CN117964478A - Preparation method of aromatic polycarboxylic acid or anhydride - Google Patents
Preparation method of aromatic polycarboxylic acid or anhydride Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 13
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000047 product Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000010899 nucleation Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 239000007858 starting material Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- -1 halide anion Chemical class 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 239000011344 liquid material Substances 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
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- 238000006243 chemical reaction Methods 0.000 description 61
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- 238000003756 stirring Methods 0.000 description 12
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- 239000012265 solid product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 7
- 229910001069 Ti alloy Inorganic materials 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
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- 229910052794 bromium Inorganic materials 0.000 description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 6
- 238000012806 monitoring device Methods 0.000 description 6
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- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical group C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229910001437 manganese ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TWNICQBDBDUTPA-UHFFFAOYSA-N 4-[(3,4-dimethylphenyl)methyl]-1,2-dimethylbenzene Chemical compound C1=C(C)C(C)=CC=C1CC1=CC=C(C)C(C)=C1 TWNICQBDBDUTPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present application provides a process for preparing an aromatic polycarboxylic acid or anhydride, said process comprising: step one: oxidizing the feedstock compound with a gaseous oxidant in the presence of a catalyst to produce a product mixture comprising an aromatic polycarboxylic acid; step two: seeding the product mixture with seed crystals of the previously prepared 1 st positional isomer product, such that the corresponding 1 st positional isomer product contained in the product mixture precipitates; step three: the 2 nd to nth positional isomer products are separated and recovered. The present application does not need to use high-purity raw materials, but uses a mixture of various positional isomers as raw materials, and simultaneously prepares and obtains various aromatic polycarboxylic acids or anhydrides in a low-cost and convenient manner.
Description
Technical Field
The present application relates to the field of chemical synthesis, and more particularly to a method for synthesizing aromatic polycarboxylic acids or anhydrides.
Background
Aromatic carboxylic acids and carboxylic anhydrides are very important industrial materials widely used for the synthesis of advanced materials such as polyesters, polyamides, etc., and one representative example is Benzophenone Tetracarboxylic Acid (BTA) and Benzophenone Tetracarboxylic Dianhydride (BTDA). FIG. 1 shows a currently existing method for synthesizing 3,3', 4' -BTDA, in short, the prior art method takes o-xylene as a raw material, and makes it undergo the condensation reaction with aldehyde (such as formaldehyde or acetaldehyde) to form 3,3', 4' -tetramethyl diphenylmethane (3, 3', 4' -TMDM), then oxidizing 3,3', 4' -TMDM into 3,3', 4' -benzophenone tetracarboxylic acid (3, 3', 4' -BTA) by using a liquid oxidant such as nitric acid, and finally carrying out an anhydration reaction according to the requirement to generate 3,3', 4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -BTDA).
However, the above prior art processes have more than one significant disadvantage. The first major drawback is that in the prior art, dilute nitric acid is mainly used as an oxidant, the process is required to be carried out under higher pressure and temperature, the product mixture contains a large amount of nitrogen-containing impurities, which are difficult to refine, and a large amount of nitrogen oxides can be discharged, and a large amount of nitrate waste acid, waste water and the like are generated, so that environmental protection and post-treatment pressure are caused.
A second major drawback is that the oxidation reaction is inefficient, and the conversion and yield of the target product are not always satisfactory, and despite numerous process improvements, the product yield is not always truly satisfactory. For this reason, one has to carry out purification operations after the oxidation reaction, which further increases the complexity and cost of the process.
A third significant drawback is that the products formed by the condensation of ortho-xylene with aldehydes are essentially three in nature, as shown by the structural formulas in the upper row of fig. 2, from left to right, including 3,3',4,4' -tetramethyl diphenylmethane (3, 3',4' -TMDM), 2, 3',4' -tetramethyl diphenylmethane (2, 3',4' -TMDM), 2', 3' -tetramethyldiphenyl methane (2, 2', 3' -TMDM). After oxidation of these three positional isomers, three positional isomers are formed as shown in the lower row of fig. 2 from left to right, respectively: 3,3',4' -benzophenone tetracarboxylic acid (3, 3',4' -TBA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -TBA), 2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -TBA), during the oxidation reaction, the three intermediate raw materials can have serious mutual influence, the yield of the target product is further obviously reduced, and the purification and separation of the target product are also extremely difficult problems. The prior art is to separate a mixture containing a plurality of TMDM positional isomers before the oxidation reaction to obtain a TMDM isomer with high purity, and then to perform the oxidation reaction to obtain the corresponding TBA isomer. However, because of the extremely close physical parameters of the three isomers of TMDM, it is difficult to purify by conventional separation means such as crystallization, rectification, extraction, etc. The above requirement for a single isomer of high purity further increases the complexity and cost of the synthesis process.
In addition, the prior art has the problems of more catalyst waste, longer reaction time, complex process route and the like, and needs to be solved.
Disclosure of Invention
The present inventors have made intensive studies with respect to the above problems, unexpectedly developed the method of the present application, and effectively solve the problems of the prior art which have been rapidly solved for a long time.
The present application provides a process for preparing an aromatic polycarboxylic acid or anhydride, said process comprising:
Step one: subjecting a starting compound, which is a compound containing at least two benzene rings and two or more C1-C6 alkyl substituents and which comprises a mixture of N positional isomer starting materials, which is also a mixture comprising N positional isomer products, N being an integer not less than 2, to an oxidation reaction using a gaseous oxidant in the presence of a catalyst to produce a product mixture comprising an aromatic polycarboxylic acid;
Step two: seeding the product mixture with seed crystals of the previously prepared 1 st positional isomer product, such that the corresponding 1 st positional isomer product contained in the product mixture precipitates;
step three: the 2 nd to nth positional isomer products are separated and recovered.
According to one embodiment of the present application, the third step includes: seeding the product mixture with seed crystals of the previously prepared 2 nd positional isomer product to precipitate the corresponding 2 nd positional isomer product contained in the product mixture, and
The 3 rd to nth positional isomer products are separated and recovered.
According to another embodiment of the application, the method further comprises the step four: the N positional isomer products are converted from carboxylic acids to anhydrides, respectively.
According to another embodiment of the application, the starting compound is a mixture of starting materials comprising the following positional isomers: 3,3',4' -tetramethyldiphenyl methane (3, 3',4' -TMDM), 2, 3',4' -tetramethyldiphenyl methane (2, 3',4' -TMDM) and 2,2', 3' -tetramethyldiphenyl methane (2, 2', 3' -TMDM). According to another embodiment of the application, the product mixture is a mixture comprising the following positional isomer products: 3,3',4' -benzophenone tetracarboxylic acid (3, 3',4' -BTA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -BTA) and 2,2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -BTA).
According to another embodiment of the application, the gaseous oxidizing agent is selected from at least one of the following: air, oxygen.
According to another embodiment of the application, prior to step one, an alkylbenzene comprising at least two C1-C6 alkyl substituents is subjected to a condensation reaction with an aldehyde to form the starting compound.
According to another embodiment of the present application, the oxidation reaction of step one is carried out at a temperature of 185 ℃ to 230 ℃.
According to another embodiment of the application, the catalyst comprises a metal cation and a halogen anion, the metal being a cation of one or more elements selected from the group consisting of: cobalt, manganese, molybdenum, nickel, copper, zinc; the halide anions are chloride, bromide, or a combination thereof. According to another embodiment of the present application, the metal cation is present in an amount of 50 to 5000ppm and the halogen anion is present in an amount of 100 to 10000ppm based on the total weight of all liquid and solid materials in the oxidation reaction of the first step.
According to another embodiment of the application, during the oxidation reaction of step one, the oxygen concentration in the gaseous oxidant after the oxidation reaction is monitored and the total concentration of oxygen is kept below 3% by volume.
According to another embodiment of the application, during the oxidation reaction of step one, the flow rate of the gaseous oxidizing agent is controlled at the following level: 0.1-1X 10 6 NL/1000 g of starting compound per minute.
The method, apparatus and device of the present application are further described in the detailed description section below with reference to the accompanying drawings.
Drawings
FIG. 1 shows a prior art process for synthesizing aromatic polycarboxylic acids/anhydrides;
FIG. 2 shows various positional isomers of TMDM and TBA.
Detailed Description
"Range" is disclosed herein in the form of lower and upper limits. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges that can be defined in this way are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for specific parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values.
In the present application, all the embodiments mentioned herein and the preferred embodiments may be combined with each other to form new technical solutions, if not specifically described.
In the present application, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically stated.
In the present application, the term "comprising" as referred to herein means open or closed unless otherwise specified. For example, the term "comprising" may mean that other components not listed may also be included, or that only listed components may be included.
One of the points of the present invention is that a raw material mixture containing two or more kinds of positional isomer raw materials is used, an oxidation reaction is carried out using a gaseous oxidizing agent to produce a product mixture containing two or more kinds of positional isomer products, and various positional isomers in the products are separated by a separation technique including a seed precipitation method to obtain various positional isomer products of high purity in high yield.
According to one embodiment of the present application, the starting materials used are compounds containing at least two benzene rings and two or more C1-C6 alkyl substituents, including the various positional isomers thereof. For example, two, three or four benzene rings may be included in the compound, which may be fused to each other or covalently linked through a C1-C6 alkylene group. The alkyl substituents may include methyl, ethyl, propyl, butyl, pentyl or hexyl, and the number of substituents may be from 2 to 10, for example from 2 to 8, or from 2 to 6, or from 4 to 6.
According to one embodiment of the present application, after undergoing the oxidation reaction, the alkyl group attached to the benzene ring is oxidized to a carboxyl group, to obtain the corresponding aromatic polycarboxylic acid. According to another embodiment of the application, the aromatic polycarboxylic acid may be subsequently subjected to an anhydrization reaction such that adjacent carboxyl groups on the benzene ring form anhydrides.
According to another embodiment of the present application, when two or more benzene rings are linked through an alkylene group, the alkylene group is oxidized to form a ketone group.
According to one embodiment of the present application, the isomers of the process of the present application as starting materials include 3,3',4' -tetramethyldiphenylmethane (3, 3',4,4' -TMDM), 2, 3',4' -tetramethyl diphenylmethane (2, 3',4' -TMDM), 2', 3' -tetramethyl diphenylmethane (2, 2', 3' -TMDM); after undergoing an oxidation reaction, 3',4' -benzophenone tetracarboxylic acid (3, 3',4' -BTA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -BTA) and 2,2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -BTA).
According to one embodiment of the application, the compound mixture having two or more benzene rings and at least two alkyl substituents used as starting material in the process of the application is prepared by condensation of C1-C6 alkyl-substituted benzene with aldehydes. According to one embodiment, it is prepared by condensation of xylenes (e.g., ortho-xylene, meta-xylene, para-xylene, or a combination of two or more thereof) with formaldehyde or acetaldehyde. The products produced include mixtures of various positional isomers (such as those described above) that can be used in the oxidation reaction of the process of the present application without additional separation.
According to a specific embodiment, the feedstock used in the present invention comprises 3,3',4' -tetramethyl diphenylmethane (3, 3',4' -TMDM), 2, 3',4' -tetramethyldiphenyl methane (2, 3',4' -TMDM) and 2,2', 3' -tetramethyldiphenyl methane (2, 2', 3' -TMDM).
The 3,3',4' -TMDM is present in an amount of from 30 to 70 mole%, for example from 35 to 65 mole%, alternatively from 40 to 60 mole%, alternatively from 45 to 58 mole%, alternatively from 50 to 55 mole%, based on the total molar amount of the starting materials, or within the numerical range obtained by combining any two of the above endpoints with each other. The 2, 3',4' -TMDM is present in an amount of from 10 to 50 mole%, such as from 15 to 45 mole%, or from 20 to 40 mole%, or from 25 to 48 mole%, or from 30 to 45 mole%, or from 35 to 42 mole%, or from 38 to 40 mole%, or a combination of any two of the above, based on the total molar amount of the starting materials. The 2,2', 3' -TMDM is present in an amount of 1 to 20 mole%, such as 2 to 15 mole%, or 3 to 12 mole%, or 4 to 10 mole%, or 5 to 9 mole%, or 6 to 8 mole%, or 6 to 7 mole%, or a combination of any two of the above endpoints, based on the total molar amount of the starting materials.
According to one embodiment of the application, the gaseous oxidizing agent is selected from at least one of the following: air, oxygen; preferably air. Controlling the flow rate of the gaseous oxidant such that the flow rate of the gaseous oxidant is controlled at the following level: 0.1 to 1X 10 6 NL/1000 g of starting compound per minute, for example 1 to 1X 10 5 NL/1000 g of starting compound per minute, or 10 to 1X 10 4 NL/1000 g of starting compound per minute, or 100 to 8000NL/1000 g of starting compound per minute, or 200 to 6000NL/1000 g of starting compound per minute, or 500 to 5000NL/1000 g of starting compound per minute, or 800 to 3000NL/1000 g of starting compound per minute, or 1000 to 2000NL/1000 g of starting compound per minute, or within a numerical range obtained by combining any two of the end values mentioned above with each other.
According to one embodiment of the application, during the oxidation reaction of said step one, the oxygen concentration in the gaseous oxidizing agent after the oxidation reaction is monitored and the concentration of oxygen in the gaseous stream exiting after the oxidation reaction is kept below 3% by volume.
According to another embodiment of the application, the oxidation reaction is judged to be complete when the concentration of oxygen in the gas stream discharged after undergoing the oxidation reaction is observed to be higher than 7% by volume.
The oxidation reaction according to the application can be carried out in any reactor which is resistant to acid corrosion, for example in ceramic reactors, glass reactors, stainless steel reactors, metal reactors with polyethylene or polytetrafluoroethylene lining, titanium alloys, zinc alloy reactors.
According to one embodiment of the application, the temperature of the oxidation reaction is 185-230 ℃, for example 190-225 ℃, or 195-220 ℃, or 200-215 ℃, or 205-210 ℃, or within the range of values obtained by combining any two of the above endpoints with each other.
According to one embodiment of the application, the catalyst comprises a metal cation and a halogen anion. The metal is a cation of one or more elements selected from the group consisting of: cobalt, manganese, molybdenum, nickel, copper, zinc; cobalt and manganese cations are preferred. The halide anions are chloride, bromide, or a combination thereof; preferably bromide. According to one embodiment of the present application, the metal cation may be added in the form of various salts thereof, such as chloride salts, bromide salts, nitrate salts, sulfate salts, phosphate salts, formate salts, acetate salts, and the like; the chloride and bromide ions may be added in the form of their salts with various counter cations or haloalkanes, such as potassium chloride, sodium chloride, potassium bromide, sodium bromide, ethyl chloride, tetrachloroethane, ethyl bromide, tetrabromoethane, and the like.
The total content of metal cations is 50 to 5000ppm, for example 100 to 4000ppm, or 200 to 3000ppm, or 300 to 2000ppm, or 400 to 1000ppm, or 500 to 800ppm, or within the numerical range obtained by combining any two of the above endpoints, based on the total weight of all liquid and solid materials in the oxidation reaction of the first step; the halogen anion content is 100-10000ppm, such as 200-9000ppm, or 300-8000ppm, or 400-7000ppm, or 500-6000ppm, or 600-5000ppm, or 700-4000ppm, or 800-3000ppm, or 900-2000ppm, or within a numerical range obtained by combining any two of the above-mentioned end values with each other.
The catalyst contains cobalt ions and manganese ions, wherein the content of the cobalt ions is 100-3000ppm, such as 200-2500, or 300-2000ppm, or 400-1800ppm, or 800-1600ppm, or 1000-1200ppm, or a numerical range obtained by combining any two end values of the cobalt ions with each other based on the total weight of all liquid and solid materials in the oxidation reaction of the first step; the manganese ion content is 100-3000ppm, such as 200-2500, or 300-2000ppm, or 400-1800ppm, or 800-1600ppm, or 1000-1200ppm, or within the range of values obtained by combining any two of the above endpoints with each other.
According to one embodiment of the application, the oxidation reaction is continued for more than 0.5-12 hours, for example 0.8-6 hours, or 1-4 hours, or 1.5-2 hours, or within the numerical range obtained by combining any two of the above endpoints with each other. According to a preferred embodiment of the application, the oxidation reaction duration may be in the range of 0.5-1.5 hours, much shorter than the duration of the prior art process, and yields superior to the prior art may be achieved.
According to an embodiment of the present application, organic matters, such as organic acids, are used as solvents for the reaction during the oxidation reaction, and examples of the organic solvents may include anhydrous formic acid and glacial acetic acid, for example. According to one embodiment of the application, the molar ratio of the total molar amount of the starting materials of the positional isomers to the solvent is from 1:1 to 1:50, and may be, for example, from 1:2 to 1:40, or from 1:3 to 1:30, or from 1:4 to 1:25, or from 1:5 to 1:20, or from 1:6 to 1:16, or from 1:8 to 1:15, or from 1:10 to 1:12, or within the numerical range obtained by combining any two of the above endpoints with each other.
According to one embodiment of the application, after the oxidation reaction has been carried out, the resulting product mixture comprises a plurality of positional isomer products, as described above, for example comprising 3,3',4,4' -benzophenone tetracarboxylic acid (3, 3',4' -BTA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -BTA) and 2,2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -BTA).
The product mixture is first subjected to a seeding-precipitation operation to separate the first positional isomer, e.g. 3,3', 4' -BTA. In this operation, a small amount (e.g., 0.001 g to 0.5 g, or 0.01 to 0.4 g, or 0.05 to 0.3 g, or 0.1 to 0.2 g) of crystals of a high purity first positional isomer product (e.g., 3', 4' -BTA) prepared in advance is added to the product mixture as seed crystals, and left for a period of time such that the corresponding first positional isomer product (e.g., 3', 4' -BTA) is precipitated from the product mixture. The rest time may be 0.5 to 6 hours, for example 1 to 4 hours, or 2 to 3 hours.
After undergoing the seeding-precipitation step described above, the remaining product mixture may be subjected to further separation steps (e.g., distillation, crystallization, fractionation, recrystallization, etc.) to separate the remaining second to nth isomer products therein, N being an integer greater than or equal to 2, e.g., N may be an integer of 2,3, 4, 5, or 6.
According to one non-limiting embodiment, the product mixture from which the first positional isomer has been removed may also be subjected to a second seeding-precipitation operation, a third seeding-precipitation operation, and up to the N-1 th seeding precipitation operation. For example, the second seeding-precipitation operation may be one in which crystals of the second positional isomer prepared in advance are added as seed crystals, e.g., 2, 3',4' -BTA is added to the product mixture from which the first positional isomer has been removed, to effect precipitation and separation of 2, 3',4' -BTA.
According to one embodiment of the present application, highly pure 3,3',4' -benzophenone tetracarboxylic acid (3, 3',4' -BTA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -BTA) and 2,2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -BTA), the respective molar yields of these three products can reach 80-90%, which is far higher than the prior art.
According to another embodiment of the application, the one or more positional isomer products isolated by the process of the application can reach a purity of 98% or more, or 99% or more, without further purification by rectification.
In the following examples, the excellent effects achieved by the process of the present application are specifically illustrated. The purpose of which is to provide a better understanding of the present application. It should be understood that these embodiments are merely illustrative and not limiting. The reagents used in the examples were commercially available as usual unless otherwise indicated. The methods and conditions used in the examples are conventional methods and conditions unless otherwise specified.
Examples
The salts used in the examples below were all of the commercially available analytical grade.
The mixture of o-xylene and formaldehyde in a molar ratio of 2:1 is heated to 130-136 ℃ and reacted with 67% sulfuric acid as a catalyst for 4 hours to synthesize a product mixture characterized by high performance liquid chromatography comprising 55 mole% 3,3',4' -TMDM,38 mole% 2, 3',4' -TMDM and 7 mole% 2,2', 3' -TMDM.
The product mixtures were used as reaction raw materials in examples 1-6 and comparative examples 1-2 below.
Example 1
120 G of the reaction raw material, 600 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (400 ppm, based on cobalt content), manganese acetate tetrahydrate (400 ppm, based on manganese content) and tetrabromoethane (1600 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.0MPa, after which the temperature was raised and maintained at 185 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 20 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction was continued for 1 hour, the oxygen concentration in the tail gas was increased to 7% or more. At the moment, stopping the reaction, cooling and decompressing, and discharging the reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.1 g of 3,3', 4' -BTA seed prepared in advance was added thereto, and left standing for 2 hours, during which time a crystalline product was precipitated. And carrying out suction filtration and separation on the product, washing the solid with deionized water for three times, and drying to obtain a crystal product. Gas chromatography analysis showed that it was a3, 3', 4' -BTA product of 99.17% purity with a molar yield of 86.81%.
The separated liquid phase is distilled for 1 hour at 125 ℃, or a rotary evaporator is distilled for 1 hour at 70 ℃ under the pressure of minus 0.095MPa to separate acetic acid, the concentrated solution is kept stand for 3 hours at room temperature to separate out solid, the solid is filtered and separated by suction, the solid is washed three times by deionized water, and the solid product is obtained after drying, and the gas chromatographic analysis shows that the solid product is a2, 3',4' -BTA product with the purity of 81.56 percent, and the molar yield is 83.24 percent.
Example two
120 G of the reaction raw material, 600 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (800 ppm, based on cobalt content), manganese acetate tetrahydrate (800 ppm, based on manganese content) and tetrabromoethane (3200 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.0MPa, after which the temperature was raised and maintained at 185 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 20 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction was continued for 1 hour, the oxygen concentration in the tail gas was increased to 7% or more. At the moment, stopping the reaction, cooling and decompressing, and discharging the reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.15 g of 3,3', 4' -BTA seed prepared in advance was added thereto, and left standing for 2 hours, during which time a crystalline product was precipitated. And carrying out suction filtration and separation on the product, washing the solid with deionized water for three times, and drying to obtain a crystal product. Gas chromatography analysis showed that it was a 3,3', 4' -BTA product of 99.23% purity with a molar yield of 89.35%.
The separated liquid phase is distilled for 1 hour at 125 ℃, or a rotary evaporator is distilled for 1 hour at 70 ℃ under the pressure of minus 0.095MPa to separate acetic acid, the concentrated solution is kept stand for 3 hours at room temperature to separate out solid, the solid is filtered and separated by suction, the solid is washed three times by deionized water, and the solid product is obtained after drying, and the gas chromatographic analysis shows that the solid product is 2, 3',4' -BTA with the purity of 82.07 percent, and the molar yield is 82.98 percent.
Example III
120 G of the reaction raw material, 1200 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (800 ppm, based on cobalt content), manganese acetate tetrahydrate (800 ppm, based on manganese content) and tetrabromoethane (3200 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.2MPa, after which the temperature was raised and maintained at 210 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 20 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction was continued for 0.5 hours, the oxygen concentration in the tail gas was increased to 7% or more. At the moment, stopping the reaction, cooling and decompressing, and discharging the reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.5 g of 3,3', 4' -BTA seed prepared in advance was added thereto, and left standing for 4 hours, during which time a crystalline product was precipitated. And carrying out suction filtration and separation on the product, washing the solid with deionized water for three times, and drying to obtain a crystal product. Gas chromatography analysis showed that it was a3, 3', 4' -BTA product of 99.10% purity with a molar yield of 88.36%.
The separated liquid phase is distilled for 1 hour at 125 ℃, or a rotary evaporator is used for rotary evaporation for 1 hour at 70 ℃ under the pressure of minus 0.095MPa to separate acetic acid, the concentrated solution is kept stand for 3 hours at room temperature to separate out solid, the solid is subjected to suction filtration and separation, the solid is washed three times by deionized water, and the solid product is obtained after drying, and the gas chromatographic analysis shows that the solid product is a2, 3',4' -BTA product with the purity of 82.23 percent, and the molar yield is 84.79 percent.
Example IV
120 G of the reaction raw material, 600 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (1600 ppm, based on cobalt content), manganese acetate tetrahydrate (1600 ppm, based on manganese content) and tetrabromoethane (1600 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.3MPa, after which the temperature was raised and maintained at 220 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 20 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction was continued for 0.8 hours, the oxygen concentration in the tail gas was increased to 7% or more. At the moment, stopping the reaction, cooling and decompressing, and discharging the reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.2 g of 3,3', 4' -BTA seed prepared in advance was added thereto, and left standing for 4 hours, during which time a crystalline product was precipitated. And carrying out suction filtration and separation on the product, washing the solid with deionized water for three times, and drying to obtain a crystal product. Gas chromatography analysis showed a 99.05% pure 3,3', 4' -BTA product in a molar yield of 89.25%.
The separated liquid phase is distilled for 1 hour at 125 ℃, or a rotary evaporator is used for rotary evaporation for 1 hour at 70 ℃ under the pressure of minus 0.095MPa to separate acetic acid, the concentrated solution is kept stand for 3 hours at room temperature to separate out solid, the solid is subjected to suction filtration and separation, the solid is washed three times by deionized water, and the solid product is obtained after drying, and the gas chromatographic analysis shows that the solid product is a2, 3',4' -BTA product with the purity of 81.84 percent, and the molar yield is 83.01 percent.
Example five
120 G of the reaction raw material, 600 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (400 ppm, based on cobalt content), manganese acetate tetrahydrate (400 ppm, based on manganese content) and tetrabromoethane (1600 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.5MPa, after which the temperature was raised and maintained at 230 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 40 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction was continued for 0.5 hours, the oxygen concentration in the tail gas was increased to 7% or more. At the moment, stopping the reaction, cooling and decompressing, and discharging the reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.2 g of 3,3', 4' -BTA seed prepared in advance was added thereto, and left standing for 2 hours, during which time a crystalline product was precipitated. And carrying out suction filtration and separation on the product, washing the solid with deionized water for three times, and drying to obtain a crystal product. Gas chromatography analysis showed that it was a3, 3', 4' -BTA product of 99.16% purity with a molar yield of 87.52%.
The separated liquid phase is distilled for 1 hour at 125 ℃, or a rotary evaporator is distilled for 1 hour at 70 ℃ under the pressure of minus 0.095MPa to separate acetic acid, the concentrated solution is kept stand for 3 hours at room temperature to separate out solid, the solid is filtered and separated by suction, the solid is washed three times by deionized water, and the solid product is obtained after drying, and the gas chromatographic analysis shows that the solid product is a2, 3',4' -BTA product with the purity of 81.11 percent, and the molar yield is 82.54 percent.
Comparative example one
In this comparative example 1, the oxidation reaction was performed at a lower temperature.
120 G of the reaction raw material, 600 g of glacial acetic acid solvent and a catalyst are added into a 2L titanium alloy material reaction kettle, wherein the reaction kettle is provided with a gas inlet, a gas outlet, a pressure monitoring device, a temperature control device, a pressure relief valve and a stirring device. The catalyst was cobalt acetate tetrahydrate (400 ppm, based on cobalt content), manganese acetate tetrahydrate (400 ppm, based on manganese content) and tetrabromoethane (1600 ppm, based on bromine content).
After the materials are added, the reaction kettle is sealed. After three purges with nitrogen, it was pressurized with air to 2.0MPa, after which the temperature was raised and maintained at 150 ℃ after the pressure had stabilized, air was continuously fed at a flow rate of 20 NL/min, stirring was continued and the reaction was started. The oxygen content of the gas outlet was monitored during the reaction, and kept at a level of less than 3%.
After the reaction lasts for 1 hour, stopping the reaction, cooling and releasing pressure, and discharging a reaction product mixture in the reaction kettle.
The reaction product mixture was cooled to room temperature, 0.5g of 3,3', 4' -BTA seed crystal prepared in advance was added thereto, no crystal precipitation was observed upon standing for 24 hours, and the total amount of BTA contained in the liquid phase was only 18.47% as characterized by high performance liquid chromatography.
This comparative example demonstrates that at lower temperatures the reaction does not proceed efficiently.
Comparative example two
In this comparative example two, the procedure of example 1 was repeated entirely, except that after completion of the oxidation reaction, the reaction product mixture in the reaction vessel was discharged and cooled to room temperature, at which time no 3,3',4' -BTA seed was added to the product mixture. After standing for 24 hours, no product precipitation was observed. After subsequent distillation to remove the acetic acid solvent, the precipitated solid was a mixture of 3,3',4' -BTA, 2, 3',4' -BTA and a small amount of 2,2', 3' -TBA, and effective separation of these positional isomers was not achieved.
Claims (10)
1. A process for preparing an aromatic polycarboxylic acid or anhydride, said process comprising:
Step one: subjecting a starting compound, which is a compound containing at least two benzene rings and two or more C1-C6 alkyl substituents and which comprises a mixture of N positional isomer starting materials, which is also a mixture comprising N positional isomer products, N being an integer not less than 2, to an oxidation reaction using a gaseous oxidant in the presence of a catalyst to produce a product mixture comprising an aromatic polycarboxylic acid;
Step two: seeding the product mixture with seed crystals of the previously prepared 1 st positional isomer product, such that the corresponding 1 st positional isomer product contained in the product mixture precipitates;
step three: the 2 nd to nth positional isomer products are separated and recovered.
2. The method of claim 1, wherein the step three comprises: seeding the product mixture with seed crystals of the previously prepared 2 nd positional isomer product to precipitate the corresponding 2 nd positional isomer product contained in the product mixture, and
The 3 rd to nth positional isomer products are separated and recovered.
3. The method of claim 1, further comprising:
step four: the N positional isomer products are converted from carboxylic acids to anhydrides, respectively.
4. The method of claim 1, wherein the starting compound is a mixture of starting materials comprising the following positional isomers: 3,3',4' -tetramethyldiphenyl methane (3, 3',4' -TMDM), 2, 3',4' -tetramethyldiphenyl methane (2, 3',4' -TMDM) and 2,2', 3' -tetramethyl diphenylmethane (2, 2', 3' -TMDM);
The product mixture is a mixture comprising the following positional isomer products: 3,3',4' -benzophenone tetracarboxylic acid (3, 3',4' -BTA), 2, 3',4' -benzophenone tetracarboxylic acid (2, 3',4' -BTA) and 2,2', 3' -benzophenone tetracarboxylic acid (2, 2', 3' -BTA).
5. The method of claim 1, wherein the gaseous oxidizing agent is selected from at least one of the following: air, oxygen.
6. The process of claim 1, wherein prior to step one, an alkylbenzene comprising at least two C1-C6 alkyl substituents is condensed with an aldehyde to form the starting compound.
7. The method of claim 1, wherein the oxidation reaction of step one is carried out at a temperature of 185 ℃ to 230 ℃.
8. The method of claim 1, wherein the catalyst comprises a metal cation and a halide anion,
The metal is a cation of one or more elements selected from the group consisting of: cobalt, manganese, molybdenum, nickel, copper, zinc;
the halide anions are chloride, bromide, or a combination thereof;
the content of the metal cations is 50-5000ppm and the content of the halogen anions is 100-10000ppm based on the total weight of all liquid and solid materials in the oxidation reaction of the first step.
9. The method of claim 1, wherein the concentration of oxygen in the oxidized gaseous oxidant is monitored during the oxidation reaction of step one and the total concentration of oxygen is maintained below 3% by volume.
10. The method of claim 1, wherein during the oxidation reaction of step one, the flow rate of the gaseous oxidant is controlled at the following level: 0.1-1X 10 6 NL/1000 g of starting compound per minute.
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