CN106631756A - Method for synthesizing organic carboxylic acid under catalysis of organic strong acid - Google Patents
Method for synthesizing organic carboxylic acid under catalysis of organic strong acid Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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Abstract
The invention discloses a method for synthesizing organic carboxylic acid under catalysis of organic strong acid. The organic carboxylic acid is prepared from raw materials olefin and carbon monoxide by virtue of an oxo-synthesis method. Reaction is performed by adopting the organic carboxylic acid as a solvent and adopting the organic strong acid as a catalyst, and the organic strong acid comprises organic acid containing a fluorine or phosphorus or chlorine or bromine strong electron withdrawing group, and also comprises organic phosphonic acid with different substituents. During reaction, the solvent and the catalyst are added at one time, the system pressure of the carbon monoxide is kept at 2 to 8MPa, olefin is added in a pressure preservation process of the carbon monoxide in a manner that liquid is added in a constant pressure dropwise addition or jetting manner and gas is added in a bubbling manner, the temperature is kept at 10 to 80 DEG C during charging and reaction, the charging time is 0.2 to 2.0 hours, reaction is kept for 1.0 to 5.0 hours after charging is completed, and after reaction is ended, a target product, i.e. the organic carboxylic acid, is obtained by a posttreatment procedure comprising a hydrolysis process. According to the method, green production is completely realized.
Description
Technical field
The present invention relates to the method that the synthetic method of organic carboxyl acid, more particularly to organic acid catalyze and synthesize organic carboxyl acid,
Belong to chemical field.
Background technology
At present the producer of each production versatic acid is produced by Koch methods substantially, and Koch reactions are the one of oxo synthesis
Quasi-representative react, the fifties in last century Germany Koch and colleagues make carbonylation of olefin with strong acid catalyst, define famous
Koch reaction.The sixties U.S. Enjay companies and Exxon companies, Holland Shell companies adopt boron trifluoride for be catalyzed
Agent, realizes the industrialized production of versatic acid, the seventies Japanese national industrial research institute improvement so that reaction condition is more warmer
With, and realize industrializing the eighties.Mainly with alkene (or alcohol) and the reaction of carbon monoxide corresponding carboxylic acid of generation.With alkene and
As a example by carbon monoxide is as raw material, organic carboxyl acid is obtained in the presence of acidic.The acidic catalyst for using is with sulfuric acid
Main, sulfuric acid is large excess of in actual production technique, and general one ton of target product of production needs concentrated sulfuric acid 2-3 tons or more
Height, and when Koch synthesis is carried out with sulfuric acid catalysis, the raising of yield is often to improve the consumption of sulfuric acid as cost, in a large number
Sulfuric acid is changed into black Waste Sulfuric Acid of the concentration in 50-70% after the completion of hydrolyzing process, although the spent acid by extracting, can take off
As diluting concentrated sulfuric acid agent part reuse after color, concentration（CN104058948A, 2014）But, after extracting in actual production process
Dilute sulfuric acid still contain a small amount of organic matter, reclaim using causing olefinic polymerization degree to increase, target product yield is substantially reduced,
Production cost is improved, and spent acid loops back that consumption is very low, at maximum up to 1/3rd of spent acid yield, therefore can not be from root
Prevent the pollution of spent acid in sheet, the accumulation of a large amount of spent acid causes the production scale of associated production enterprise to be restricted.
Therefore, the new catalyst of searching replaces sulfuric acid to carry out carbonylation synthesis becomes industry urgent problem.In recent years
Come, also there is the report in terms of some correlative studys：With alkene, water and carbon monoxide as raw material, under the catalysis of concentrated acid-carbonyl copper
Synthesis versatic acid, alkene in reaction raw materials：The mol ratio of sulfuric acid is 1：（6-12）, the reaction separation method of application enhancements, necessarily
Avoid that dilute sulfuric acid discharge capacity in existing process is big, with serious pollution defect in degree（CN IO2718646 A）, but can not be from
Fundamentally prevent the pollution of spent acid, in terms of using isobutene and carbon monoxide synthesis pivalic acid, using modified strong acidic ion
Liquid improves the meltage of carbon monoxide in inorganic acid as solvent and catalyst, and the side of versatic acid is prepared under lower pressure
Method（CN 105218354 A）, due to ionic liquid it is expensive, it is difficult to realize industrialization target；Fan little Bin is using sulfonic acid tree
Fat, five silicon type borosilicate zeolites and SO4 2-/ZrO2The solid acid catalysts such as type, the conversion ratio of isobutene is up to 34.8%,
Pivalic acid yield is only capable of reaching 19.2%, does not also industrialize meaning（" Synthesis of Pivalic Acid Catalyzed by Solid Acid research ", Hebei industry
University's Master's thesis, 2002）.
The content of the invention
It is an object of the invention in overcoming current organic carboxyl acid to synthesize, environment is seriously polluted, low yield cannot industrialization
Etc. aspect exist problem, there is provided a kind of method that organic acid catalyzes and synthesizes organic carboxyl acid.
To realize the purpose of the present invention, following technical schemes are employed：Organic acid catalyzes and synthesizes the side of organic carboxyl acid
Method, including alkene and carbon monoxide is adopted for raw material, by oxo synthesis organic carboxyl acid is prepared, and described oxo synthesis refers to
Koch reacts, and described reaction adopts organic carboxyl acid for solvent, adopts organic acid and carry out for catalyst, described organic acid
Including fluorine-containing or phosphorus or the organic acid of chlorine or bromine strong electron-withdrawing group group, including fluorine replaces entirely or partially substituted carboxylic acid or sulfonic acid,
Full replacement or partially substituted carboxylic acid or sulfonic acid, bromine replace or partially substituted carboxylic acid or sulfonic acid chlorine entirely, described organic acid
Also include the organic phospho acid with different substituents, including the organic phospho acid of following structural formula：R1-PO3H2、H2O3P-(CH2)n-
PO3H2、R2-CH=CH-PO3H2、H2O3P-C(R3)OH -PO3H2, in above structural formula：N is integer；R1For alkyl or cycloalkyl；
R2For alkyl or aryl； R3For alkyl；Described alkene is the alkene that carbon number is 2-9, during reaction, solvent and catalyst one
Secondary property is added, and carbon monoxide keeps system pressure 2-8MPa, alkene liquid in carbon monoxide pressure maintaining period to adopt constant pressure dropping
Or spray regime is added, gas is added using bubbling mode, temperature is maintained at 10-80 DEG C when feeding and reacting, and feed time is
0.2-2.0 hours, after keeping 1.0-5.0 hours, reaction to terminate after the completion of charging, the postprocessing working procedures through including hydrolytic process
Obtain target product organic carboxyl acid；Further, described alkene is propylene or butylene or amylene or hexene or heptene or octene
Or nonene, if above-mentioned alkene has isomers, described alkene can also be the isomers of above-mentioned alkene；Described organic carboxylic
Acid is formic acid or acetic acid or propionic acid or butyric acid or valeric acid, if above-mentioned organic carboxyl acid has isomers, described organic carboxyl acid is
It can also be the isomers of above-mentioned organic carboxyl acid；Further, described postprocessing working procedures are：Reaction terminates rear pressure release blowing,
Solid catalyst is filtered out, reactant liquor is hydrolyzed, 40-100 DEG C of hydrolysis temperature, hydrolysis time 0.5 to 1.0 hours；Divide after hydrolysis
Liquid is separated, and organic phase vacuum distillation obtains organic carboxyl acid；Further, in reaction the feeding quantity of each material with solvent organic carboxyl acid
For radix calculating, catalyst weight consumption is the 0.05-5.0% of organic carboxyl acid weight basis；Alkene mole dosage is organic carboxyl acid
0.1-0.5 times of molar basis；Carbon monoxide keeps system pressure 2-8MPa in reaction；Further, each material in reaction
Feeding quantity is calculated by radix of solvent organic carboxyl acid, and catalyst weight consumption is the 0.1-3.0% of organic carboxyl acid weight basis；Alkene
Hydrocarbon mole dosage is 0.2-0.4 times of organic carboxyl acid molar basis；Carbon monoxide keeps system pressure 3-6MPa in reaction；Enter one
Step, in charging and reaction, temperature is maintained at 20-60 DEG C, and feed time is 0.5-1.0 hours, and 2.0- is kept after the completion of charging
4.0 hour；Further, the volume that water is added when hydrolyzing in described postprocessing working procedures is 1/8th of solvent volume consumption
To 1/2nd；Further, reaction terminates rear pressure release blowing in postprocessing working procedures, filters out solid catalyst recovery and uses；
Hydrolysis water is mutually recycled, the contained organic acid of 5 extractions of the Jing with after of circulation, continues to return circulating system.
The present invention positive Advantageous Effects be：This method can be used to synthesize the organic carboxyl acid of carbon number 4-12,
With advantages below：1st, organic carboxyl acid is adopted（Including carbon number for 1-5 straight or branched carboxylic acid, specially formic acid, acetic acid, third
Acid, butyric acid, valeric acid and its isomers, such as pivalic acid）Used as solvent and proton replenishers, reaction passes through vacuum fractionation after terminating
Solvent can be reclaimed all, simultaneously because solvent sheet provides a large amount of protons as system, it is to avoid the use of a large amount of catalyst, be made
The catalyst for obtaining catalytic amount is capable of achieving being normally carried out for reaction, greatly reduces reaction cost；2nd, green strong acid is employed
Property material replace sulfuric acid as catalyst, using the organic acid of catalytic amount, usage amount is less, and reaction system is steady, keeps away
Exempt from the generation of the side reactions such as olefinic polymerization, substantially increase the selectivity of alkene, solid catalyst Jing simple filtrations after reaction
It is i.e. recyclable and recycle, produce without spent acid, realize greenization production；3rd, the catalyst for using it is little to metal protection or
Person is corrosion-free, reduces corrective maintenance and maintenance cost；4th, solvent for use recoverable of the present invention, water is mutually followed completely after hydrolysis
Ring is used, and whole operations fully achieve greenization production without discharging of waste liquid.
Specific embodiment
Separately below using pivalic acid and new certain herbaceous plants with big flowers acid synthetic schemes as embodiment, the present invention, but the present invention are further described
Scope be not limited to these embodiments.
Embodiment 1：Fluorine-containing organic acid catalysis isobutene, carbon monoxide synthesis pivalic acid
In fixed volume autoclave（It is configured with stirring, thermometer boss, nonene feeder, carbon monoxide bottom insert canal）In, 45
Add the pivalic acid of 1.5 times of amount of isobutyl olefinic substance as solvent at DEG C, add the trifluoro second of the amount 0.1% of isobutyl olefinic substance
Acid, leads to CO gas displacement gas reactor, is then charged with CO gas to 4.0MPa, is then slowly added dropwise meter in advance
Measured isobutene, control system temperature keep 45 DEG C, drip within about 0.5 hour, then be incubated 1.5 hours, during use
Carbon monoxide keeps system pressure in 4.0MPa；After completion of the reaction pressure release, blowing, filtering catalyst, add isobutyl in reactant liquor
The deionized water of 1.5 times of the amount of olefinic substance, hydrolyzes 0.5 hour at 70 DEG C, and point liquid is separated, and lower floor's water mutually reclaims Posterior circle and makes
With upper organic phase enters rectification under vacuum operation, and front-end volatiles mutually merge reuse with water, collect target product pivalic acid, yield 84%
（Calculate by isobutene input amount）, product purity 99.0-99.9%（Agilent7890A gas chromatograph-mass spectrometers are analyzed）.
Embodiment 2：Fluorine-containing organic acid catalysis nonene, carbon monoxide synthesize new certain herbaceous plants with big flowers acid
In fixed volume autoclave（It is configured with stirring, thermometer boss, nonene feeder, carbon monoxide bottom insert canal）In, 40
Add the propionic acid of 1.5 times of amount of nonene material as solvent at DEG C, add the trifluoromethane sulfonic acid of the amount 0.1% of nonene material,
Logical CO gas replace gas reactor, are then charged with CO gas to 5.0MPa, are then slowly added dropwise metering in advance
Good nonene, control system temperature is kept for 40 DEG C, is dripped within about 0.5 hour, is then incubated 1.5 hours, during use an oxygen
Change carbon and keep system pressure in 5.0MPa；After completion of the reaction pressure release, blowing, filtering catalyst, add nonene material in reactant liquor
2.0 times of amount of deionized water, hydrolyze 1.0 hours 1 at 60 DEG C, be directly entered rectification under vacuum operation, the first cut water is abandoned
Go or reuse, reclaim the second cut solvent propionic acid, collect the new certain herbaceous plants with big flowers acid of target product, yield 85%（Calculate by nonene input amount）, produce
Product purity 99.0-99.9%（Agilent7890A gas chromatograph-mass spectrometers are analyzed）.
Embodiment 3：Alkyl phosphonic acid catalyzing iso-butane alkene, carbon monoxide synthesis pivalic acid
In fixed volume autoclave（It is configured with stirring, thermometer boss, nonene feeder, carbon monoxide bottom insert canal）In, 50
Add the pivalic acid of 2.0 times of amount of isobutyl olefinic substance as solvent at DEG C, add the hydroxyl second of the amount 0.1% of isobutyl olefinic substance
Fork di 2 ethylhexyl phosphonic acid（HEDP）, lead to CO gas displacement gas reactor, CO gas are then charged with to 5.0MPa, Ran Houhuan
Slowly the isobutene for measuring in advance is added dropwise, control system temperature is kept for 50 DEG C, dripped within about 0.5 hour, and then insulation 1.0 is little
When, during with carbon monoxide keep system pressure in 5.0MPa；Pressure release, blowing after completion of the reaction, filtering catalyst, reactant liquor
The deionized water of 2.0 times of the amount of middle addition isobutyl olefinic substance, hydrolyzes 1.0 hours at 60 DEG C, and point liquid is separated, and lower floor's water phase is returned
Receive Posterior circle to use, upper organic phase enters rectification under vacuum operation, front-end volatiles mutually merge reuse with water, collect target product spy penta
Acid, yield 80%（Calculate by isobutene input amount）, product purity 99.0-99.9%（Agilent7890A gas chromatograph-mass spectrometers point
Analysis）.
Embodiment 4：Alkyl phosphonic acid catalysis nonene, carbon monoxide synthesize new certain herbaceous plants with big flowers acid
In fixed volume autoclave（It is configured with stirring, thermometer boss, nonene feeder, carbon monoxide bottom insert canal）In, 40
Add the propionic acid of 2.0 times of amount of nonene material as solvent at DEG C, add the HEDP of the amount 0.1% of nonene material, lead to an oxidation
Carbon gas displacement gas reactor, is then charged with CO gas to 4.0MPa, is then slowly added dropwise the nonene for measuring in advance,
Control system temperature keep 40 DEG C, drip within about 0.5 hour, then be incubated 1 hour, during with carbon monoxide keep system
Pressure is in 4.0MPa；Pressure release, blowing after completion of the reaction, filtering catalyst adds 2.5 times of amount of nonene material in reactant liquor
Deionized water, hydrolyzes 1.0 hours at 60 DEG C, is directly entered rectification under vacuum operation, and the first cut water is discarded or reuse, reclaims the
Two cut solvent propionic acid, collect the new certain herbaceous plants with big flowers acid of target product, yield 82%（Calculate by nonene input amount）, product purity 99.0-
99.9%（Agilent7890A gas chromatograph-mass spectrometers are analyzed）.
Claims (8)
1. the method that organic acid catalyzes and synthesizes organic carboxyl acid, including alkene and carbon monoxide is adopted for raw material, is closed by carbonyl
Organic carboxyl acid is prepared into method, described oxo synthesis refers to that Koch reacts, it is characterised in that：Described reaction adopts organic carboxyl acid
For solvent, adopt organic acid and carry out for catalyst, described organic acid includes fluorine-containing or phosphorus or chlorine or bromine strong electron-withdrawing group
The organic acid of group, including fluorine replace entirely partially substituted carboxylic acid or sulfonic acid, chlorine replace entirely or partially substituted carboxylic acid or sulfonic acid,
Bromine replaces or partially substituted carboxylic acid or sulfonic acid entirely, and described organic acid also includes the organic phospho acid with different substituents,
Including the organic phospho acid of following structural formula：R1-PO3H2、H2O3P-(CH2)n-PO3H2、R2-CH=CH-PO3H2、H2O3P-C(R3)OH
-PO3H2, in above structural formula：N is integer；R1For alkyl or cycloalkyl； R2For alkyl or aryl； R3For alkyl；Described
Alkene is the alkene that carbon number is 2-9, and during reaction, solvent and catalyst are disposably added, and carbon monoxide keeps system pressure
2-8MPa, liquid is added alkene using constant pressure dropping or spray regime in carbon monoxide pressure maintaining period, gas adopts bubbling side
Formula is added, and temperature is maintained at 10-80 DEG C when charging and reaction, and feed time is 0.2-2.0 hours, and 1.0- is kept after the completion of charging
5.0 hours, after reaction terminates, through including that the postprocessing working procedures of hydrolytic process obtain target product organic carboxyl acid.
2. the method that organic acid according to claim 1 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Described alkene
For propylene or butylene or amylene or hexene or heptene or octene or nonene, if above-mentioned alkene has isomers, described alkene
It can also be the isomers of above-mentioned alkene；Described organic carboxyl acid is formic acid or acetic acid or propionic acid or butyric acid or valeric acid, if above-mentioned
Organic carboxyl acid there is isomers, described organic carboxyl acid be can also be above-mentioned organic carboxyl acid isomers.
3. the method that organic acid according to claim 1 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Described rear place
Science and engineering sequence is：Reaction terminates rear pressure release blowing, filters out solid catalyst, reactant liquor is hydrolyzed, 40-100 DEG C of hydrolysis temperature, water
0.5 to 1.0 hours solution time；Point liquid is separated after hydrolysis, and organic phase vacuum distillation obtains organic carboxyl acid.
4. the method that organic acid according to claim 1 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Each thing in reaction
The feeding quantity of matter is calculated by radix of solvent organic carboxyl acid, and catalyst weight consumption is the 0.05- of organic carboxyl acid weight basis
5.0%；Alkene mole dosage is 0.1-0.5 times of organic carboxyl acid molar basis；Carbon monoxide keeps system pressure 2- in reaction
8MPa。
5. the method that organic acid according to claim 1 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Each thing in reaction
The feeding quantity of matter is calculated by radix of solvent organic carboxyl acid, and catalyst weight consumption is the 0.1- of organic carboxyl acid weight basis
3.0%；Alkene mole dosage is 0.2-0.4 times of organic carboxyl acid molar basis；Carbon monoxide keeps system pressure 3- in reaction
6MPa。
6. the method that organic acid according to claim 1 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：In charging and instead
Seasonable temperature is maintained at 20-60 DEG C, and feed time is 0.5-1.0 hours, and 2.0-4.0 hours are kept after the completion of charging.
7. the method that organic acid according to claim 3 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Described rear place
The volume that water is added when hydrolyzing in science and engineering sequence is 1st/1 to two/8ths of solvent volume consumption.
8. the method that organic acid according to claim 3 catalyzes and synthesizes organic carboxyl acid, it is characterised in that：Postprocessing working procedures
Middle reaction terminates rear pressure release blowing, filters out solid catalyst recovery and uses；Hydrolysis water is mutually recycled, and circulates 5 Jing with after
The contained organic acid of extraction, continues to return circulating system.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317194A (en) * | 2018-09-30 | 2019-02-12 | 安阳师范学院 | A kind of catalyst and application for one-step synthesis Cyclic dipeptides |
| CN111359659A (en) * | 2020-03-17 | 2020-07-03 | 西南化工研究设计院有限公司 | Catalyst for synthesizing tertiary carboxylic acid, application of catalyst and synthetic method of tertiary carboxylic acid |
| CN113548957A (en) * | 2021-07-30 | 2021-10-26 | 西南化工研究设计院有限公司 | Production method of tertiary carbonic acid |
| CN114534792A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Method for preparing organic carboxylic acid by olefin hydrocarboxylation |
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| CN1324340A (en) * | 1998-10-22 | 2001-11-28 | 荷兰解决方案研究有限公司 | Process and the manufacture of alpha, alpha-branched carboxylic acids |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317194A (en) * | 2018-09-30 | 2019-02-12 | 安阳师范学院 | A kind of catalyst and application for one-step synthesis Cyclic dipeptides |
| CN111359659A (en) * | 2020-03-17 | 2020-07-03 | 西南化工研究设计院有限公司 | Catalyst for synthesizing tertiary carboxylic acid, application of catalyst and synthetic method of tertiary carboxylic acid |
| CN111359659B (en) * | 2020-03-17 | 2021-02-09 | 西南化工研究设计院有限公司 | Catalyst for synthesizing tertiary carboxylic acid, application of catalyst and synthetic method of tertiary carboxylic acid |
| CN114534792A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Method for preparing organic carboxylic acid by olefin hydrocarboxylation |
| CN114534792B (en) * | 2020-11-24 | 2023-06-16 | 中国科学院大连化学物理研究所 | Method for preparing organic carboxylic acid by olefin hydrocarboxylation |
| CN113548957A (en) * | 2021-07-30 | 2021-10-26 | 西南化工研究设计院有限公司 | Production method of tertiary carbonic acid |
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