CN103524323B - Method for catalytically synthesizing o-benzoylbenzoic acid by virtue of metal oxide supported solid superacid - Google Patents
Method for catalytically synthesizing o-benzoylbenzoic acid by virtue of metal oxide supported solid superacid Download PDFInfo
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- CN103524323B CN103524323B CN201310486773.0A CN201310486773A CN103524323B CN 103524323 B CN103524323 B CN 103524323B CN 201310486773 A CN201310486773 A CN 201310486773A CN 103524323 B CN103524323 B CN 103524323B
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- metal oxide
- benzoylbenzoic acid
- benzene
- solid superacid
- catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for catalytically synthesizing o-benzoylbenzoic acid by virtue of metal oxide supported solid superacid and relates to a chemical synthesis process. The metal oxide supported solid superacid is taken as a catalyst, the metal oxide supported solid superacid, phthalic anhydride and excessive anhydrous dry benzene are added into an acidproof high pressure kettle, and a Friedel-Crafts acylation reaction, namely an o-benzoylbenzoic acid synthesis reaction, is carried out; after the reaction is finished, the mixture containing the o-benzoylbenzoic acid product is heated, so that the o-benzoylbenzoic acid product is fully dissolved in benzene, then vacuum filtering and separation are carried out to recycle a solid catalyst, filter liquor is placed into a distillation device to be heated in an oil bath, so that excessive benzene is evaporated out, so that the o-benzoylbenzoic acid product is obtained. The method for catalytically synthesizing o-benzoylbenzoic acid by virtue of the metal oxide supported solid superacid has the advantages that the metal oxide supported solid superacid with high catalytic activity is taken as a catalyst, an aluminium trichloride catalyst in the Friedel-Crafts acylation reaction in the traditional anthraquinone synthesis method is replaced, pollution is hardly caused, the method for catalytically synthesizing o-benzoylbenzoic acid is environment-friendly, the solid superacid is easy to recycle, and the solid superacid can be repeatedly used with high activity.
Description
Technical field
The present invention relates to chemical synthesis process, particularly the synthesis technical field of o-benzoylbenzoic acid.
Background technology
Anthraquinone is widely used in the fields such as printing and dyeing, medicine, papermaking, agricultural chemicals as a kind of important industrial chemicals and organic intermediate.The major industry method that China produces anthraquinone is Phthalic Anhydride and two-step approach, and anthraquinone two-step synthesis method refers to first uses anhydrous AlCl
3make catalyzer, the Friedel-Crafts acylation reaction of catalysis benzene and phthalic anhydride, generate o-benzoylbenzoic acid, and then generate anthraquinone with vitriol oil dehydration closed-loop.The method need consume a large amount of AlCl
3with the vitriol oil; equipment corrosion is serious; and produce a large amount of spent acid contaminate environment; therefore find new catalyst particularly important to replace aluminum chloride and sulphuric acid catalysis to synthesize anthraquinone, and the improvement of phthalic anhydride two-step synthesis method mainly concentrates in the improvement of the first step Friedel-Crafts acylation reaction catalyzer.
Solid super-strong acid overcomes the shortcoming of liquid strong acid, is easily separated with liquid-phase reaction system as catalyzer, recyclablely reuses.In heterogeneous catalytic reaction, metal oxide-loaded type solid super strong acid heat stability is obviously better than other catalyzer of the same type, and corrosion device, the advantage such as free from environmental pollution receive increasing concern because its catalytic activity is high, selectivity is good, active ingredient not easily runs off, not.
The research of metal oxide-loaded type solid super-strong acid is just becoming recent domestic and is seeking one of focus of novel green effective catalyst, and has been widely used in the aspects such as alkane isomerization, alkylation, olefin oligomerization, cracking, acidylate, esterification and dehydration of alcohols.But the research replacing Friedel-Crafts acylation reaction used catalyst aluminum chloride in conventional synthesis anthraquinone process with metal oxide-loaded type solid super-strong acid but has no report always.Therefore, metal oxide-loaded type solid superacid as catalyst synthesis o-benzoylbenzoic acid is significant to " green chemical industry " future development for its suitability for industrialized production.
Summary of the invention
The object of the invention is to propose a kind of eco-friendly o-benzoylbenzoic acid green synthesis process with prospects for commercial application.
Technical solution of the present invention is: with metal oxide-loaded type solid super-strong acid for catalyzer, be added in acidproof autoclave with Tetra hydro Phthalic anhydride together with excessive anhydrous dry benzene, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition; After reaction terminates, product is fully dissolved in benzene the mixture heating comprising product, then isolated by vacuum filtration reclaims solid catalyst, and filtrate is put into water distilling apparatus oil bath heating and steamed excessive benzene, obtains product o-benzoylbenzoic acid.
As synthesis catalyzer that o-benzoylbenzoic acid uses, in metal oxide-loaded type solid super-strong acid, carrier is ZrO
2, the metal oxide active component of load is WO
3, MoO
3.
The solid super acid catalyst reclaimed in the present invention is through manipulation of regeneration and can be recycled after vacuum-drying.The present invention adopts the metal oxide-loaded type solid super-strong acid of high catalytic activity as catalyzer; replace Friedel-Crafts acylation reaction used catalyst aluminum chloride in conventional synthesis anthraquinone process; not only " three wastes " pollute few; environmentally friendly; and solid super acid catalyst reclaiming is easy; high reactivity can be kept to reuse, on the basis of Optimal reaction conditions, thus propose the green synthesis process of o-benzoylbenzoic acid.As can be seen here, metal oxide-loaded type solid super-strong acid is used for o-benzoylbenzoic acid synthesis and there is good prospects for commercial application, higher economic benefit and social benefit can be produced.
Separately, the molar ratio of Tetra hydro Phthalic anhydride of the present invention and anhydrous dry benzene is 1: 3 ~ 7; The molar ratio of described Tetra hydro Phthalic anhydride and metal oxide-loaded type solid super-strong acid is 1: 0.1 ~ 0.5.The consumption of reclaiming catalyzer is identical with the consumption of live catalyst.
Embodiment
One, metal oxide-loaded type solid super-strong acid is prepared
By a certain amount of ZrOCl
28H
2o mixes with a certain proportion of ammonium metawolframate (or ammonium molybdate) solution, drips ammoniacal liquor under agitation, regulates pH to 8 ~ 9, still aging, filters and washs to can't detect Cl
?ion.Metal oxide-loaded type solid super-strong acid WO is obtained through high-temperature roasting 3h after 110 DEG C of dryings
3/ ZrO
2or MoO
3/ ZrO
2.Stand-by.
Two, o-benzoylbenzoic acid is synthesized:
Embodiment 1:
9.61g Tetra hydro Phthalic anhydride, the anhydrous dry benzene of 31.2mL and 2.27g metal oxide-loaded type solid super-strong acid WO is added in for the acidproof autoclave of rhythmic reaction
3/ ZrO
2, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition.
After reaction terminates, the mixture comprising product is heated to 40 ~ 60 DEG C, product is fully dissolved in benzene, then isolated by vacuum filtration reclaims solid catalyst, filtrate is put into water distilling apparatus oil bath heating and is steamed excessive benzene, obtains product o-benzoylbenzoic acid, productive rate 75.6%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 2:
9.61g Tetra hydro Phthalic anhydride, the anhydrous dry benzene of 31.2mL and 2.16g metal oxide-loaded type solid super-strong acid MoO is added in for the acidproof autoclave of rhythmic reaction
3/ ZrO
2, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition.
After reaction terminates, the mixture comprising product is heated to 40 ~ 60 DEG C, product is fully dissolved in benzene, then isolated by vacuum filtration reclaims solid catalyst, filtrate is put into water distilling apparatus oil bath heating and is steamed excessive benzene, obtains product o-benzoylbenzoic acid, productive rate 71.5%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 3:
9.61g Tetra hydro Phthalic anhydride, the anhydrous dry benzene of 35.1mL and 2.27g metal oxide-loaded type solid super-strong acid WO is added in for the acidproof autoclave of rhythmic reaction
3/ ZrO
2, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition.
After reaction terminates, the mixture comprising product is heated to 40 ~ 60 DEG C, product is fully dissolved in benzene, then isolated by vacuum filtration reclaims solid catalyst, filtrate is put into water distilling apparatus oil bath heating and is steamed excessive benzene, obtains product o-benzoylbenzoic acid, productive rate 74.5%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 4:
9.61g Tetra hydro Phthalic anhydride, the anhydrous dry benzene of 31.2mL and 2.65g metal oxide-loaded type solid super-strong acid WO is added in for the acidproof autoclave of rhythmic reaction
3/ ZrO
2, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition.
After reaction terminates, the mixture comprising product is heated to 40 ~ 60 DEG C, product is fully dissolved in benzene, then isolated by vacuum filtration reclaims solid catalyst, filtrate is put into water distilling apparatus oil bath heating and is steamed excessive benzene, obtains product o-benzoylbenzoic acid, productive rate 74.9%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 5:
Add the metal oxide-loaded type solid super-strong acid WO of 9.61g Tetra hydro Phthalic anhydride, the anhydrous dry benzene of 31.2mL and 2.27g reclaiming in for the acidproof autoclave of rhythmic reaction
3/ ZrO
2, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition.
After reaction terminates, the mixture comprising product is heated to 40 ~ 60 DEG C, product is fully dissolved in benzene, then isolated by vacuum filtration reclaims solid catalyst, filtrate is put into water distilling apparatus oil bath heating and is steamed excessive benzene, obtains product o-benzoylbenzoic acid, productive rate 75.3%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
As seen from the above-described embodiment, in o-benzoylbenzoic acid building-up reactions, with metal oxide-loaded type solid super-strong acid WO
3/ ZrO
2target product productive rate is obtained higher as catalyzer.
Claims (4)
1. the method for metal oxide-loaded type solid superacid as catalyst synthesis o-benzoylbenzoic acid, with Tetra hydro Phthalic anhydride and anhydrous dry benzene for raw material, carry out Friedel-Crafts acylation reaction, it is characterized in that with metal oxide-loaded type solid super-strong acid for catalyzer, Tetra hydro Phthalic anhydride is added in acidproof autoclave together with excessive anhydrous dry benzene, heat temperature raising, carries out Friedel-Crafts acylation reaction and o-benzoylbenzoic acid building-up reactions under 1.5 ~ 4MPa pressure, 200 ~ 230 DEG C of temperature condition; After reaction terminates, make product be dissolved in benzene the mixture heating comprising product, then isolated by vacuum filtration reclaims solid catalyst, and filtrate is put into water distilling apparatus oil bath heating and steamed excessive benzene, obtains product o-benzoylbenzoic acid; In described metal oxide-loaded type solid super-strong acid, carrier is ZrO
2, the metal oxide active component of described load is WO
3, MoO
3.
2. method according to claim 1, is characterized in that the molar ratio of described Tetra hydro Phthalic anhydride and anhydrous dry benzene is 1: 3 ~ 7.
3. method according to claim 1, is characterized in that the molar ratio of described Tetra hydro Phthalic anhydride and metal oxide-loaded type solid super-strong acid is 1: 0.1 ~ 0.5.
4. method according to claim 1, is characterized in that the mixture comprising product to be heated to 40 ~ 60 DEG C, product is dissolved in benzene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379092A (en) * | 1980-12-16 | 1983-04-05 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the preparation of anthraquinone and its substituted derivatives |
| US4496760A (en) * | 1982-09-01 | 1985-01-29 | Pcuk Produits Chimiques Ugine Kuhlmann | Process of decomposition of a complex of ortho-benzoyl benzoic acid, hydrogen fluoride and boron trifluoride |
| US4666632A (en) * | 1986-07-08 | 1987-05-19 | The Halcon Sd Group, Inc. | Process for the preparation of anthraquinone |
| CN101973876A (en) * | 2010-10-12 | 2011-02-16 | 扬州大学 | Synthesis method of acetylsalicylic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4781862A (en) * | 1986-07-08 | 1988-11-01 | Montvale Process Company, Inc. | Process for the preparation of anthraquinone |
-
2013
- 2013-10-17 CN CN201310486773.0A patent/CN103524323B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379092A (en) * | 1980-12-16 | 1983-04-05 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the preparation of anthraquinone and its substituted derivatives |
| US4496760A (en) * | 1982-09-01 | 1985-01-29 | Pcuk Produits Chimiques Ugine Kuhlmann | Process of decomposition of a complex of ortho-benzoyl benzoic acid, hydrogen fluoride and boron trifluoride |
| US4666632A (en) * | 1986-07-08 | 1987-05-19 | The Halcon Sd Group, Inc. | Process for the preparation of anthraquinone |
| CN101973876A (en) * | 2010-10-12 | 2011-02-16 | 扬州大学 | Synthesis method of acetylsalicylic acid |
Non-Patent Citations (3)
| Title |
|---|
| Friedel–Crafts acylation of toluene catalyzed by solid superacids;Kazushi Arata等;《Applied Catalysis A: General》;20000501;213–219 * |
| Friedel–Crafts Benzoylation of Alkylbenzenes with Benzoic Anhydride Catalyzed by Solid Superacids;Hideo Nakamura等;《Bull. Chem. Soc. Jpn》;20041009;1893–1896 * |
| 催化合成邻苯甲酰苯甲酸的研究;周千名等;《湖南化工》;19940228(第2期);32-35 * |
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