CN106883116A - A kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol - Google Patents
A kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol Download PDFInfo
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- CN106883116A CN106883116A CN201510933531.0A CN201510933531A CN106883116A CN 106883116 A CN106883116 A CN 106883116A CN 201510933531 A CN201510933531 A CN 201510933531A CN 106883116 A CN106883116 A CN 106883116A
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- Prior art keywords
- toluene
- catalyst
- benzoic acid
- benzaldehyde
- ergol
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method that condition of no solvent Toluene prepares benzoic acid, benzaldehyde, phenmethylol, Ergol.The method makes toluene carry out oxidation reaction with toluene as raw material, with molecular oxygen as oxygen source under the catalytic action of ferriferous oxide load gold catalyst, obtains benzoic acid, benzaldehyde, Ergol.By regulating catalyst load capacity, under optimum reaction condition, the conversion ratio of toluene is 25% to the present invention, and the selectivity of benzoic acid is 46%, and benzaldehyde is selectively 14%, and Ergol is selectively 22%.The present invention has economy and Environmental costs low；Product and catalyst are easily separated, and post processing is simple to wait remarkable advantage, with good application prospect.
Description
Technical field
The present invention relates to the method with load type gold catalyst catalysis oxidation toluene.It is solvent-free,
Without preparing benzoic acid, benzaldehyde, Ergol under the conditions of soda acid co-catalyst.
Background introduction：
, used as simplest aromatic acid, it is in medicine, dyestuff, plasticizer and food preservative for benzoic acid
Had a very wide range of applications Deng field.Current industrial production benzoic acid is mainly by toluene liquid
Phase oxidation is obtained.And direct oxidation method prepare benzoic acid would generally along with accessory substance benzaldehyde,
The generation of phenmethylol and benzoic acid Bian ester.Although the production of accessory substance is difficult to avoid that, these are secondary
Product itself unit price be often higher than several times of benzoic acid, such that it is able to effectively improve production line
The output value and profit.
Industrially, in traditional organic solvent liquid-phase oxidation of toluene method it is general with iron, cobalt, manganese, nickel,
Cerium salt is major catalyst, is carried out under the auxiliary of soda acid co-catalyst.In the catalyst system and catalyzing,
Substantial amounts of transition metal salt is remained after reaction in solution, subsequent processes are complicated, and organic waste
Thing environmental pollution is big, therefore a kind of environmentally friendly, safety simple to operate of development, atom warp
Ji property reaction scheme high has very important meaning.
It is solvent-free, meet very much the reaction theory without liquid-phase oxidation of toluene method under the conditions of soda acid co-catalyst.
But so far, the patent related to the method, research report are very few, industrial metaplasia is realized
That produces is even more very little, and its reason essentially consists in that toluene conversion is low, and product yield is limited,
Catalyst amount is big, high cost, and difficult recovery, causes the market competitiveness not strong.Patent No.
The Chinese patent of CN102219662 discloses one kind and is not using organic solvent condition Toluene system
Standby benzaldehyde, phenmethylol, the method for benzoic acid Bian ester.But the method uses manganese salt and cerium salt etc.
Soluble catalyst is aoxidized to toluene, and toluene conversion is catalyzed only 10% or so
Agent consumption is big, remains substantial amounts of transition metal salt in solution after reaction and is difficult to separate, to economical and
Environmental protection is all very unfavorable.Therefore for this kind of reaction, search out a kind of with high activity, high selection
Property and easily reclaim heterogeneous catalyst be then particularly important.
Document 1 (Science, 2011,331.195) finds bimetallic catalyst Au-Pd/C in toluene
Show good activity in oxidation, and metal component different ratio to such oxidation reaction
Show good selectivity.The major product of the method is benzoic acid Bian ester, and other height are additional
Value byproduct is less, and economic benefit is limited, and bimetallic catalyst load capacity is higher, cost
It is high.
Document 2 (Chem.Commun., 2012,48.8431) is continuing using foregoing bimetal Au-Pd
On the basis of catalyst, toluene oxidation is showed at a lower temperature using Lewis acid carriers
Go out high activity and selectivity.But catalyst is equally using Au the and Pd bimetallics that load capacity is higher
Catalyst, therefore economic worth is not high.
The content of the invention
It is an object of the invention to toluene as raw material, under condition of no solvent, using Au/FeOxCatalysis
Agent, oxidation reaction is carried out by oxidant of molecular oxygen, primary product be benzoic acid, phenmethylol,
Benzaldehyde and Ergol.
To achieve the above object, the present invention uses following technical scheme:
With high-specific surface area ferriferous oxide as carrier, with gold as activated centre, using coprecipitation or leaching
Stain method prepares catalyst, and active component content is 0.01-1wt%.
React on and carry out in closed autoclave, the initial pressure in reactor during oxygen room temperature is
0.1-2MPa, reaction temperature is 150-200 DEG C, and the reaction time is no less than 2 hours.
The addition of described load type gold catalyst is the 2%-10% of toluene by weight, preferably 2%
- 5%.
Advantageous Effects
1) under the conditions of the solvent-free co-catalyst without soda acid, using Au/FeOxCatalyst preparation goes out benzene
Formic acid, benzaldehyde, the method for Ergol, with safety simple to operate, atom
It is aobvious that economy is high, catalyst preparation process is simple, recovery is easy, product is easily separated etc.
Write advantage；
2) under optimum reaction condition, the conversion ratio of toluene can reach more than 25%, and high attached
The selectivity of value added chemicals benzoic acid is 46%, and benzaldehyde is selectively 14%, benzene first
Acid benzyl ester is selectively 22%.
Specific embodiment
Following implementation be will be helpful to understand the present invention, but protection scope of the present invention is not limited to
In these examples：
Embodiment 1
1.5 grams of toluene add 15ml pressure reaction stills, while to 0.05 gram (0.05 of addition in reactor
Wt%) Au/FeOxAutoclave was heated to 150 DEG C by catalyst, enclosed high pressure kettle through 25 minutes,
It is passed through oxygen to be reacted, maintenance reaction pressure is 1.0Mpa, after reacting 7 hours, stops
Reaction, is down to room temperature.Mixture gas chromatogram fixative detection, toluene conversion 4.4%,
Benzoic acid 12%, benzaldehyde 71%, phenmethylol 7%.
Embodiment 2
1.5 grams of toluene add 15ml autoclaves, while to 0.05 gram (0.05 of addition in reactor
Wt%) Au/FeOxAutoclave was heated to 150 DEG C by catalyst, enclosed high pressure kettle through 25 minutes,
It is passed through oxygen to be reacted, maintenance reaction pressure is 1.0Mpa, after reacting 24 hours, is stopped
Only react, be down to room temperature.Mixture gas chromatogram fixative detection, toluene conversion 25%,
Benzoic acid 46%, benzaldehyde 14%, Ergol 22%.
Embodiment 3
1.5 grams of toluene add 15ml autoclaves, while to 0.05 gram (0.5 of addition in reactor
Wt%) Au/FeOxAutoclave was heated to 150 DEG C by catalyst, enclosed high pressure kettle through 25 minutes,
It is passed through oxygen to be reacted, maintenance reaction pressure is 1.0Mpa, after reacting 7 hours, stops
Reaction, is down to room temperature.Mixture gas chromatogram fixative detection, toluene conversion 9.3%,
Benzaldehyde 25%, benzoic acid 58%, Ergol 1%.
Embodiment 4-19
1.5 grams of toluene add 15ml autoclaves, while to 0.05 gram of difference of addition in reactor
The load type metal catalyst of loading, enclosed high pressure kettle heated autoclave through 25 minutes
To 150 DEG C, it is passed through oxygen and is reacted, maintenance reaction pressure is 1.0Mpa, reaction 7 is small
Shi Hou, stops reaction, is down to room temperature.Mix products are detected with gas chromatogram fixative.Reaction
The results detailed in Table.
* the reaction time is 24 hours.
By table as can be seen that using FeO proposed by the inventionxCarrier shown in toluene oxidation compared with
Good activity.And the Au/FeO as prepared by the present inventionxCatalyst, uses in comparison example 4-19
The catalyst for arriving has conversion ratio higher.In addition, while principal product benzoic acid is obtained,
Accessory substance benzaldehyde and benzoic acid Bian ester also can effectively improve the output value of toluene oxidation production line
And profit.
Claims (8)
1. a kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol, including
Following step：With toluene as raw material, with molecular oxygen as oxygen source, in the catalysis of ferriferous oxide gold-supported
Making toluene under the catalytic action of agent carries out oxidation reaction, obtains benzoic acid, benzaldehyde, benzoic acid
One or two or more kinds in benzyl ester.
2. method according to claim 1, it is characterised in that：The Au catalyst is single former
Son or nano catalyst, preferably monatomic Au catalyst.
3. method according to claim 1, it is characterised in that：Iron oxidation in the catalyst
Thing is the oxyhydroxide of di-iron trioxide, ferroso-ferric oxide or iron.
4. the method according to claim 1,2 or 3, it is characterised in that：Load type gold is catalyzed
Gold loading is 0.01%-3%, preferably 0.1-1% in agent.
5. method according to claim 1, it is characterised in that：It is described in the oxidation reaction
The consumption of load type gold catalyst is the 2%-10% of toluene quality, preferably 4%.
6. method according to claim 1, it is characterised in that：Oxygen pressure in the oxidation reaction
It is 0.5-2.0MPa, preferably oxygen pressure is 1.0-2.0MPa, most preferably 1.5MPa.
7. method according to claim 1, it is characterised in that：The reaction temperature of the oxidation reaction
It is 120-200 DEG C to spend, and preferably reaction temperature is 150-180 DEG C, most preferably 150 DEG C.
8. method according to claim 1, it is characterised in that：During the reaction of the oxidation reaction
Between be 5-10h, most preferably 7h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510933531.0A CN106883116A (en) | 2015-12-15 | 2015-12-15 | A kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol |
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| CN201510933531.0A CN106883116A (en) | 2015-12-15 | 2015-12-15 | A kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075882A (en) * | 2019-05-09 | 2019-08-02 | 南京工程学院 | A kind of application of transition metal composite oxide catalytic agent in catalysis toluene oxidation synthesizing benzoic acids benzyl ester |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB281307A (en) * | 1926-11-24 | 1929-05-24 | Selden Co | Catalytic oxidation of organic compounds |
| CN101531576A (en) * | 2009-04-03 | 2009-09-16 | 苏州大学 | Method for preparing benzaldehyde through styrene catalytic oxidation |
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN102219662A (en) * | 2011-04-27 | 2011-10-19 | 武汉万园寺药业有限公司 | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene |
| CN102513104A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method |
| CN102964230A (en) * | 2012-11-20 | 2013-03-13 | 东南大学 | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation |
-
2015
- 2015-12-15 CN CN201510933531.0A patent/CN106883116A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB281307A (en) * | 1926-11-24 | 1929-05-24 | Selden Co | Catalytic oxidation of organic compounds |
| CN101531576A (en) * | 2009-04-03 | 2009-09-16 | 苏州大学 | Method for preparing benzaldehyde through styrene catalytic oxidation |
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN102219662A (en) * | 2011-04-27 | 2011-10-19 | 武汉万园寺药业有限公司 | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene |
| CN102513104A (en) * | 2011-11-24 | 2012-06-27 | 浙江大学 | Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method |
| CN102964230A (en) * | 2012-11-20 | 2013-03-13 | 东南大学 | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation |
Non-Patent Citations (2)
| Title |
|---|
| 尉继英，等: "低温氧化催化剂的制备及其失活机理研究", 《中国环境科学学会室内环境与健康分会学术年会》 * |
| 韩文: "氧化铁纳米片负载金催化剂制备及催化甲苯氧化性能", 《北京工业大学硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075882A (en) * | 2019-05-09 | 2019-08-02 | 南京工程学院 | A kind of application of transition metal composite oxide catalytic agent in catalysis toluene oxidation synthesizing benzoic acids benzyl ester |
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Application publication date: 20170623 |