CN109096090A - A kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid - Google Patents
A kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid Download PDFInfo
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- CN109096090A CN109096090A CN201811005659.0A CN201811005659A CN109096090A CN 109096090 A CN109096090 A CN 109096090A CN 201811005659 A CN201811005659 A CN 201811005659A CN 109096090 A CN109096090 A CN 109096090A
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- 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
Abstract
The invention discloses a kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid, the catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid is carbon material.Non-metal carbon material is applied in the reaction of paraxylene catalysis oxidation synthesis p-methylbenzoic acid by the present invention for the first time, heterogeneous solid catalyst using non-metal carbon material as the catalytic oxidation, the catalytic activity of carbon material is higher, the conversion ratio of paraxylene is higher, the selectivity of p-methylbenzoic acid is higher, can be by being directly separated by filtration recycling and recycling.Moreover, the carbon material stability is good, reusable, from a wealth of sources, cheap, non-corrosive, environmental-friendly, high mechanical strength, large specific surface area, the application field of new carbon catalyst can be extended with substituted metal catalyst.
Description
Technical field
The invention belongs to organic synthesis applied technical fields, are used for paraxylene catalysis oxidation more particularly, to one kind
The catalyst of synthesis p-methylbenzoic acid and a kind of preparation method of p-methylbenzoic acid.
Background technique
P-methylbenzoic acid is in the substances such as a kind of industrial chemicals and synthetic drug that purposes is extremely wide, dyestuff, fragrance
Mesosome is widely used in the various fields such as medicine, pesticide, photosensitive material, organic pigment.Currently, the system of p-methylbenzoic acid
Preparation Method mainly has dimethylbenzene nitric acid oxidation method, dimethylbenzene air oxidation process and toluene carbonylation-oxidizing process etc., wherein diformazan
Benzene air oxidation process is most economical effective method.
Mainly use United States Patent (USP) US2833816 disclosed to two however, industrially preparing p-methylbenzoic acid at present
The Co-Mn-Br that toluene is reaction raw materials, air or oxygen is oxidant, acetic acid is solvent, bromide is promotor is homogeneously urged
Change system, but this method there are p-methylbenzoic acid yields low, perishable reactor wall, environment easy to pollute and catalyst difficulty recycling benefit
With the problems such as so that economic benefit is lower, needs to improve and improve.The Chinese patent of Publication No. CN1333200A discloses one kind
The heterogeneous catalysis catalytic air oxidation diformazan being made of monometallic porphyrin or μ-oxygen bimetallic porphyrin or their immobilized object
The method of benzene synthesizing methyl benzoic acid, tolyl aldehyde and methyl benzoic acid, but target product p-methylbenzoic acid poor selectivity.
The Chinese patent of Publication No. CN101462948A discloses a kind of by imine compound or quinones with Dg-
The method that the nonmetal catalyzed system catalytic air of bi-component or dioxygen oxidation dimethylbenzene for closing object composition prepare p-methylbenzoic acid,
But the bi-component non-metallic catalyst of imine compound or quinones composition is expensive, and can not recycle and repeat benefit
With.
In view of deficiency existing for above-mentioned all kinds of catalyst, need to develop a kind of highly selective, easy recycling, reusable
Catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid.
Summary of the invention
The present invention is to overcome catalyst choice described in the above-mentioned prior art low and the defect of difficult recycling, provides one
Catalyst of the kind for paraxylene catalysis oxidation synthesis p-methylbenzoic acid, the catalyst have selectivity height, catalytic activity
Higher, easy recycling, reusable advantage.
Another object of the present invention is to provide a kind of preparation methods of p-methylbenzoic acid.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid, the catalyst are carbon material.
Catalyst of the present invention using carbon material as paraxylene catalysis oxidation synthesis p-methylbenzoic acid is a kind of non-
Homogeneous solid catalyst.Carbon material is capable of the α C-H bond of activating oxygen molecule and paraxylene molecule, to reduce oxygen molecule oxidation
The activation energy of paraxylene reaction, and then it is catalyzed the progress of p xylene oxidation reaction.But the passivation due to carboxyl to phenyl ring, makes
P-methylbenzoic acid is further oxidized to p -carboxybenzaldehyde and terephthalic acid (TPA) reaction needs to overcome higher reaction activation
Can, that is, need more stringent reaction condition.Under lower reaction temperature and pressure condition, carbon material is difficult to decrease to methyl
Benzoic acid is further oxidized to the activation energy of p -carboxybenzaldehyde and terephthalic acid (TPA) reaction, therefore primary product is to methylbenzene first
Acid.Therefore, the catalytic activity of carbon material is higher so that the conversion ratio of paraxylene is higher, the selectivity of p-methylbenzoic acid compared with
It is high.Also, carbon material can be by being directly separated by filtration recycling and recycling, effectively save cost.
Preferably, the carbon material is carbon nanotube, nitrogen doped carbon nanotube, diamond, graphite or active carbon.
It is highly preferred that the carbon material is carbon nanotube.
The big pi bond characteristic electron of carbon nanotube graphite flake layer can be accelerated with the phenyl ring of paraxylene by π-πconjugation
The oxidation of paraxylene can obtain higher conversion ratio and target product selectivity.
The present invention protects a kind of preparation method of p-methylbenzoic acid simultaneously, and the preparation method includes the following steps:
S1. paraxylene, solvent and above-mentioned catalyst are uniformly mixed, are carried out instead after being passed through the oxidant containing oxygen molecule
It answers；
S2. the mixture separating-purifying after S1. being reacted, obtains p-methylbenzoic acid.
Preferably, the weight ratio of the catalyst and paraxylene is (0.001~0.12): 1.
It is highly preferred that the catalyst and paraxylene weight ratio are (0.005~0.12): 1.
Catalyst is conducive to the oxidation of paraxylene, with the increase of catalyst amount, the selectivity of p-methylbenzoic acid
First increase and declines afterwards.Catalyst is very few, so that the conversion ratio of paraxylene is lower；Catalyst excess can further be catalyzed oxygen molecule
Aoxidizing p-methylbenzoic acid is the by-products such as p -carboxybenzaldehyde and terephthalic acid (TPA).
Most preferably, the catalyst and paraxylene weight ratio are 0.023: 1.
Preferably, the temperature of the reaction is 80~250 DEG C.
It is highly preferred that the temperature of the reaction is 120~250 DEG C.
It is further preferred that the temperature of the reaction is 160~200 DEG C.
Still further preferably, the temperature of the reaction is 160 DEG C.
Preferably, the pressure of the reaction is 0.1~5MPa.
It is highly preferred that the pressure of the reaction is 1~5MPa.
It is further preferred that the pressure of the reaction is 1.5~3MPa.
Still further preferably, the pressure of the reaction is 1.8MPa.
Preferably, the time of the reaction is 0.1~20h.
It is highly preferred that the time of the reaction is 1~10h.
It is further preferred that the time of the reaction is 6h.
The temperature of reaction, pressure and time are too low, and the catalytic activity of carbon material is smaller, and the conversion ratio of paraxylene is lower；
The temperature of reaction, pressure and time are excessively high so that p-methylbenzoic acid further by oxygen molecule be oxidized to p -carboxybenzaldehyde and
The by-products such as terephthalic acid (TPA) reduce the selectivity of p-methylbenzoic acid.
Preferably, the solvent is the organic solvent to dissolve each other with paraxylene and its oxidation product.
It is highly preferred that the solvent is acetonitrile, n,N-Dimethylformamide, dimethyl sulfoxide, acetone, n-hexane, acetic acid
Ethyl ester or 1,4- dioxane.
It is further preferred that the solvent is acetonitrile, n,N-Dimethylformamide or dimethyl sulfoxide.
Still further preferably, the solvent is dimethyl sulfoxide.
The solubility of paraxylene and target product p-methylbenzoic acid is in acetonitrile, N,N-dimethylformamide and dimethyl
It is larger in sulfoxide；And acetonitrile, n,N-Dimethylformamide and dimethyl sulfoxide are more stable, it is difficult to are catalyzed by carbon material.
Preferably, the oxidant containing oxygen molecule is oxygen and/or air.
Preferably, the separating-purifying includes the steps that be separated by solid-liquid separation by mixture and further carry out to mixed liquor
The step of purification.
Preferably, catalyst is also obtained in step S2. after separating-purifying, the catalyst can be recycled and reused for step S1..
Specific step is as follows for the preparation method of above-mentioned p-methylbenzoic acid:
S1: reactant paraxylene, solvent and solid catalyst are added in reactor and mixed, is then sonicated to be formed
Suspension；The solid catalyst is carbon material, and the carbon material is carbon nanotube, nitrogen doped carbon nanotube, diamond, graphite
Or active carbon；The solvent is the organic solvent to dissolve each other with paraxylene and its oxidation product；The catalyst with to two
The weight ratio of toluene is (0.001~0.12): 1；
S2: being heated to 80~250 DEG C for resulting suspension, is passed through oxygen or air oxidant, and holding pressure is
0.1~5MPa reacts 0.1~20h；
S3: after reaction to step S2, separating reaction mixture, obtains solid catalyst and containing anti-
Answer the liquid mixture of product, unreacted reactant and solvent；
S4: by the liquid mixture separating-purifying in step S3, target product p-methylbenzoic acid is obtained.
Compared with prior art, the beneficial effects of the present invention are:
Non-metal carbon material is applied to the reaction of paraxylene catalysis oxidation synthesis p-methylbenzoic acid by the present invention for the first time
In, the heterogeneous solid catalyst using non-metal carbon material as the catalytic oxidation, the catalytic activity of carbon material is higher,
The conversion ratio of paraxylene is higher, and the selectivity of p-methylbenzoic acid is higher, can be by being directly separated by filtration recycling and repeating benefit
With.
Moreover, the carbon material stability it is good, it is reusable, from a wealth of sources, cheap, non-corrosive, environmental-friendly,
High mechanical strength, large specific surface area can extend the application field of new carbon catalyst with substituted metal catalyst.
Detailed description of the invention
Fig. 1 is the gas chromatogram of the liquid phase mixture after embodiment 1 is reacted.
Specific embodiment
The invention will be further described With reference to embodiment, but embodiments of the present invention are not limited to
This.Raw material in embodiment can be by being commercially available；Unless stated otherwise, the present invention uses reagent, method and apparatus for
The art conventional reagent, method and apparatus.
In Examples 1 to 31 and comparative example 1, the analysis of reaction product is in 6820 gas phase of Agilent that capillary column is housed
It is carried out in chromatography.
Embodiment 1
4.3g paraxylene is added in a closed reaction kettle with acetonitrile, solid catalyst carbon nanotube and is mixed, shape
At suspension is mixed, it is then sonicated to form suspension (frequency 40KHz, power 200W and time are 15min).Wherein, second
The volume ratio of nitrile and paraxylene is 6:1, is 0.023:1 as the carbon nanotube of catalyst and the weight ratio of paraxylene, i.e.,
Catalyst amount is 100mg.The mixing suspension is heated to 160 DEG C under stiring, is passed through oxygen.Due to reaction process constantly with
Stoichiometry specific consumption oxygen, therefore constantly mended during reacting progress by the stable-pressure device and flowmeter that are connected with source of oxygen
It is oxygenated and keeps pressure constant in 1.8MPa.After reaction 6 hours, liquid-solid phase mixture is released from reaction kettle bottom, is separated by filtration,
Solid catalyst and the liquid phase mixture containing unreacted reactant and reaction product are obtained, which is divided
Analysis is to determine the conversion ratio reacted and selectivity.
Embodiment 2~7
Embodiment 2~7 the difference from embodiment 1 is that, the pressure of embodiment 2~7 is 1.5MPa, and temperature is respectively 80
DEG C, 120 DEG C, 160 DEG C, 180 DEG C, 200 DEG C and 250 DEG C；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 8~12
Embodiment 8~12 the difference from embodiment 1 is that, the pressure of embodiment 8~12 be respectively 0.1MPa, 1MPa,
1.5MPa, 3MPa and 5MPa；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 13~16
Embodiment 13~16 the difference from embodiment 1 is that, the catalyst amount of embodiment 13~16 be respectively 10mg,
50mg, 200mg and 500mg；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 17~20
Embodiment 17~20 the difference from embodiment 1 is that, the reaction time of embodiment 17~20 be respectively 0.1h,
10h, 15h and 20h；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 21~24
Embodiment 21~24 the difference from embodiment 1 is that, the solid catalyst of embodiment 21~24 is respectively nitrating carbon
Nanotube (nitrogen content 2.12%), active carbon, graphite and diamond；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 25~30
Embodiment 25~30 the difference from embodiment 1 is that, the solvent of embodiment 25~30 is respectively dimethyl sulfoxide, N,
Dinethylformamide, acetone, n-hexane, ethyl acetate and 1,4- dioxane；
Other raw material dosages and operating procedure are same as Example 1.
Embodiment 31
Carbon nano-tube catalyst after embodiment 1 is reacted is cleaned and dried, and carries out embodiment 1 again, same measurement is to two
The conversion ratio of toluene and the selectivity of p-methylbenzoic acid.So analogize, this catalyst circulation is used 5 times, measured result
It is shown in Table 2.
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that, catalyst is not added in comparative example 1；
Other raw material dosages and operating procedure are same as Example 1.
The correlated condition setting and result of reaction are influenced in 1 Examples 1 to 30 of table and comparative example 1
When table 1 is that paraxylene catalysis oxidation synthesizes p-methylbenzoic acid in Examples 1 to 30 and comparative example 1, influence anti-
The correlated condition setting answered and gained paraxylene conversion and p-methylbenzoic acid selectivity result.
Fig. 1 is the gas chromatogram of the liquid phase mixture after embodiment 1 is reacted, paraxylene, p-methylbenzoic acid, to first
The retention time of base benzyl alcohol and p-tolyl aldehyde is respectively 1.928min, 8.243min, 5.964 min and 5.197min.
It being computed, 1 gained paraxylene conversion of embodiment is 47.2%, and target product p-methylbenzoic acid is selectively 80.4%,
The selectivity of other by-products is respectively to methylbenzyl alcohol 3.1%, p-tolyl aldehyde 16.5%.
Examples 1 to 7 is the research to reaction temperature, the results showed that with the raising of reaction temperature, target product is to first
The selectivity presentation of yl benzoic acid first increases the trend reduced afterwards；Reaction temperature is lower, active smaller, the paraxylene of carbon material
Conversion ratio it is lower；Reaction temperature is excessively high so that p-methylbenzoic acid further by oxygen molecule be oxidized to p -carboxybenzaldehyde and
The by-products such as terephthalic acid (TPA), so that making the selectivity of p-methylbenzoic acid reduces.Reaction temperature is within the scope of 160~200 DEG C
Other temperature are significantly better than, and are preferably, to illustrate that the reaction condition is mild at 160 DEG C.
Embodiment 1,8~12 is the research to reaction pressure, the results showed that with the increase of reaction pressure, target product
The selectivity presentation of p-methylbenzoic acid first increases the trend reduced afterwards；Hypotony causes conversion ratio too low, to methylbenzene first
The selectivity of acid is relatively low；Hypertonia makes p-methylbenzoic acid further be oxidized to p -carboxybenzaldehyde and right by oxygen molecule
The by-products such as phthalic acid cause the selectivity of p-methylbenzoic acid to reduce.Reaction pressure is significant excellent within the scope of 1.5~3MPa
It is preferably in other pressure, and in 1.8MPa.
Embodiment 1,13~16 and comparative example 1 are the research to catalyst amount, the results showed that right when catalyst is not added
The conversion ratio of dimethylbenzene is only 7.5%, and the selectivity of p-methylbenzoic acid is only 5.2%；Catalyst is conducive to paraxylene
Oxidation, with the increase of catalyst amount, the selectivity of p-methylbenzoic acid is first continuously increased, and 100~200mg this
In range preferably；After the dosage of catalyst is more than 200mg, the selectivity of p-methylbenzoic acid is gradually reduced, this is because mistake
It is the by-products such as p -carboxybenzaldehyde and terephthalic acid (TPA) that the catalyst of amount, which is further catalyzed oxygen molecule oxidation p-methylbenzoic acid,.
Therefore, it is preferably that the dosage of catalyst, which is 100 mg,.
Embodiment 1,17~20 is the research to the reaction time, the results showed that the extension in reaction time is conducive to diformazan
The oxidation of benzene.With the increase in reaction time, the selectivity of p-methylbenzoic acid first increases, when reacted between more than 6h after, it is right
The selectivity of methyl benzoic acid is gradually reduced, this is because the reaction time is too long so that p-methylbenzoic acid is further by oxygen molecule
It is oxidized to the by-products such as p -carboxybenzaldehyde and terephthalic acid (TPA).Therefore, it is preferably that the reaction time, which is 6h,.
Embodiment 1,21~24 is the research to solid catalyst.Carbon material being capable of activating oxygen molecule and paraxylene molecule
α C-H bond, to reduce the activation energy of oxygen molecule oxidation of p-xylene oxidation reaction, and then be catalyzed p xylene oxidation reaction
Progress.But the passivation due to carboxyl to phenyl ring, so that p-methylbenzoic acid is further oxidized to p -carboxybenzaldehyde and to benzene
Dioctyl phthalate reaction needs to overcome higher reaction activity, that is, needs more stringent reaction condition, such as higher reaction temperature
Degree and pressure etc..Carbon material is under lower reaction temperature and pressure condition, it is difficult to reduce p-methylbenzoic acid and further aoxidize
For the activation energy that p -carboxybenzaldehyde and terephthalic acid (TPA) react, therefore principal product is p-methylbenzoic acid.The result shows that: carbon nanometer
Pipe shows best paraxylene conversion and p-methylbenzoic acid selectivity.This is because carbon nanotube graphite flake layer is big
Pi bond characteristic electron can accelerate the oxidation of paraxylene with the phenyl ring of paraxylene by π-πconjugation, therefore can obtain higher
Conversion ratio and target product selectivity.
Embodiment 1,25~30 is the research to solvent, the results showed that paraxylene and target product p-methylbenzoic acid
Solubility it is larger in acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide；And acetonitrile, N,N-dimethylformamide
It is more stable with dimethyl sulfoxide, it is difficult to be catalyzed by carbon material.The paraxylene conversion that presents and to methyl when solvent is acetonitrile
Benzoic acid is selectively best.Therefore, organic solvent is preferably acetonitrile, N, N- dimethylformamide or dimethyl sulfoxide, further
Preferably acetonitrile.
2 carbon nano-tube catalyst stability experiment result of table
| The catalyst number used | 1 | 2 | 3 | 4 | 5 |
| Paraxylene conversion | 47.2% | 47.8% | 47.3% | 46.8% | 48.2% |
| P-methylbenzoic acid selectivity | 80.4% | 79.6% | 80.7% | 81.1% | 80.8% |
Embodiment 31 is to the results are shown in Table 2 to the research of carbon nano-tube catalyst stability.Result of study shows: repetition makes
With carbon nano-tube catalyst 5 times, the conversion ratio of paraxylene and the selectivity of p-methylbenzoic acid change less, illustrate that carbon is received
Mitron can be recycled, so as to reduce the cost of catalyst.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of catalyst for paraxylene catalysis oxidation synthesis p-methylbenzoic acid, which is characterized in that the catalyst
For carbon material.
2. catalyst according to claim 1, which is characterized in that the carbon material be carbon nanotube, nitrogen doped carbon nanotube,
Diamond, graphite or active carbon.
3. catalyst according to claim 2, which is characterized in that the carbon material is carbon nanotube.
4. a kind of preparation method of p-methylbenzoic acid, which comprises the steps of:
S1. paraxylene, solvent and the described in any item catalyst of claim 1 ~ 3 are uniformly mixed, are passed through containing oxygen molecule
Oxidant after reacted；
S2. the mixture separating-purifying after S1. being reacted, obtains p-methylbenzoic acid.
5. the preparation method according to claim 4, which is characterized in that the weight ratio of the catalyst and paraxylene is
(0.001 ~ 0.12): 1；Preferably, the weight ratio of the catalyst and paraxylene is (0.005 ~ 0.12): 1.
6. the preparation method according to claim 4, which is characterized in that the temperature of the reaction is 80 ~ 250 DEG C；It is preferred that
Ground, the temperature of the reaction are 120 ~ 250 DEG C；It is highly preferred that the temperature of the reaction is 160 ~ 200 DEG C.
7. the preparation method according to claim 4, which is characterized in that the pressure of the reaction is 0.1 ~ 5 MPa；It is preferred that
Ground, the pressure of the reaction are 1 ~ 5 MPa；It is highly preferred that the pressure of the reaction is 1.5 ~ 3 MPa.
8. the preparation method according to claim 4, which is characterized in that the time of the reaction is 0.1 ~ 20 h；Preferably,
The time of the reaction is 1 ~ 10 h.
9. the preparation method according to claim 4, which is characterized in that the solvent be and paraxylene and its oxidation product
The organic solvent to dissolve each other；Preferably, the solvent be acetonitrile,N, NDimethylformamide, dimethyl sulfoxide, acetone, just oneself
Alkane, ethyl acetate or 1,4- dioxane；It is highly preferred that the solvent be acetonitrile,N, NDimethylformamide or dimethyl
Sulfoxide.
10. the preparation method according to claim 4, which is characterized in that be also catalyzed after separating-purifying in step S2.
Agent, the catalyst can be recycled and reused for step S1..
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724053A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing sulfoxide |
| CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN114621065A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Oxidant and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63141945A (en) * | 1986-12-04 | 1988-06-14 | Mitsubishi Gas Chem Co Inc | Production of high-purity o-toluic acid |
| US5142097A (en) * | 1991-05-31 | 1992-08-25 | E. I. Du Pont De Nemours And Company | Recovery and recycle of acetic acid in an oxidation process |
| CN106187750A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of method that dimethylbenzene liquid phase catalytic oxidation prepares phthalic acid |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
-
2018
- 2018-08-30 CN CN201811005659.0A patent/CN109096090A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63141945A (en) * | 1986-12-04 | 1988-06-14 | Mitsubishi Gas Chem Co Inc | Production of high-purity o-toluic acid |
| US5142097A (en) * | 1991-05-31 | 1992-08-25 | E. I. Du Pont De Nemours And Company | Recovery and recycle of acetic acid in an oxidation process |
| CN106187750A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of method that dimethylbenzene liquid phase catalytic oxidation prepares phthalic acid |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
Non-Patent Citations (2)
| Title |
|---|
| GRIGORIY SEREDA ET AL: "Photoactivated and photopassivated benzylic oxidation catalyzed by pristine and oxidized carbons", 《CATALYSIS COMMUNICATIONS》 * |
| 曹永海等: "纳米碳材料催化液相选择性氧化的研究进展", 《化工学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724053A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing sulfoxide |
| CN112724053B (en) * | 2019-10-29 | 2023-03-31 | 中国石油化工股份有限公司 | Method for preparing sulfoxide |
| CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN112778106B (en) * | 2019-11-05 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN114621065A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Oxidant and preparation method and application thereof |
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