CN103508862A - Method for preparing terephthalaldehyde through catalytic oxidation - Google Patents
Method for preparing terephthalaldehyde through catalytic oxidation Download PDFInfo
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- CN103508862A CN103508862A CN201310481953.XA CN201310481953A CN103508862A CN 103508862 A CN103508862 A CN 103508862A CN 201310481953 A CN201310481953 A CN 201310481953A CN 103508862 A CN103508862 A CN 103508862A
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- terephthalaldehyde
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- 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
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- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
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Abstract
The invention discloses a method for preparing terephthalaldehyde through catalytic oxidation. The method is characterized in that a fluorination agent is adopted to catalyze sodium chloride so as to obtain the only product of p-dichloro benzene, and the selectivity of the p-dichloro benzene to a product is improved, so that the total yield is improved greatly; the p-dichloro benzene is oxidized to obtain the terephthalaldehyde, manganese dioxide is used as an oxidation agent, and 98 wt% of sulfuric acid is added, so that the catalytic oxidation effect is enhanced, and the conversion rate of the p-dichloro benzene is increased; all used raw materials are environment-friendly and cheap and are easy-to-get industrial products, so that the hazard of chlorine gas chloridization for the traditional industry can be eliminated.
Description
Technical field
The present invention relates to a kind of method of preparing terephthalaldehyde, be specifically related to a kind of method that catalyzed oxidation is prepared terephthalaldehyde.
Background technology
Terephthalaldehyde application at home and the experimental study of suitability for industrialized production, experienced the course of more than 20 years, expansion and usage quantity along with its range of application increased in recent years, formed market potential large, the fine chemical product kind that vitality is strong is the important intermediate of preparation medicine, spices, dyestuff, plastics, white dyes.Its series product benzyl dichloride, aldehydic acid etc. have also become industry kind of certain scale.
At present industrially mainly by p-xylene oxidation, hydrolysis, obtain, its manufacture is used hypertoxic chlorine, and produces the hydrogen chloride gas of severe corrosive, contaminate environment in the time of etching reactor, and can generate multiple chloro intermediate product, terephthalaldehyde yield is reduced.Liu Yan ice Master's thesis (research of the preparation of Fe-Mo-Ni catalyzer, sign and catalyzed oxidation p-Xylol thereof. Guangxi University) in reported that it is eco-friendly friendly process that p-Xylol partial oxidation is prepared terephthalaldehyde, wherein use Ni to carry out modification to Fe-Mo catalyzer, catalyzer after modification can significantly improve the selectivity of transformation efficiency and the terephthalaldehyde of p-Xylol, but aforesaid method, because catalyzer preparation is complicated and expensive being only suitable for produced in laboratory room small-sized, is not suitable for industrial mass production.
Summary of the invention
The object of the present invention is to provide a kind of catalyzed oxidation to prepare the method for terephthalaldehyde, described method adopts fluorination reagent catalytic chlorination sodium to obtain unique product to benzene dichloro, has improved the selectivity to product to benzene dichloro, and total recovery improves greatly.
The technical solution that realizes the object of the invention is:
Catalyzed oxidation is prepared a method for terephthalaldehyde, and described method is as follows:
(1) p-Xylol is dissolved in solvent acetonitrile, and adds wherein the two benzsulfamides of fluorine reagent N-fluoro and sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor;
(2) in the mixed solution of santochlor, add 98wt% sulfuric acid and Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours;
(3) reaction finishes rear mixed solution cold filtration, and filtrate regulates pH to 6 ~ 7 with NaOH solution, washes separated organic layer, and organic layer obtains terephthalaldehyde crude product after underpressure distillation, and crude product recrystallization obtains terephthalaldehyde after being dried.
Wherein, in step (1), the mol ratio of the two benzsulfamides of p-Xylol and N-fluoro is 1:0.1 ~ 0.5, and the mol ratio of p-Xylol and sodium-chlor is 1:1.
In step (2), the volume ratio of 98wt% sulphuric acid and p-Xylol is 2 ~ 4:1, and the mol ratio of Manganse Dioxide add-on and dimethylbenzene is 1:1.
In step (3), NaOH solution regulates pH to 6 ~ 7, the ethanol that recrystallization is 1:1 by volume ratio and the mixed solution of water.
Compared with prior art, its remarkable advantage is in the present invention: (1) described method adopts fluorination reagent catalytic chlorination sodium to obtain unique product to benzene dichloro, has improved the selectivity to product to benzene dichloro, and total recovery improves greatly; (2) benzene two oxychlorinations are obtained to terephthalaldehyde, oxidising agent used is Manganse Dioxide, adds 98wt% sulfuric acid catalysis oxidation effectiveness to strengthen and makes benzene dichloro transformation efficiency raise; (3) raw materials used is all the industry of the environmental protection cheapness product that are easy to get, and has eliminated the danger of traditional industry by chlorinated with chlorine.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 catalyzed oxidation of the present invention is prepared the method flow diagram of terephthalaldehyde.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend.
Catalyzed oxidation is prepared a method for terephthalaldehyde, described method following (as Fig. 1):
(1) p-Xylol is dissolved in solvent acetonitrile, and adds wherein the two benzsulfamides of fluorine reagent N-fluoro and sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor;
(2) in the mixed solution of santochlor, add 98wt% sulfuric acid and Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours;
(3) react and finish rear mixed solution cold filtration, filtrate regulates pH to neutral with NaOH solution, washes separated organic layer, and organic layer obtains terephthalaldehyde crude product after underpressure distillation, and crude product recrystallization obtains terephthalaldehyde after being dried.
Reaction equation:
Embodiment 1
10.6g p-Xylol is dissolved in 200mL solvent acetonitrile and adds reactor, and add wherein the two benzsulfamides of 3.15g fluorine reagent N-fluoro and 5.8g sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor; Mixed solution is not treated add wherein 98wt% sulfuric acid (with p-Xylol volume ratio be 1:2) and 8.69g Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours; Reaction finishes rear mixed solution cold filtration, filtrate regulates pH to 6 ~ 7 with NaOH solution, wash separated organic layer, organic layer obtains terephthalaldehyde crude product after underpressure distillation, the ethanol that crude product is 1:1 by 100mL volume ratio and water mixed liquid recrystallization, after dry, obtain terephthalaldehyde 8.65g, yield 64.5%.
Embodiment 2
10.6g p-Xylol is dissolved in 200mL solvent acetonitrile and adds reactor, and add wherein the two benzsulfamides of 15.75g fluorine reagent N-fluoro and 5.8g sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor; Mixed solution is not treated add wherein 98wt% sulfuric acid (with p-Xylol volume ratio be 1:4) and 8.69g Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours; Reaction finishes rear mixed solution cold filtration, filtrate regulates pH to 6 ~ 7 with NaOH solution, wash separated organic layer, organic layer obtains terephthalaldehyde crude product after underpressure distillation, the ethanol that crude product is 1:1 by 100mL volume ratio and water mixed liquid recrystallization, after dry, obtain terephthalaldehyde 10.36g, yield 77.3%.
Embodiment 3
21.2g p-Xylol is dissolved in 400mL solvent acetonitrile and adds reactor, and add wherein the two benzsulfamides of 25.52g fluorine reagent N-fluoro and 11.6g sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor; Mixed solution is not treated add wherein 98wt% sulfuric acid (with p-Xylol volume ratio be 1:4) and 17.38g Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours; Reaction finishes rear mixed solution cold filtration, filtrate regulates pH to 6 ~ 7 with NaOH solution, wash separated organic layer, organic layer obtains terephthalaldehyde crude product after underpressure distillation, the ethanol that crude product is 1:1 by 100mL volume ratio and water mixed liquid recrystallization, after dry, obtain terephthalaldehyde 20.7g, yield 77.2%.
Claims (4)
1. catalyzed oxidation is prepared a method for terephthalaldehyde, it is characterized in that described method is as follows:
(1) p-Xylol is dissolved in solvent acetonitrile, and adds wherein the two benzsulfamides of fluorine reagent N-fluoro and sodium-chlor, under room temperature, reaction obtains the mixed solution of santochlor;
(2) in the mixed solution of santochlor, add 98wt% sulfuric acid and Manganse Dioxide, room temperature is heated to reflux temperature, reacts 5 ~ 7 hours;
(3) react and finish rear mixed solution cold filtration, filtrate regulates pH to neutral with NaOH solution, washes separated organic layer, and organic layer obtains terephthalaldehyde crude product after underpressure distillation, and crude product recrystallization obtains terephthalaldehyde after being dried.
2. catalyzed oxidation is prepared the method for terephthalaldehyde according to claim 1, it is characterized in that: in step (1), p-Xylol is 1:0.1 ~ 0.5 with the mol ratio of N-fluoro pair benzsulfamides, and the mol ratio of p-Xylol and sodium-chlor is 1:1.
3. catalyzed oxidation is prepared the method for terephthalaldehyde according to claim 1, it is characterized in that: in step (2), the volume ratio of 98wt% sulphuric acid and p-Xylol is 2 ~ 4:1, and the mol ratio of Manganse Dioxide add-on and dimethylbenzene is 1:1.
4. catalyzed oxidation is prepared the method for terephthalaldehyde according to claim 1, it is characterized in that: in step (3), NaOH solution regulates pH to 6 ~ 7, the ethanol that recrystallization is 1:1 by volume ratio and the mixed solution of water.
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| CN201310481953.XA CN103508862A (en) | 2013-10-16 | 2013-10-16 | Method for preparing terephthalaldehyde through catalytic oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879737A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of refining methd of terephthalaldehyde |
| CN109879739A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of refining methd of terephthalaldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328374A (en) * | 1979-07-05 | 1982-05-04 | Mitsubishi Gas Chemical Co., Inc. | Process for the production of aromatic dialdehydes |
| US4335052A (en) * | 1979-11-29 | 1982-06-15 | Dynamit Nobel Aktiengesellschaft | Method of preparing substituted benzaldehydes |
| CN101306968A (en) * | 2008-06-30 | 2008-11-19 | 浙江工业大学 | Process for synthesizing halogenated compounds by oxygenizing and halogenating reaction |
| CN101786934A (en) * | 2010-02-08 | 2010-07-28 | 江西科技师范学院 | Preparation method of aromatic formaldehyde |
-
2013
- 2013-10-16 CN CN201310481953.XA patent/CN103508862A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328374A (en) * | 1979-07-05 | 1982-05-04 | Mitsubishi Gas Chemical Co., Inc. | Process for the production of aromatic dialdehydes |
| US4335052A (en) * | 1979-11-29 | 1982-06-15 | Dynamit Nobel Aktiengesellschaft | Method of preparing substituted benzaldehydes |
| CN101306968A (en) * | 2008-06-30 | 2008-11-19 | 浙江工业大学 | Process for synthesizing halogenated compounds by oxygenizing and halogenating reaction |
| CN101786934A (en) * | 2010-02-08 | 2010-07-28 | 江西科技师范学院 | Preparation method of aromatic formaldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 杨咏梅等: "对苯二甲醛合成工艺研究", 《江苏化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879737A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of refining methd of terephthalaldehyde |
| CN109879739A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of refining methd of terephthalaldehyde |
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Application publication date: 20140115 |