CN108276273A - A kind of method that metal oxide oxidation catalyst oxidation prepares benzoic acid - Google Patents
A kind of method that metal oxide oxidation catalyst oxidation prepares benzoic acid Download PDFInfo
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- CN108276273A CN108276273A CN201810191982.5A CN201810191982A CN108276273A CN 108276273 A CN108276273 A CN 108276273A CN 201810191982 A CN201810191982 A CN 201810191982A CN 108276273 A CN108276273 A CN 108276273A
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- toluene
- catalyst
- acetate
- benzoic acid
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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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Abstract
The invention discloses a kind of methods that metal oxide oxidation catalyst oxidation prepares benzoic acid.It is as follows：Step 1), by toluene, catalyst, ligand, oxidant and additive in a solvent, react 4~15h at 70~110 DEG C of temperature, the gauge pressure of 1.0 5.0MPa；Wherein：The catalyst is any in cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate, manganese nitrate, acetylacetone cobalt, ferric acetyl acetonade or ammonium ceric nitrate；The oxidant is any in air, oxygen or hydrogen peroxide；Additive is any in sodium carbonate, sodium acetate or sodium hydroxide；Step 2), after oxidation reaction, filtering removal catalyst adds extraction agent and water, and the organic phase obtained after extraction is concentrated, purifying obtains benzoic acid.The present invention is environmentally protective, and reaction condition is mild, product yield high.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, it is related to a kind of method of synthesizing benzoic acids more particularly to a kind of metal
The method that oxide catalyst oxidation prepares benzoic acid.
Background technology
Benzoic acid also known as benzoic acid are colourless, tasteless flat crystal.122.13 DEG C of fusing point, 249 DEG C of boiling point are relatively close
Spend 1.2659 (15/4 DEG C).It distils rapidly at 100 DEG C, its steam has very strong irritation, easily causes to cough after sucking.It is micro-
It is dissolved in water, is soluble in the organic solvents such as ethyl alcohol, ether.Benzoic acid is weak acid, stronger than aliphatic acid.Their chemical property is similar,
Can forming salt, ester, carboxylic acid halides, amide, acid anhydrides etc., be all not easy to be aoxidized.Benzoic acid and sodium benzoate can be used as latex, toothpaste, fruit
The bacteriostatic agent of sauce or other food can also make the mordant of dyeing and red ink paste used for seals.It is also used as the intermediate of pharmacy and dyestuff, is used
In producing plasticizer and fragrance etc., also as the antirust agent of steel equipment.
The synthetic method of benzoic acid includes mainly：
(1) the direct liquid phase oxidation of toluene：The technique is divided into three parts：(toluene partial oxidation generates for oxidation reaction part
Benzoic acid), distillation fraction (removing unreacted toluene), rectifying part (first remove light component, after obtain benzoic acid, it is remaining
Heavy constituent goes benzyl ester tower to handle).(Abdel-Rahman L H,Abu-Dief A M,Adam M S S,et al.Some New
Nano-sized Mononuclear Cu(II)Schiff Base Complexes:Design,Characterization,
Molecular Modeling and Catalytic Potentials in Benzyl Alcohol Oxidation[J]
.Catalysis Letters,2016,146(8):1-24.Tang S,Liang B,Wu P,et al.Kinetics of
liquid-phase oxidation of toluene to benzoic acid by air[J].Chemical Reaction
Engineering&Technology,2005.Yu L,Hong W,Zhang Z H,et al.Intramolecular
Sandwich Complexation of Light Lanthanoid Nitrates with Bis(benzo-12-crown-4)
s:Enhanced Selectivity for Eu[J].Journal of Inclusion Phenomena and
Macrocyclic Chemistry,1999,34(2):189-197.)。
This three parts is all intermittently operated, and there is the energy used and generation waste heat all there is wave crest, trough phenomenon, react
Heat cannot efficiently use, and rectifying part high energy consumption, equipment is not only small and more, the deficiencies of, while food pharmaceutical grade is using water-soluble
Method produces, and consumes a large amount of tap water and steam, wastewater flow rate is big and processing is difficult.
(2) phthalic anhydride heats decarboxylation method：(Kumagai S,Grause G,Kameda T,et
al.Improvement of the Benzene Yield During Pyrolysis of Terephthalic Acid
Using a CaO Fixed-Bed Reactor[J].Industrial&Engineering Chemistry Research,
2011,50(11).Kumagai S,Grause G,Kameda T,et al.Decomposition of Gaseous
Terephthalic Acid in the Presence of CaO[J].Industrial&Engineering Chemistry
Research,2011,50(4):1831-1836.Masuda T,Miwa Y,Tamagawa A,et al.Degradation of
waste poly(ethylene terephthalate)in a steam atmosphere to recover
terephthalic acid and to minimize carbonaceous residue[J].Polymer
Degradation&Stability,1997,58(3):315-320.)。
This reaction in, except main reaction in addition to also have side reaction generation, make in product contain a small amount of biphenyl, phthalic acid,
Benzophenone etc..It is current external small lot production pharmaceutical grade benzoic acid prevailing because usual objectionable impurities is less in product
Method, but the preparation manipulation process of high purity product is cumbersome, it is of high cost.
(3) benzotrichloride Hydrolyze method：Toluene and chlorine carry out optical chlorinating reaction under the conditions of certain temperature and pressure, then again
It carries out that benzoic acid crude product is obtained by the reaction with water.(Tang Shengwei, Liang Bin, Wu Pan wait the dynamics of liquid-phase oxidation of toluene reaction process
Study [J] Chemical Reaction Engineerings and technique, 2005,21 (4):333-339.).
This method step is more, and by-product is more and hardly possible detaches, and needs to consume chlorine, the environmental pollutions such as HCl/water solution of discharge
Seriously, therefore, benzaldehyde or benzyl alcohol by-product, the supplement side that object recycles is made in this method typically just chlorination toluene hydrolysis
Method.
Invention content
For the problems of the prior art, the purpose of the present invention is to provide a kind of using toluene as the catalysis oxidation system of raw material
The method of standby high-quality benzoic acid.The method of the present invention is catalyst using metal oxide, and catalytic activity is high, reaction product yield
Height, reaction condition is mild, environmentally protective.
The present inventor passes through the study found that using toluene as raw material, in the common of organo-metallic catalyst, ligand and oxidant
Under effect, the benzoic acid of high-quality is produced, reactive chemistry formula is as follows：
Technical scheme of the present invention is specifically described as follows.
A kind of method that metal oxide oxidation catalyst oxidation prepares benzoic acid, is as follows：
Step 1), by toluene, catalyst, ligand, oxidant and additive in a solvent, in 70~110 DEG C of temperature,
4~15h is reacted under the gauge pressure of 1.0-5.0MPa；Wherein：The catalyst be selected from cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate,
It is any in manganese nitrate, acetylacetone cobalt, ferric acetyl acetonade or ammonium ceric nitrate；The oxidant is selected from air, oxygen or peroxide
Change any in hydrogen；Additive is any in sodium carbonate, sodium acetate or sodium hydroxide；
Step 2), after oxidation reaction, filtering removal catalyst adds extraction agent and water, is obtained after extraction
Organic phase is concentrated, purifying obtains benzoic acid.
In the present invention, in step 1), the molar ratio of catalyst and toluene is 1:1000~1:50.
In the present invention, in step 1), the molar ratio of catalyst and toluene is 1:200~1:50.
In the present invention, in step 1), ligand be selected from pyridine, 2,2- bipyridyls, Phen, triethylamine, acetylacetone,2,4-pentanedione,
It is any in EDTA or ethylenediamine；The molar ratio of ligand and toluene is 1:100~1:20.
In the present invention, in step 1), the molar ratio of ligand and toluene is 1:100~1:50.
In the present invention, in step 1), when oxidant is hydrogen peroxide, using 30wt% hydrogen peroxide, hydrogen peroxide and toluene
Molar ratio be 1:1~5:1.
In the present invention, in step 1), the molar ratio of additive and toluene is 1:100~1:10.
In the present invention, in step 1), the volume mass ratio of solvent and toluene is 1:1~20:1mL/g.
In the present invention, in step 1), reaction temperature be 70~110 DEG C, gauge pressure 1.0-2.0MPa, the reaction time be 8~
10h.When gauge pressure is 0, reaction pressure is normal pressure.
In the present invention, in step 2), extraction agent is any in ether, ethyl acetate or dichloromethane；At purifying
Reason uses column chromatography.
Compared to the prior art, the beneficial effects are mainly as follows the following aspects：
(1) the oxidation reaction stage selects organo-metallic catalyst, avoids the use of initiator, particular avoid halogen
The use of plain class initiator, can produce and obtain high-quality, the benzoic acid without containing initiator, and obtained product can be used for eating
The fields such as product, medicine, detergents and cosmetic.
(2) when oxidation reaction uses hydrogen peroxide as oxidant, product only has water, without other pollutants, has warp
The characteristics of Ji, environmental protection, green high-efficient..
(3) reaction condition of the present invention is mild, product yield high, easy to operate, easily controllable, is suitable for industrialized production.
Specific implementation mode
The content of present invention is further explained and described below by way of specific implementation mode, but case study on implementation is understood not to
Limiting the scope of the invention.
Embodiment 1
By the toluene of 0.9214g (0.01mol), the cobalt acetate of 0.0025g (1mol%), 0.005482g (1equiv)
The solvent acetic acid and 7.971 × 10 of ammonium ceric nitrate, the sodium carbonate of 0.0106g (0.1equiv) and 4mL-3G's (0.1equiv)
Pyridine ligand is put into dry reaction test tube, after being warming up to 110 DEG C, air is constantly passed through into reaction tube, in pressure
(gauge pressure) is to stop reaction under 1MPa after insulation reaction 20h, is extracted reaction system 3 times with ethyl acetate, obtained product
Solvent is removed under reduced pressure, column chromatography for separation obtains benzoic acid, obtains product 1.1480g, yield 94%.The core of obtained benzoic acid
The chemical shift of magnetic hydrogen spectrum is as follows：1H NMR (501MHz, DMSO) δ 12.97 (s, 1H), 7.96 (d, J=7.2Hz, 2H), 7.62
(t, J=7.4Hz, 1H), 7.50 (t, J=7.7Hz, 2H；The chemical shift of the carbon spectrum of obtained benzoic acid is as follows：13C NMR
(126MHz,DMSO)δ167.79(s),133.30(s),131.24(s),129.73(s),129.01(s).
Embodiment 2
By the toluene of 0.9214g (0.01mol), the cobalt acetate of 0.0025g (1mol%), 0.005482g (1equiv)
Ammonium ceric nitrate, the acetic acid sodium additives of 0.0082g (0.1equiv) and 8mL solvents diethyl malonate and 7.971 × 10-3g
The pyridine ligand of (0.1equiv), puts into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, it is noted that first checks equipment using preceding
Whether there is damage, be added solvent and raw material into hydrothermal reaction kettle container, after stirring and dissolving, when being blown into one section of nitrogen into container
Between, so that system is in inert atmosphere, hydrothermal reaction kettle lid, which is tightened, in use adds catalyst and place it in baking oven, rises
Temperature connects oxygen tank to after 100 DEG C, and it is 1MPa or so to make pressure (gauge pressure), after insulation reaction 8h, stops reaction.Wait for autoclave body certainly
It so is cooled to room temperature unlatching kettle cover, is extracted reaction system 3 times with ethyl acetate, solvent, column is removed under reduced pressure in obtained product
Chromatography obtains benzoic acid, obtains product 1.0624g, yield 87%.
Embodiment 3
By the toluene of 0.9214g (0.01mol), the cobalt acetate of 0.0025g (1mol%), 0.0060g (1.1equiv)
The sodium acetate trihydrate of ammonium ceric nitrate, 0.0272g (0.0002mol), the hydrogen peroxide and 6mL of the 30wt% of 0.015mol are molten
Agent acetic acid and 7.971 × 10-3The pyridine ligand of g (0.1equiv) is put into dry and clean pressure pipe, is warming up to 80
After DEG C, in the case where pressure (gauge pressure) is 1MPa after insulation reaction 10h, stop reaction, extracted reaction system 3 times with ethyl acetate,
Solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains benzoic acid, obtains product 1.1723g, yield 96%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention, used herein is each
A bibliography, which is hereby incorporated by reference.
Claims (10)
1. a kind of method that metal oxide oxidation catalyst oxidation prepares benzoic acid, which is characterized in that be as follows：
Step 1), by toluene, catalyst, ligand, oxidant and additive in a solvent, in 70~110 DEG C of temperature, 1.0-
5.0MPa gauge pressure under react 4~15h；Wherein：The catalyst is selected from cobalt acetate, manganese acetate, cerous acetate, cobalt nitrate, nitric acid
It is any in manganese, acetylacetone cobalt, ferric acetyl acetonade or ammonium ceric nitrate；The oxidant is selected from air, oxygen or hydrogen peroxide
In it is any；Additive is any in sodium carbonate, sodium acetate or sodium hydroxide；
Step 2), after oxidation reaction, filtering removal catalyst adds extraction agent and water, what is obtained after extraction is organic
Mutually concentrated, purifying obtains benzoic acid.
2. according to the method described in claim 1, it is characterized in that, in step 1), the molar ratio of catalyst and toluene is 1:
1000~1:50.
3. method according to claim 1 or 2, which is characterized in that in step 1), the molar ratio of catalyst and toluene is 1:
200~1:50.
4. according to the method described in claim 1, it is characterized in that, in step 1), ligand is selected from pyridine, 2,2- bipyridyls, neighbour
It is any in phenanthroline, triethylamine, acetylacetone,2,4-pentanedione, EDTA or ethylenediamine；The molar ratio of ligand and toluene is 1:100~1:20.
5. method according to claim 1 or 4, which is characterized in that in step 1), the molar ratio of ligand and toluene is 1:
100~1:50.
6. according to the method described in claim 1, it is characterized in that, in step 1), when oxidant is hydrogen peroxide, use
The molar ratio of 30wt% hydrogen peroxide, hydrogen peroxide and toluene is 1:1~5:1.
7. according to the method described in claim 1, it is characterized in that, in step 1), the molar ratio of additive and toluene is 1:100
~1:10.
8. according to the method described in claim 1, it is characterized in that, in step 1), the volume mass ratio of solvent and toluene is 1:1
~20:1mL/g.
9. according to the method described in claim 1, it is characterized in that, in step 1), reaction temperature is 70~110 DEG C, and gauge pressure is
1.0-2.0MPa, reaction time are 8~10h.
10. according to the method described in claim 1, it is characterized in that, in step 2), extraction agent is selected from ether, ethyl acetate
Or it is any in dichloromethane；Purification process uses column chromatography.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608793A (en) * | 2020-12-10 | 2021-04-06 | 河南中烟工业有限责任公司 | Preparation method and application of pyrone fragrant raw material capable of highlighting sweet taste characteristic of Chinese-style cigarette |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing phenylformic acid through liquid phase oxidation of methylbenzene |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
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2018
- 2018-03-08 CN CN201810191982.5A patent/CN108276273A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing phenylformic acid through liquid phase oxidation of methylbenzene |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608793A (en) * | 2020-12-10 | 2021-04-06 | 河南中烟工业有限责任公司 | Preparation method and application of pyrone fragrant raw material capable of highlighting sweet taste characteristic of Chinese-style cigarette |
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Application publication date: 20180713 |