CN107175128A - Liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid - Google Patents

Liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid Download PDF

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CN107175128A
CN107175128A CN201610139914.5A CN201610139914A CN107175128A CN 107175128 A CN107175128 A CN 107175128A CN 201610139914 A CN201610139914 A CN 201610139914A CN 107175128 A CN107175128 A CN 107175128A
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catalyst
acid
salt
liquid phase
catalyst according
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CN107175128B (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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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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))
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to the catalyst that liquid phase oxidation prepares aromatic multi-carboxy acid, the problem of bromine consumption is too high in catalyst present in prior art is mainly solved.Catalyst includes Co salt, Mn salt, Group IVB metal salt, bromine-containing compound and 4 substituent N hydroxyphthalimides, wherein Co by weight:Mn:Group IVB metal:Br:4 substituent N hydroxyphthalimides are 500:(200~300):(10~50):(1000~2000):The technical scheme of (50~100), preferably solves the technical problem, is prepared available for paraxylene liquid phase oxidation in Production of Terephthalic Acid.

Description

Liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid
Technical field
The present invention relates to the catalyst that liquid phase oxidation prepares aromatic multi-carboxy acid.
Background technology
P-phthalic acid, is commonly called as PTA, is the base stock for synthesizing polyethylene terephthalate (PET), its Demand sustainable growth, it is contemplated that 2015, global PTA demand is up to 50,000,000 tons.At present, PTA life Production technology is mainly paraxylene (PX) oxidation of Amoco-MC companies exploitation, hydrofinishing two-step process, oxygen Change step and use Co-Mn-Br antigravity systems, using acetic acid as solvent；Hydrogenation is main by terephthalaldehydic acid (4-CBA) Addition is p-methylbenzoic acid (p-TA), is then centrifuged for, water elution is removed.
PTA production technologies form Amoco, three wells, tetra- kinds of main patents of ICI, Eastman in evolution Technology.The common ground of these four technologies be use Amoco-MC liquid phase catalytic oxidation methods, catalyst be cobalt-manganese- Bromine system, solvent is acetic acid, is a difference in that polytechnic oxidizing reaction temperature is different (from 160 DEG C to 225 DEG C), phase Process conditions, reactor types, the flow scheme design answered are also different.ICI and Amoco reaction temperature highests, three wells - Amoco temperature is placed in the middle, and Eastman is minimum, is referred to as high-temperature oxydation, the oxidation of middle temperature and low temperature oxidation technology.
No matter which kind of technique is used, is required for bromine as co-catalyst, bromine corrosivity is very strong, especially under the high temperature conditions, Therefore all reactors are all using expensive titanium；Meanwhile, excessive bromine can cause the generation of side reaction, cause solvent With the loss of raw material.The scholar of lot of domestic and international replaces in research reduction bromine content or completely bromine.United States Patent (USP) US7985875(Process for preparing aromatic polycarboxylic acid by liquid phase oxidation) A kind of effect using brominated ionic liquid as bromine source as co-catalyst acquirement as traditional catalyst is described, but This is without the content for fundamentally reducing bromine.United States Patent (USP) US6153790 (Method to produce aromatic Dicarboxylic acids using cobalt and zirconium catalysts) use mol ratio 7:1 cobalt and zirconium are as urging Agent, use bromine source useless, yield of terephthalic acid is more than 95%；But catalyst amount is big, more than 5wt%.
The content of the invention
One of technical problems to be solved by the invention are the problem of bromine content are high in catalyst present in prior art, are carried Bromine consumption is low, target product yield is high, impurity contains in the catalyst of feed flow phase oxidation preparation aromatic multi-carboxy acid, the catalyst The characteristics of measuring low.
The two of the technical problems to be solved by the invention are the paraxylene using one of the above-mentioned technical problem catalyst The method that liquid phase oxidation prepares terephthalic acid (TPA).
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Liquid phase oxidation prepares aromatic multi-carboxy acid Catalyst, described catalyst includes Co salt, Mn salt, Group IVB metal salt, bromine-containing compound and 4- substituents - HP, wherein Co by weight:Mn:Group IVB metal:Br:4- substituent-N- hydroxyls neighbour's benzene Dicarboximide is 500:(200~300):(10~50):(1000~2000):(50~100).
In above-mentioned technical proposal, described aromatic series disulfonate is selected from 4- substituents-HP choosing From 4- (1,4- benzoquinonyls)-HP, 4- (1,4- naphthoquinones -2- bases)-HP, At least one of 4- (9,10- anthraquinone -1- bases)-HP, preferably 4- substituents-N- hydroxyls neighbour's benzene two Carboximide is selected from the adjacent benzene two of 4- (1,4- benzoquinonyls)-HP, 4- (9,10- anthraquinone -1- bases)-N- hydroxyls At least one of carboximide.
In above-mentioned technical proposal, the bromine-containing compound preferably is selected from least one of inorganic bromide and bromo-hydrocarbons.
In above-mentioned technical proposal, the Co salt is preferably cobalt acetate.
In above-mentioned technical proposal, the Mn salt is preferably manganese acetate.
In above-mentioned technical proposal, the Group IVB metal salt is at least one of acetic acid zirconium, acetic acid hafnium.
In above-mentioned technical proposal, the inorganic bromide preferably is selected from hydrogen bromide or alkali metal bromide.
In above-mentioned technical proposal, the bromo-hydrocarbons preferably is selected from least one of tetrabromoethane, four N-Propyl Bromides, tetrabromobutane. The specific the position of substitution of wherein described bromine in bromo-hydrocarbons is not particularly limited.Described bromo-hydrocarbons is for example but not limited to At least one of 1,1,2,2- tetrabromoethanes, 1,1,1,2- tetrabromoethanes, the N-Propyl Bromides of 1,1,2,2- tetra-, 2,2,3,3- tetrabromobutanes.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Paraxylene liquid phase oxidation is prepared to benzene two The method of formic acid, described method includes paraxylene using acetic acid as solvent, in any one of one of above-mentioned technical problem In the presence of the catalyst terephthalic acid (TPA) is obtained with oxidant reaction.
In above-mentioned technical proposal, described oxidant is preferably the gas of the oxygen containing simple substance.For example it is but not limited to oxygen, sky Gas, oxygen-nitrogen mixture, oxygen air mixture, oxygen-nitrogen mixture etc..
In above-mentioned technical proposal, the temperature of the reaction is preferably 160~250 DEG C.
In above-mentioned technical proposal, the pressure of the reaction is preferably 0.8~2.0MPa.
In above-mentioned technical proposal, the time of the reaction is preferably 1~5h.
In above-mentioned technical proposal, the oxidant of the reaction is preferably air, and mass space velocity is 2~5h-1。
In the present invention mass space velocity of various gases be in gas mass velocity and initial reaction raw material paraxylene quality it Than.
The product of the embodiment of the present invention and comparative example, the sample that will be analyzed first is completely dissolved into dimethyl sulfoxide (DMSO), and PX is adopted With gas chromatographic analysis, other materials are analyzed using high performance liquid chromatography (HPLC).
Bromine consumption declines compared with traditional catalyst in the method that p xylene oxidation of the present invention prepares terephthalic acid (TPA), catalyst More than 30% (the well technique bromine contents of BP- tri- are 1500ppmw), the yield of terephthalic acid (TPA) reaches more than 97%.
The key problem in technology of the inventive method is catalyst addition Group IVB metal acetate salt of the present invention and 4- substituent-N- hydroxyls Base phthalimide, mutually synergy, achieve preferable effect；Experiment shows：While addition acetic acid zirconium, Acetic acid hafnium, zinc acetate, 4- (1,4- benzoquinonyls)-HP, 4- (9,10- anthraquinone -1- bases)-N- hydroxyls are adjacent BIDA catalyst oxidation effectiveness preferably, PX conversion ratios 100%, terephthalic acid (TPA) (TA) high income is up to 99.0% More than.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP) it is well mixed after plus Enter autoclave, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、 25ppmw Zr4+, 1000ppmw bromines and 80ppmw 4- (1,4- benzoquinonyls)-HP.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 2】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Hafnium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP) it is well mixed after add Autoclave, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、25ppmw Hf4+, 1000ppmw bromines and 80ppmw 4- (1,4- benzoquinonyls)-HP.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 3】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, 1,1,2,2- tetrabromoethanes, 4- (9,10- anthraquinone -1- bases)-HP) it is well mixed after Autoclave is added, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、 25ppmw Zr4+, 1000ppmw bromines and 80ppmw 4- (9,10- anthraquinone -1- bases)-N- hydroxyls phthalyl it is sub- Amine.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 4】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Hafnium, 1,1,2,2- tetrabromoethanes, 4- (9,10- anthraquinone -1- bases)-HP) it is well mixed after Autoclave is added, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、 25ppmw Hf4+, 1000ppmw bromines and 80ppmw 4- (9,10- anthraquinone -1- bases)-N- hydroxyls phthalyl it is sub- Amine.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 5】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, acetic acid hafnium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP) mixing Autoclave is added after uniform, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmw Hf4+, 1000ppmw bromines and 80ppmw 4- (1,4- benzoquinones Base)-HP.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 6】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, acetic acid hafnium, 1,1,2,2- tetrabromoethanes, 4- (9,10- anthraquinone -1- bases)-HP) it is mixed Uniform rear addition autoclave is closed, it is closed；Wherein in terms of mixture weight, Co containing 500ppmw2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmw Hf4+, 1000ppmw bromines and 80ppmw 4- (9,10- anthraquinones -1- Base)-HP.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 7】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP, 4- (9,10- anthraquinones -1- Base)-HP) it is well mixed after add autoclave, it is closed；Wherein with mixture weight Gauge, Co containing 500ppmw2+、250ppmw Mn2+、25ppmw Zr4+, 1000ppmw bromines and 40ppmw The adjacent benzene of 4- (1,4- benzoquinonyls)-HP, 40ppmw4- (9,10- anthraquinone -1- bases)-N- hydroxyls Dicarboximide.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 8】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Hafnium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP, 4- (9,10- anthraquinones -1- Base)-HP) it is well mixed after add autoclave, it is closed；Wherein with mixture weight Gauge, Co containing 500ppmw2+、250ppmw Mn2+、25ppmw Hf4+, 1000ppmw bromines and 40ppmw The adjacent benzene of 4- (1,4- benzoquinonyls)-HP, 40ppmw 4- (9,10- anthraquinone -1- bases)-N- hydroxyls Dicarboximide.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Embodiment 9】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
6) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, acetic acid Zirconium, acetic acid hafnium, 1,1,2,2- tetrabromoethanes, 4- (1,4- benzoquinonyls)-HP, 4- (9,10- Anthraquinone -1- bases)-HP) it is well mixed after add autoclave, it is closed；Wherein with mixed Polymer weight, Co containing 500ppmw2+、250ppmw Mn2+、12.5ppmw Zr4+、12.5ppmw Hf4+、 1000ppmw bromines and 40ppmw 4- (1,4- benzoquinonyls)-HP, 40ppmw 4- (9,10- anthraquinone -1- bases)-HP.
7) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
8) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
9) switched at 186 DEG C with air, air quality air speed is 4h-1, the constant reaction 180min of keeping temperature.
10) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl Sulfoxide is completely dissolved solid, takes out and uses the unreacted paraxylene of gas chromatographic analysis, high performance liquid chromatography Analyze terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and Terephthalaldehydic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Comparative example 1】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, 1,1,2,2- Tetrabromoethane) it is well mixed after add autoclave, it is closed；In terms of mixture weight, wherein containing 500ppmw Co2+、250ppmw Mn2+With 1000ppmw bromines.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, mass space velocity is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6%, CO2Content control 1.0~1.5% it Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
【Comparative example 2】
React with magnetic stirring apparatus, air shooter, reflux condensing tube, thermocouple, the 1000ml of rupture disk titanium Carried out in material autoclave, mixing speed is 400rpm, is heated by circulating hot oil.Reactions steps are as follows：
1) 80g paraxylene, 400g acetic acid and 20g catalyst acetic acids solution (are contained into cobalt acetate, manganese acetate, 1,1,2,2- Tetrabromoethane) it is well mixed after add autoclave, it is closed；In terms of mixture weight, wherein containing 500ppmw Co2+、250ppmw Mn2+With 1500ppmw bromines.
2) nitrogen for adding 2.0MPa carries out 30min air seal test, and pressure, which declines, in 30min is not more than 0.1MPa To be qualified.
3) nitrogen is added, mass space velocity is 4h-1, and agitator is started, stir speed (S.S.) is 400rpm, is warming up to 186 DEG C, It is 1.0MPa to keep pressure simultaneously.
4) switched at 186 DEG C with air, mass space velocity is 4h-1, the constant reaction 180min of keeping temperature.
5) nitrogen is switched to again after completely reacted, room temperature is cooled to, and reactor pressure release to normal pressure adds dimethyl sulfoxide (DMSO) Solid is completely dissolved, takes out and uses the unreacted paraxylene of gas chromatographic analysis, efficient liquid phase chromatographic analysis Terephthalic acid (TPA) (TA), p-methylbenzoic acid (p-TA), to first hydroxybenzoic acid (HMBA) and to aldehyde Yl benzoic acid (4-CBA).
Tail gas uses infrared on line analysis, and tail Control for Oxygen Content is between 3~6wt%, CO2Content is controlled in 1.0~1.5wt% Between, catalyst formulation is shown in Table 1, and product analysis the results are shown in Table 2.
Table 1
Table 2
PX (wt%) HMBA (ppmw%) 4-CBA (ppmv%) P-TA (ppmv%) TA (wt%)
Embodiment 1 0 1213 1674 1698 99.49
Embodiment 2 0 1105 1523 1712 99.50
Embodiment 3 0 1120 1599 1615 99.48
Embodiment 4 0 998 1608 1422 99.52
Embodiment 5 0 1011 1510 1311 99.58
Embodiment 6 0 915 1450 1250 99.68
Embodiment 7 0 857 1438 1051 99.65
Embodiment 8 0 900 1425 1000 99.70
Embodiment 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 (10)

1. liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid, including Co salt, Mn salt, Group IVB metal salt, brominated chemical combination Thing and 4- substituents-HP, wherein Co by weight:Mn:Group IVB metal:Br:4- takes Dai Ji-HP is 500:(200~300):(10~50):(1000~2000):(50~100).
2. catalyst according to claim 1, it is characterized in that described 4- substituents-HP choosing It is sub- from 4- (1,4- benzoquinonyls)-HP, 4- (1,4- naphthoquinones -2- bases)-N- hydroxyls phthalyl At least one of amine, 4- (9,10- anthraquinone -1- bases)-HP.
3. catalyst according to claim 1, it is characterized in that the bromine-containing compound is selected from inorganic bromide and bromo-hydrocarbons At least one of.
4. catalyst according to claim 1, it is characterized in that the Co salt is cobalt acetate.
5. catalyst according to claim 1, it is characterized in that the Mn salt is manganese acetate.
6. catalyst according to claim 1, it is characterized in that the Group IVB metal salt be in acetic acid zirconium, acetic acid hafnium extremely Few one kind.
7. catalyst according to claim 3, it is characterized in that the inorganic bromide is selected from hydrogen bromide or alkali metal bromination Thing.
8. catalyst according to claim 3, it is characterized in that the bromo-hydrocarbons is selected from tetrabromoethane, four N-Propyl Bromides, four At least one of NBB.
9. the method that paraxylene liquid phase oxidation prepares terephthalic acid (TPA), described method includes paraxylene using acetic acid to be molten Agent, in the presence of catalyst any one of claim 1~8 with oxidant reaction obtain terephthalic acid (TPA).
10. method according to claim 9, it is characterised in that described oxidant is the gas of the oxygen containing simple substance.
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CN113617363A (en) * 2021-08-30 2021-11-09 武汉强丰新特科技有限公司 Supported multi-metal oxide catalyst and preparation method and application thereof

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CN113617363B (en) * 2021-08-30 2023-03-17 武汉强丰新特科技有限公司 Supported multi-metal oxide catalyst and preparation method and application thereof

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