CN107011152A - The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid - Google Patents
The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid Download PDFInfo
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- CN107011152A CN107011152A CN201610059041.7A CN201610059041A CN107011152A CN 107011152 A CN107011152 A CN 107011152A CN 201610059041 A CN201610059041 A CN 201610059041A CN 107011152 A CN107011152 A CN 107011152A
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- Prior art keywords
- catalyst
- paraxylene
- selectivity
- methylbenzoic acid
- catalysis oxidation
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Links
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000003426 co-catalyst Substances 0.000 claims abstract description 14
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001868 cobalt Chemical class 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid, paraxylene, major catalyst cobalt salt and co-catalyst nitrogen-containing heterocycle compound are added into reactor, control 0.4~1.0MPa of reacting kettle inner pressure, then heat to 80~180 DEG C, react 60-180min, the mass ratio of major catalyst and paraxylene is 0.01~0.1%, and the mol ratio of major catalyst and co-catalyst is 1:0.1~10.It is without the use of bromide in this method, reduces equipment investment cost and environmental pollution, also without the use of solvent, reduces the operating cost that solvent separation is brought, and the reaction time is short, mild condition, and the selectivity of target product p-methylbenzoic acid is good.
Description
Technical field
The present invention relates to a kind of method of Selectivity for paraxylene catalysis oxidation p-methylbenzoic acid.
Background technology
P-methylbenzoic acid can be used as the intermediate of medicine, agricultural chemicals, organic pigment etc., be important fine chemical material and
Product.At present, the main source of p-methylbenzoic acid is paraxylene and air-liquid-phase catalytic oxidation production terephthalic acid (TPA)
Byproduct.
United States Patent (USP) US2833816 discloses the PX and sky for using Co-Mn-Br homogeneous catalysis systems, acetic acid as solvent
Gas-liquid phase oxidation produces the method for terephthalic acid (TPA) and p-methylbenzoic acid, and is worldwide widely applied, should
Method employs bromide to be needed to use titanium as accelerator, therefore consersion unit, and due to having used substantial amounts of acetic acid conduct
Solvent, therefore accordingly need the process that acetic acid is separated from water；Publication No. CN1333200 Chinese patent discloses one kind
Catalytic air oxidation dimethylbenzene into methyl benzoic acid, tolyl aldehyde and methyl benzoic acid method, from biological enzymatic structure
The heterogeneous catalysis of similar monometallic porphyrin or μ-oxygen bimetallic porphyrin or their immobilized thing composition, can be prevented effectively from
The generation of deep oxidation product, the PX conversion ratios of the method are between 8~15%, and the reaction time is 8~12h, and primary product is
Tolyl aldehyde, methylbenzyl alcohol and methyl benzoic acid, p-methylbenzoic acid poor selectivity；Publication No.
CN101462948A Chinese patent discloses a kind of in the non-gold of bi-component being made up of imine compound or quinones
Belong under catalyst system and catalyzing effect, the method that dimethylbenzene prepares methyl benzoic acid with air or oxygen, this method is prepared to methylbenzene first
Without using any metallic catalyst in acid, reaction condition is gentleer, is being without using the reaction time in the case of solvent
12~24h, the reaction time is longer.
The content of the invention
The purpose of the present invention be the deficiency existed for p-methylbenzoic acid production technology in the prior art there is provided one kind to two
Without using bromide and solvent in the method that methylbenzene selective catalysis oxidation prepares p-methylbenzoic acid, the technical process, reaction
Time is short, mild condition, and target product selectivity is good.
To achieve the above object, the technical solution adopted by the present invention is：
The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid：Paraxylene, master are added into reactor
Catalyst and co-catalyst, control 0.4~1.0MPa of reacting kettle inner pressure, then heat to 80~180 DEG C, reaction
60-180min；
The major catalyst is cobalt salt, and the co-catalyst is nitrogen-containing heterocycle compound；
The mass ratio of the major catalyst and paraxylene is 0.01~0.1%；
The mol ratio of the major catalyst and co-catalyst is 1:0.1~10.
Further, any one of the major catalyst in cobalt acetate, cobalt naphthenate or cobalt iso-octoate.
Further, the co-catalyst is any one in pyridine, imidazoles, benzimidazole or their derivative.
Further, the mol ratio of the major catalyst and co-catalyst is preferably 1：0.5~10, more preferably 1：
1~5.
Beneficial effect：Prepared by selective catalytic oxidation paraxylene of the present invention is not required to make in p-methylbenzoic acid, technical process
With bromide, equipment investment cost and environmental pollution are reduced；Also it is without the use of solvent, reduces the fortune that solvent separation is brought
Row cost；And the reaction time is short, mild condition, the selectivity of target product p-methylbenzoic acid is good.
Embodiment
The embodiment to the present invention is described in detail below, it should be noted however that the protection of the present invention
Scope is not limited to these specific embodiments, but determined by claims.
Embodiment 1
500g paraxylene (4.71mol), 0.42g Cobalt diacetate tetrahydrate catalyst are added into 1000mL stirred autoclaves
(0.0017mol) and 0.2g benzimidazoles (0.0017mol), kettle cover closing, N2Replace and pressurize is to 0.9MPa, stir
Mix rotating speed is 800rpm, is heated to 170 DEG C, is passed through air and is reacted, and reaction temperature rises to 175 DEG C and controlled warm herein
Degree reaction, the reaction time is 120min.After reaction terminates, normal temperature is cooled the temperature to, pressure is down to normal pressure, produces.
Product is analyzed using external standard method on Agilent 7890A gas chromatographs.Test result is：Paraxylene is converted
Rate 15.41%, p-methylbenzoic acid selectivity 57.65%, terephthalic acid (TPA) selectivity 38.53%, p -carboxybenzaldehyde selection
Property 2.48%, other 1.34%.
Embodiment 2- embodiments 9
Embodiment 2-9 technological parameter is shown in Table 1, and remaining is same as Example 1.
The embodiment 2-9 of table 1 technological parameter
Comparative example
500g paraxylene (4.71mol), 0.42g Cobalt diacetate tetrahydrates catalyst (0.0017mol) are added into reactor,
Without co-catalyst, kettle cover closing, N2Replace and pressurize be to 0.9MPa, speed of agitator is 800rpm, is heated to 170 DEG C,
It is passed through air to be reacted, reaction temperature rises to 175 DEG C and controlled in this thermotonus, and the reaction time is 60~180min.
After reaction terminates, normal temperature is cooled the temperature to, pressure is down to normal pressure, produces.Product made from embodiment 1-9 is used into external standard
Method is analyzed on Agilent 7890A gas chromatographs, and is contrasted with the analysis result of comparative example, and analysis result is shown in
Table 2：
Table 2
Selectivity using the p-methylbenzoic acid of product made from present invention process it can be seen from the test result of upper table is remote
Better than comparative example, the conversion ratio of paraxylene is also above comparative example.
Claims (5)
1. a kind of method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid, it is characterised in that add into reactor
Enter paraxylene, major catalyst and co-catalyst, control 0.4~1.0MPa of reacting kettle inner pressure, then heat to 80~180 DEG C,
React 60-180min；
The major catalyst is cobalt salt, and the co-catalyst is nitrogen-containing heterocycle compound；
The mass ratio of the major catalyst and paraxylene is 0.01~0.1%；
The mol ratio of the major catalyst and co-catalyst is 1:0.1~10.
2. the method that Selectivity for paraxylene catalysis oxidation as claimed in claim 1 prepares p-methylbenzoic acid, its feature exists
In any one of the major catalyst in cobalt acetate, cobalt naphthenate or cobalt iso-octoate.
3. the method that Selectivity for paraxylene catalysis oxidation as claimed in claim 1 prepares p-methylbenzoic acid, its feature exists
In the co-catalyst is any one in pyridine, imidazoles, benzimidazole or their derivative.
4. the method that the Selectivity for paraxylene catalysis oxidation as described in claim 1 or 2 or 3 prepares p-methylbenzoic acid, its
It is characterised by, the mol ratio of the major catalyst and co-catalyst is 1：0.5~10.
5. the method that Selectivity for paraxylene catalysis oxidation as claimed in claim 4 prepares p-methylbenzoic acid, its feature exists
In the mol ratio of the major catalyst and co-catalyst is 1：1~5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610059041.7A CN107011152A (en) | 2016-01-27 | 2016-01-27 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610059041.7A CN107011152A (en) | 2016-01-27 | 2016-01-27 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107011152A true CN107011152A (en) | 2017-08-04 |
Family
ID=59439176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610059041.7A Pending CN107011152A (en) | 2016-01-27 | 2016-01-27 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096090A (en) * | 2018-08-30 | 2018-12-28 | 岭南师范学院 | A kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid |
| CN109456152A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene |
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|---|---|---|---|---|
| CN1363546A (en) * | 2002-01-16 | 2002-08-14 | 泰兴市化工七厂 | Homogeneous oxidizing process for preparing 3,5-dimethylbenzoic acid from sym-tritoluene |
| CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
| CN101146755A (en) * | 2005-03-31 | 2008-03-19 | 科学与工业研究委员会 | Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water |
| CN101177393A (en) * | 2006-11-08 | 2008-05-14 | 扬州市刘氏化工有限公司 | Process for producing methyl benzoic acid by paraxylene |
| CN101462948A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Method for producing methyl benzoie acid by catalytic oxidation of dimethylbenzene |
| CN101623654A (en) * | 2008-07-11 | 2010-01-13 | 中国科学院大连化学物理研究所 | Application of N-hydroxy compound containing nitrogen aromatic ring in hydrocarbon oxidation |
| CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
-
2016
- 2016-01-27 CN CN201610059041.7A patent/CN107011152A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1363546A (en) * | 2002-01-16 | 2002-08-14 | 泰兴市化工七厂 | Homogeneous oxidizing process for preparing 3,5-dimethylbenzoic acid from sym-tritoluene |
| CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
| CN101146755A (en) * | 2005-03-31 | 2008-03-19 | 科学与工业研究委员会 | Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456152A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene |
| CN109456152B (en) * | 2017-09-06 | 2021-10-29 | 中国科学院大连化学物理研究所 | Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene |
| CN109096090A (en) * | 2018-08-30 | 2018-12-28 | 岭南师范学院 | A kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid |
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