CN114181075A - Method for producing isophthalic acid by oxidizing m-xylene - Google Patents
Method for producing isophthalic acid by oxidizing m-xylene Download PDFInfo
- Publication number
- CN114181075A CN114181075A CN202010959248.6A CN202010959248A CN114181075A CN 114181075 A CN114181075 A CN 114181075A CN 202010959248 A CN202010959248 A CN 202010959248A CN 114181075 A CN114181075 A CN 114181075A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- xylene
- salt
- isophthalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 111
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 44
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 23
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000011572 manganese Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 bromine compound Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 21
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 63
- 239000000203 mixture Substances 0.000 description 58
- 239000007788 liquid Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 42
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 40
- 239000002994 raw material Substances 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000012265 solid product Substances 0.000 description 18
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 238000001816 cooling Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 9
- 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 9
- 238000002156 mixing Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 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 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing isophthalic acid by oxidizing m-xylene, which mainly solves the problem that the prior art has low transmittance of isophthalic acid products when m-xylene is oxidized to synthesize isophthalic acid. The invention relates to a method for producing isophthalic acid by adopting m-xylene oxidation, which comprises the steps of adding benzoic acid, taking acetic acid as a solvent in the presence of a catalyst, and carrying out liquid-phase oxidation reaction on an oxidant and m-xylene to synthesize the isophthalic acid, wherein the catalyst comprises Co salt, Mn salt and a bromine-containing compound, and the method comprises the following steps: the Co salt accounts for 200-300 parts by weight of Co; the Mn salt accounts for 400-600 parts by weight of Mn; the bromine-containing compound is calculated by Br and accounts for 100-1000 parts by weight, so that the technical problem is well solved, and the method can be used for synthesizing isophthalic acid through oxidizing m-xylene.
Description
Technical Field
The invention relates to a method for producing isophthalic acid by oxidizing meta-xylene.
Background
Purified isophthalic Acid (hereinafter referred to as PIA or IPA, english name); the refined isophthalic acid is used for synthesizing special fibers with fatigue strength superior to that of the fibers and producing products such as unsaturated polyester, alkyd resin, printing ink resin, insulating varnish, polyester modified coloring agent, paint and the like. Currently, there are major production plants in the world, such as Amoco, Amoco Belgium chemical company, Japan A.G. chemical company, Italy SISAS company, etc., and the total production capacity is nearly 30 ten thousand tons/year, which is the most important direction for the consumption of m-xylene in foreign countries.
The production of the isophthalic acid generally adopts the liquid phase oxidation of m-xylene (MX), acetic acid cobalt and manganese acetate are used as catalysts, tetrabromoethane or methyl ethyl ketone or acetaldehyde is used as an accelerant, acetic acid is used as a solvent, the reaction temperature is 100-250 ℃, the pressure is generally 1-5 MPa, and the time is 1-3 h; and (3) hydrogenating the 3-CBA to obtain m-TA by adopting palladium carbon catalyst at high temperature, and finally centrifuging and washing with water to remove the m-TA to obtain the polyester-grade PIA. .
No matter which process is adopted, bromine is needed as a cocatalyst, the bromine has strong corrosivity, and particularly under the high-temperature condition, so all reactors adopt expensive titanium materials; meanwhile, the product has color due to containing a small amount of macromolecular organic matters and metal impurities which are not removed completely, thereby limiting the application range of the PTA. US4211882(Process for producing terephthalic acid) adds the fourth component F, Ni, Eu and other elements to raise the chroma of the product.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low light transmittance of the product in the prior art, and provides a novel method for producing isophthalic acid by oxidizing m-xylene, which has the characteristic of high light transmittance of the obtained product.
The second technical problem to be solved by the invention is the problem of low light transmittance of the product in the prior art, and a novel catalyst is provided, and the use of the catalyst improves the light transmittance of the isophthalic acid product.
In order to solve one of the above technical problems, the first aspect of the present invention adopts the following technical solutions:
technical solution of the first aspect
A method for producing isophthalic acid by oxidizing m-xylene comprises the step of carrying out liquid-phase oxidation reaction on m-xylene and an oxidant by taking acetic acid as a solvent in the presence of a catalyst to synthesize the isophthalic acid, wherein the catalyst comprises a Co salt, a Mn salt and a bromine-containing compound, and the method comprises the following steps:
the Co salt accounts for 200-300 parts by weight of Co;
the Mn salt accounts for 400-600 parts by weight of Mn;
the bromine-containing compound is 100 to 1000 parts by weight in terms of Br.
The benzoic acid is added into a reaction system for the oxidation synthesis of the m-xylene, so that the 340nm light transmittance and the 400nm transmittance of the product can be improved, and the content of main impurities in the product can be reduced.
In the first aspect of the present invention, the benzoic acid is 100 to 1000 parts by weight, for example, but not limited to, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, and the like.
In the first aspect of the present invention, the amount of the Co salt is, for example, 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight, or the like, without limitation.
In the first aspect of the present invention, the Mn salt may be, for example, in the range of the parts by weight, 410 parts by weight, 420 parts by weight, 430 parts by weight, 450 parts by weight, 460 parts by weight, 470 parts by weight, 480 parts by weight, 490 parts by weight, 500 parts by weight, 510 parts by weight, 520 parts by weight, 530 parts by weight, 540 parts by weight, 550 parts by weight, 560 parts by weight, 570 parts by weight, 580 parts by weight, 590 parts by weight, and the like, as non-limiting examples.
In the first aspect of the present invention, the bromide is in the range of Br by weight, and may be exemplified by, but not limited to, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, and the like.
In the first aspect of the present invention, the oxidizing agent is preferably a gas containing elemental oxygen. Such as, but not limited to, oxygen, air, oxygen nitrogen mixtures, oxygen air mixtures, oxygen nitrogen mixtures, and the like.
In the first aspect of the present invention, the mass ratio of acetic acid to m-xylene is preferably 2 to 10, and non-limiting examples of the mass ratio of acetic acid to m-xylene may be 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and the like.
In the first aspect of the present invention, the reaction temperature is preferably 150 to 300 ℃, for example, but not limited to, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, etc.
In the first aspect of the present invention, the reaction pressure is preferably 1.0 to 5.0MPa, and examples thereof include, but are not limited to, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 2.0MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa, 3.0MPa, 3.2MPa, 3.4MPa, 3.6MPa, 3.8MPa, 4.0MPa, 4.2MPa, 4.4MPa, 4.6MPa, 4.8MPa, and the like.
In the technical scheme of the first aspect, the reaction time is preferably 30-300 min. For example, but not limited to, reaction times of 60min, 90min, 120min, 150min, 180min, 210min, 250min, 280min, and the like.
In the first aspect of the present invention, the oxidant is preferably air, and the air space velocity (the ratio of the gas volume flow rate to the volume of the liquid raw material mixture) is 2-5 h-1. For example, but not limited to, an air space velocity of 2.5h-1、3.0h-1、3.5h-1、4.0h-1、4.5h-1And so on.
In the first aspect of the present invention, the Co salt is preferably cobalt acetate.
In the first aspect of the present invention, the Mn salt is preferably manganese acetate.
In the first aspect of the present invention, the bromide is a bromide-containing compound that is soluble in pure water or acetic acid, preferably HBr or tetrabromoethane.
In order to solve the second technical problem, a second aspect of the present invention is as follows:
second aspect of the invention
A catalyst for the oxidation of isophthalic acid to produce isophthalic acid comprising a Co salt, a Mn salt, a bromine-containing compound, and benzoic acid, wherein:
the Co salt accounts for 200-300 parts by weight of Co;
the Mn salt accounts for 400-600 parts by weight of Mn;
100-1000 parts by weight of bromine-containing compound calculated by Br;
100 to 1000 parts by weight of benzoic acid.
In the second aspect of the present invention, the amount of the Co salt is, for non-limiting example, 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight, or the like.
In the second aspect of the present invention, the Mn salt may be, for example, in the range of the parts by weight, 410 parts by weight, 420 parts by weight, 430 parts by weight, 450 parts by weight, 460 parts by weight, 470 parts by weight, 480 parts by weight, 490 parts by weight, 500 parts by weight, 510 parts by weight, 520 parts by weight, 530 parts by weight, 540 parts by weight, 550 parts by weight, 560 parts by weight, 570 parts by weight, 580 parts by weight, 590 parts by weight, and the like, as non-limiting examples.
In the second aspect, the bromide is in the range of Br by weight, and may be, by way of non-limiting example, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, or the like.
In the second aspect of the present invention, the benzoic acid is 100 to 1000 parts by weight, for example, but not limited to, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, and the like.
In the second aspect of the present invention, the Co salt is preferably cobalt acetate.
In the second aspect of the present invention, the Mn salt is preferably manganese acetate.
In the second aspect of the present invention, the bromide is a bromide-containing compound that is soluble in pure water or acetic acid, preferably HBr or tetrabromoethane.
In the products of the examples and comparative examples of the present invention, the sample to be analyzed was first completely dissolved in dimethyl sulfoxide, PX was analyzed by gas chromatography, and other substances were analyzed by High Performance Liquid Chromatography (HPLC).
And analyzing Co and Mn in the product by adopting ICP.
The color of the product is expressed by the transmittance of the product: ultraviolet transmittance measurement: accurately weighing (3.25 +/-0.01) g of PTA sample in a 50mL beaker, adding 30mL of 4moL/L diluted ammonia water, stirring and dissolving, quantitatively transferring to a 50mL volumetric flask, and adding 4moL/L diluted ammonia water to the scale. The UV transmittance was measured at a wavelength of 400nm at 340nm using a UV spectrophotometer model A16 from PE, USA, after filtration through a 1.2m membrane into a 5cm cuvette.
According to the method for preparing the isophthalic acid by oxidizing the m-xylene, the content of Co and Mn in a product is less than 0.5ppmw, the product is pure white, and the transmittance at 340nm is more than 35%; the ultraviolet transmittance of 400nm is more than 80 percent, and better effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 2 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 300ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of the liquid feed mixture) and stirring is startedThe stirrer was heated to 200 ℃ at a stirring speed of 400rpm while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 3 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 800ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the volume of air relative to liquid feed)Volume ratio of mixture), the reaction was carried out for 90min while keeping the temperature constant.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 4 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at 400rpm and the temperature was raised to 190 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 5 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started, the stirring speed was 400rpm, and the temperature was raised to 210 ℃ while maintaining the pressure at 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 6 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 60 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
[ example 7 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of benzoic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the temperature was kept constant for 120 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide to completely dissolve the solid product, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). ICP analyzes the Co and Mn content in the product; the ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
Comparative example 1
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide solid product for complete dissolution, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). And analyzing the contents of Co and Mn in the product by ICP. The ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
Comparative example 2
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) uniformly mixing m-xylene, acetic acid, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, benzoic acid and tetrabromoethane to obtain a liquid raw material mixture, wherein the liquid raw material mixture contains 100g of m-xylene, 800g of acetic acid, 250ppmw of cobalt, 500ppmw of manganese, 500ppmw of isophthalic acid and 300ppmw of bromine, adding the liquid raw material mixture into an autoclave, and sealing.
2) Adding 3.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1(space velocity is the ratio of the volume of nitrogen to the volume of liquid feed mixture) and the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 200 ℃ while maintaining a pressure of 3.0 MPa.
4) Switching with air at 200 deg.C, air airspeed of 4h-1(space velocity is the ratio of the volume of air to the volume of liquid feed mixture) and the reaction was maintained at constant temperature for 90 min.
5) Switching to nitrogen again after the reaction, cooling to room temperature, relieving pressure of the reaction kettle to normal pressure, completely filtering the oxidized product, washing with acetic acid for three times, drying to obtain a solid product, adding dimethyl sulfoxide solid product for complete dissolution, taking out, analyzing unreacted m-xylene by gas chromatography, and analyzing Isophthalic Acid (IA), 3-methylbenzoic acid (m-TA) and 3-carboxybenzaldehyde (3-CBA) by high performance liquid chromatography; benzoic Acid (BA). And analyzing the contents of Co and Mn in the product by ICP. The ultraviolet transmittance is measured at the wavelength of 340nm and 400nm by an ultraviolet spectrophotometer.
The catalyst formulation is shown in Table 1, and the product analysis results are shown in Table 2.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
TABLE 1
TABLE 2
Claims (10)
1. A method for producing isophthalic acid by oxidizing m-xylene comprises the steps of adding benzoic acid in the presence of a catalyst, taking acetic acid as a solvent, and carrying out liquid-phase oxidation reaction on an oxidant and the m-xylene to synthesize the isophthalic acid, wherein the catalyst comprises a Co salt, a Mn salt and a bromine-containing compound, and the method comprises the following steps:
the Co salt accounts for 200-300 parts by weight of Co;
the Mn salt accounts for 400-600 parts by weight of Mn;
the bromine-containing compound is 100 to 1000 parts by weight in terms of Br.
2. The method according to claim 1, wherein the benzoic acid is used in an amount of 100 to 1000 parts by weight.
3. The method of claim 1, wherein the oxidizing agent is an elemental oxygen-containing gas.
4. The method according to claim 1, wherein the mass ratio of acetic acid to m-xylene is 2 to 20.
5. The method according to claim 1, wherein the reaction temperature is 150 to 300 ℃. And/or the reaction pressure is 1.0-5.0 MPa.
6. The method according to claim 1, wherein the reaction time is 30 to 300 min.
7. The method as set forth in claim 1, wherein the Co salt is cobalt acetate.
8. The method as set forth in claim 1, wherein the Mn salt is manganese acetate.
9. The method as set forth in claim 1, wherein said bromine compound is a bromine-containing compound soluble in pure water or acetic acid.
10. A catalyst for the oxidation of isophthalic acid to produce isophthalic acid comprising a Co salt, a Mn salt, a bromine-containing compound, and benzoic acid, wherein:
the Co salt accounts for 200-300 parts by weight of Co;
the Mn salt accounts for 400-600 parts by weight of Mn;
100-1000 parts by weight of bromine-containing compound calculated by Br;
100 to 1000 parts by weight of benzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010959248.6A CN114181075B (en) | 2020-09-14 | 2020-09-14 | Method for producing isophthalic acid by oxidizing meta-xylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010959248.6A CN114181075B (en) | 2020-09-14 | 2020-09-14 | Method for producing isophthalic acid by oxidizing meta-xylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181075A true CN114181075A (en) | 2022-03-15 |
| CN114181075B CN114181075B (en) | 2024-01-05 |
Family
ID=80600750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010959248.6A Active CN114181075B (en) | 2020-09-14 | 2020-09-14 | Method for producing isophthalic acid by oxidizing meta-xylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181075B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165135A (en) * | 1996-02-13 | 1997-11-19 | 三菱化学株式会社 | Process for producing aromatic carboxylic acid |
| CN1209801A (en) * | 1995-12-30 | 1999-03-03 | 鲜京工业股份有限公司 | Process for producing terephthalic acid |
| CN102060686A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Method for producing aromatic carboxylic acid by using nitrogen heterocyclic ring compound as oxidation accelerator |
| CN103012120A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing terephthalic acid by oxidation refining process |
| CN104418730A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method for terephthalic acid |
-
2020
- 2020-09-14 CN CN202010959248.6A patent/CN114181075B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209801A (en) * | 1995-12-30 | 1999-03-03 | 鲜京工业股份有限公司 | Process for producing terephthalic acid |
| CN1165135A (en) * | 1996-02-13 | 1997-11-19 | 三菱化学株式会社 | Process for producing aromatic carboxylic acid |
| CN102060686A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Method for producing aromatic carboxylic acid by using nitrogen heterocyclic ring compound as oxidation accelerator |
| CN103012120A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing terephthalic acid by oxidation refining process |
| CN104418730A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method for terephthalic acid |
Non-Patent Citations (4)
| Title |
|---|
| MATTHIAS J. BEIER 等: "Selective side-chain oxidation of alkyl aromatic compounds catalyzed by cerium modified silver catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 331, pages 40 - 49, XP027340006 * |
| 吴鑫干, 何斌鸿, 王艳辉, 张旭东, 阳卫军: "高纯度对苯二甲酸的生产技术进展", 现代化工, no. 01, pages 18 - 22 * |
| 尤侯平;刘建新;邢跃军;: "富氧条件下对二甲苯氧化反应的研究", 石油化工, no. 09, pages 870 - 874 * |
| 杨学萍: "对二甲苯氧化制对苯二甲酸催化体系的研究进展", 工业催化, no. 06, pages 25 - 29 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181075B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR970000136B1 (en) | Process for producing highly purified benzenedicarboxylic acid isomers | |
| JP2504461B2 (en) | Manufacturing method of high quality terephthalic acid | |
| TWI355378B (en) | Process for producing a high purity aromatic polyc | |
| JP2006528682A (en) | Method for heating crude carboxylic acid slurry in post-oxidation zone by adding steam | |
| CN110452392B (en) | Preparation method of cobalt-based metal organic framework material and application of cobalt-based metal organic framework material in p-xylene oxidation reaction | |
| CN106431887B (en) | Preparation method of trimesic acid | |
| TWI518063B (en) | Process for producing terephthalic acid | |
| JPH02184652A (en) | Preparation of aromatic polycarboxylic acid | |
| CN101365673B (en) | Method for high-purity terephthalic acid preparation | |
| US6018077A (en) | Process for producing 2,6-naphthalenedicarboxylic acid | |
| CN114181075B (en) | Method for producing isophthalic acid by oxidizing meta-xylene | |
| CN101914003A (en) | Method for producing aromatic carboxylic acids by liquid-phase catalytic oxidation of alkyl aromatics | |
| CN112645812A (en) | Start-up method for preparing terephthalic acid by liquid-phase oxidation of paraxylene | |
| CN114369099B (en) | Method for preparing pyromellitic dianhydride by liquid-phase oxidation | |
| CN105085536B (en) | A kind of preparation method of tetraphenylporphines | |
| CN105198890B (en) | A kind of production method of tetraphenylporphines | |
| WO2022085746A1 (en) | Method for producing fluorenone | |
| CN114478243A (en) | Method for synthesizing dihydroxy dimethyl terephthalate by oxygen catalytic oxidation method | |
| CN103420909B (en) | A kind of liquid phase catalytic oxidation is prepared the method for dichloro quinolinic acid | |
| CN1417193A (en) | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid | |
| CN110002988A (en) | It is a kind of for producing the two-stage temperature lifting type oxidation technology of p-phthalic acid | |
| JPWO2002088066A1 (en) | Purification method of aromatic polycarboxylic acid | |
| CN114054085B (en) | Catalyst composition and method for synthesizing isophthalic acid by oxidizing metaxylene | |
| KR100896516B1 (en) | Preparation method of terephthalic acid | |
| JPH1053557A (en) | Production of 2,6-naphthalenedicarboxylic acid having high purity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |