthraquinone-1-yl) -N-hydroxyphthalimide; the IVB group metal salt is at least one of zirconium acetate and hafnium acetate.
2. The catalyst according to claim 1, wherein the bromine-containing compound is at least one selected from the group consisting of inorganic bromides and brominated hydrocarbons.
3. The catalyst of claim 1 wherein said Co salt is cobalt acetate.
4. The catalyst of claim 1, wherein the Mn salt is manganese acetate.
5. The catalyst of claim 2, characterized in that the inorganic bromide is selected from hydrogen bromide or an alkali metal bromide.
6. The catalyst of claim 2, wherein the brominated hydrocarbon is at least one member selected from the group consisting of tetrabromoethane, tetrabromopropane, and tetrabromobutane.
7. A method for preparing terephthalic acid by liquid-phase oxidation of p-xylene, which comprises reacting p-xylene with an oxidant in the presence of a catalyst according to any one of claims 1 to 6 in the presence of acetic acid as a solvent to obtain terephthalic acid.
8. The method of claim 7, wherein the oxidizing agent is an elemental oxygen-containing gas.
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