CN105481685A - One-step method for synthesizing salicylic acid with phenol and supercritical carbon dioxide - Google Patents
One-step method for synthesizing salicylic acid with phenol and supercritical carbon dioxide Download PDFInfo
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- CN105481685A CN105481685A CN201410527330.6A CN201410527330A CN105481685A CN 105481685 A CN105481685 A CN 105481685A CN 201410527330 A CN201410527330 A CN 201410527330A CN 105481685 A CN105481685 A CN 105481685A
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- phenol
- supercritical
- step synthesis
- potassium carbonate
- salicylic acid
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- 238000000034 method Methods 0.000 title claims abstract description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 15
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title abstract description 8
- 229960004889 salicylic acid Drugs 0.000 title abstract description 8
- 239000001569 carbon dioxide Substances 0.000 title abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 5
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 16
- 235000015320 potassium carbonate Nutrition 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 235000011181 potassium carbonates Nutrition 0.000 claims description 14
- 229960001860 salicylate Drugs 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 24
- 230000009466 transformation Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 229960004025 sodium salicylate Drugs 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSVICRMDTZSTDC-UHFFFAOYSA-N 2-acetyloxybenzoic acid Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CC(=O)OC1=CC=CC=C1C(O)=O LSVICRMDTZSTDC-UHFFFAOYSA-N 0.000 description 1
- AZEIRPAUJXANCS-UHFFFAOYSA-N 4-ethoxybenzamide Chemical compound CCOC1=CC=C(C(N)=O)C=C1 AZEIRPAUJXANCS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- -1 Xantimetten Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YEVMULNVFDCUTD-UHFFFAOYSA-L disodium 2-oxido-5-[(4-sulfophenyl)diazenyl]benzoate Chemical compound OC1=C(C(=O)[O-])C=C(C=C1)N=NC1=CC=C(C=C1)S(=O)(=O)[O-].[Na+].[Na+] YEVMULNVFDCUTD-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PYOZTOXFQNWBIS-UHFFFAOYSA-N phenol;sodium Chemical compound [Na].OC1=CC=CC=C1 PYOZTOXFQNWBIS-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a one-step method for synthesizing salicylic acid with phenol and supercritical carbon dioxide, and relates to the technical field of salicylic acid synthesis. According to the method, supported potassium carbonate is adopted as a catalyst, and salicylic acid is synthesized with phenol and supercritical carbon dioxide. According to the invention, supported potassium carbonate is adopted as the catalyst, such that the product can be easily separated from the catalyst. A traditional process flow is simplified, and pickling and washing processes in the traditional processes are eliminated, such that the method is a green and clean production process. With the method, phenol conversion rate and salicylic acid selectivity are improved, and continuous production is realized. With the method, the phenol conversion rate can reach 100%, and the salicylic acid selectivity is up to 99.3%.
Description
Technical field
The present invention relates to a kind of by phenol and the salicylic method of supercritical co one-step synthesis, belong to Whitfield's ointment synthesis technical field.
Background technology
Whitfield's ointment has another name called salicylic acid, is the important intermediate in the fields such as medicine, dyestuff, chemical industry preparation.In medicine industry, Whitfield's ointment is mainly used in the production of the medicines such as ethoxybenzamide, Xantimetten, acetylsalicylic acid (acetylsalicylic acid); In dyestuffs industries, Whitfield's ointment is for the preparation of chrome fast yellow rd, direct brown 3G N, acid chrome yellow etc.; Whitfield's ointment also can be used as vulcanization of rubber delayer and disinfection preservative etc.
Known salicylic synthetic method is all take phenol as raw material, is first reacted into phenol sodium with sodium hydroxide solution, then passes into carbonic acid gas at normal pressure or middle pressure and carry out carboxylation reaction, then obtain Whitfield's ointment with sulfuric acid acidation.Its shortcoming is that per pass conversion is low, environmental pollution is large, phenol consumption and to recycle energy consumption large etc.
Chinese patent CN1733684 proposes a kind of novel supercritical phase salicylic acid synthesis process.Phenol and sodium hydroxide solution neutralize and make phenol sodium salt by this technique, dry, grind solid sodium phenol as reactant.In autoclave, with sodium phenylate and carbonic acid gas for reactant, generate sodium salicylate through overcritical homogeneous phase carboxylation reaction, acidifying obtains Whitfield's ointment.High purity bigcatkin willow acid product is obtained after refining further.Gas-solid phase inhomogeneous reaction in traditional technology is become homogeneous reaction by the method, and service temperature reduces, speed of reaction is fast, phenol consumption reduces.Its shortcoming still needs to carry out acidifying, water washing process, and environmental pollution is large; In the preparation process of sodium phenylate, sodium phenylate need be carried out repeatedly drying, grind with unwatering, flow process is loaded down with trivial details.
Chinese patent CN200410046076 proposes one with phenol, calcium hydroxide, carbonic acid gas, sulfuric acid for the salicylic method of Material synthesis.Concrete grammar adds metabisulfite solution in phenol, then with calcium hydroxide reaction, produce calcium phenylate or calcium sulfate simultaneously, finally can obtain sodium phenylate solution and calcium sulfate; After the filtrate obtained and sodium phenylate dehydration, pass into carbonic acid gas, carboxylation generates sodium salicylate; By the sodium salicylate of acquisition and sulfuric acid reaction, obtain Whitfield's ointment and sodium sulfate; The metabisulfite solution of acquisition is used for the raw material of next reaction.The advantage of the method replaces sodium hydroxide with calcium hydroxide at a low price, and recycle sodium sulfate reduces production cost, but this reaction sulfuric acid dosage is large, three industrial wastes and environmental pollution weight.
It take ionic liquid as the method for catalyzer salicylate that Chinese patent CN101811962 discloses a kind of.Ionic liquid, phenol add in autoclave by the method, pass into cooled carbonic acid gas and react after sealing.Its advantage is by phenol and carbon dioxide one-step salicylate, is a kind of atomic economy reaction, and technique is simple, environmental friendliness, catalyzer and unreacted raw material can recycle and reuse.Shortcoming is that ionic-liquid catalyst is expensive, and at high temperature easily decomposes, and is not suitable for industrial production.
In the prior art, Xu Mingxian etc. are " salt of wormwood catalysis of phenol is at supercritical CO
2the experimental study of middle salicylate " [J]. colleges and universities' chemical engineering journal, 2011 (3); TakayukiIijima is at " K
2cO
3-catalyzeddirectsynthesisofsalicylicacidfromphenolandsupe rcriticalCO
2" to each provide a kind of take salt of wormwood as the method for catalyzer, phenol and carbon dioxide one-step salicylate to [J] .AppliedCatalysisA:General345 (2008) 12-17, Whitfield's ointment yield 68.3%, selectivity 98.5%.The method technique is simple, but aftertreatment is complicated, and catalyzer is difficult to recycle and reuse.
Above-mentioned Whitfield's ointment synthetic method is all carry out in autoclave, belongs to indirect or semi-successive cultivation technique, cannot realize continuous prodution.
Summary of the invention
The object of the present invention is to provide a kind of by phenol and the salicylic method of supercritical co one-step synthesis, this process simplify conventional process flow, improve the transformation efficiency of phenol and salicylic selectivity, achieve continuous prodution.
Of the present invention is with load salt of wormwood for catalyzer by phenol and the salicylic method of supercritical co one-step synthesis, by phenol and supercritical co salicylate.
Phenol and supercritical co continue through fixed-bed tube reactor, can realize continuous prodution.
Described load potassium carbonate catalyst, after active ingredient salt of wormwood is mixed with homogeneous solution, is prepared from by kneading method.After salt of wormwood homogeneous solution mixes with carrier, binding agent, kneading, shaping, dry, roasting, obtained finished catalyst.
Described load potassium carbonate catalyst is made up of the raw material of following weight percentage: salt of wormwood 10% ~ 25%, carrier 70% ~ 89%, binding agent 1% ~ 5%.
Described load potassium carbonate catalyst carrier is one or more in aluminum oxide, silicon oxide, gac or molecular sieve, preferred gac.
The binding agent of described load potassium carbonate catalyst is one or more in diluted acid, Attapulgite or aluminium glue.
Described load potassium carbonate catalyst profile is bar shaped or spherical.
The technique of described salicylate is successive reaction, and supercritical co consumption is much larger than phenol, and load potassium carbonate catalyst loadings is determined by fixed-bed tube reactor size used.
In the technique of described salicylate, temperature of reaction is 160 ~ 200 DEG C, preferably 180 DEG C ~ 190 DEG C.
In the technique of described salicylate, reaction pressure is 7.6 ~ 10Mpa, preferred 8Mpa.
In the technique of described salicylate, reaction velocity is 0.1 ~ 2h
-1, preferably 0.3 ~ 0.5h
-1.
Supercritical co has the special ability of dissolving other materials, and the Whitfield's ointment generated in reaction is dissolved in wherein.The present invention adopts loading type salt of wormwood as catalyzer, makes reaction product and catalyst separating simply, simplifies traditional technology, achieve the recycle and reuse of catalyzer.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention adopts loading type salt of wormwood as catalyzer, makes product and catalyst separating simple, simplifies conventional process flow, and eliminates pickling in traditional technology, water washing process, belongs to green process for cleanly preparing;
(2) invention increases the transformation efficiency of phenol and salicylic selectivity, achieve continuous prodution.Phenol conversion can reach 100%, and salicylic selectivity is up to 99.3%.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but do not limit enforcement of the present invention.
Raw materials usedly be commercially available prod.
The preparation of load potassium carbonate catalyst:
Salt of wormwood is mixed with the certain mass mark aqueous solution by the first step; Carrier and binding agent mix by second step; Solution of potassium carbonate joins in the mixture of carrier and caking agent by the 3rd step, mediates evenly, extruded moulding.After catalyzer drying at room temperature for some time after shaping, 500 DEG C of roasting 5h, obtain load potassium carbonate catalyst.
Embodiment 1
Take gac as carrier, aluminium glue prepares the catalyzer of different salt of wormwood charge capacity for binding agent.In fixed-bed tube reactor, temperature 190 DEG C, pressure 8Mpa, air speed 0.3h
-1under condition, by phenol and supercritical co salicylate, investigate different salt of wormwood charge capacity Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affects.Concrete outcome is in table 1.
Table 1 different salt of wormwood charge capacity Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect
Embodiment 2
With salt of wormwood charge capacity 15%, other condition is with embodiment 1, and investigation different carriers Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect.Concrete outcome is in table 2.
Table 2 different carriers Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect
Whitfield's ointment building-up reactions:
Take gac as carrier, the catalyst loading that salt of wormwood charge capacity 15% obtains is in fixed-bed tube reactor, and phenol and supercritical co continue through reactor and generate Whitfield's ointment.Investigate differing temps, pressure, air speed Pyrogentisinic Acid transformation efficiency and Whitfield's ointment optionally to affect.
Embodiment 3
Under catalyzer, reaction pressure, air speed same case, investigation differential responses temperature Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect in table 3.
Table 3 differing temps Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect
Embodiment 4
Under catalyzer, temperature, air speed same case, investigation differential responses pressure Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect in table 4.
Table 4 pressure Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect
Embodiment 5
Under catalyzer, temperature of reaction, pressure same case, investigation differential responses air speed Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect in table 5.
Table 5 air speed Pyrogentisinic Acid's transformation efficiency and Whitfield's ointment optionally affect
Claims (9)
1. by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: with load salt of wormwood for catalyzer, by phenol and supercritical co salicylate.
2. according to claim 1 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: load potassium carbonate catalyst, after active ingredient salt of wormwood is mixed with homogeneous solution, is prepared from by kneading method.
3. according to claim 1 and 2 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: load potassium carbonate catalyst is made up of the raw material of following weight percentage: salt of wormwood 10% ~ 25%, carrier 70% ~ 89%, binding agent 1% ~ 5%.
4. according to claim 3 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: load potassium carbonate catalyst carrier is one or more in aluminum oxide, silicon oxide, gac or molecular sieve.
5. according to claim 4 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: load potassium carbonate catalyst carrier is gac.
6. according to claim 3 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: the binding agent of load potassium carbonate catalyst is one or more in diluted acid, Attapulgite or aluminium glue.
7. according to claim 1 and 2 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: be 160 ~ 200 DEG C by the temperature of reaction of phenol and supercritical co salicylate.
8. according to claim 1 and 2 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: be 7.6 ~ 10Mpa by the reaction pressure of phenol and supercritical co salicylate.
9. according to claim 1 and 2 by phenol and the salicylic method of supercritical co one-step synthesis, it is characterized in that: be 0.1 ~ 2h by the reaction velocity of phenol and supercritical co salicylate
-1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410527330.6A CN105481685B (en) | 2014-10-09 | 2014-10-09 | By phenol and the salicylic method of supercritical carbon dioxide one-step synthesis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410527330.6A CN105481685B (en) | 2014-10-09 | 2014-10-09 | By phenol and the salicylic method of supercritical carbon dioxide one-step synthesis |
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| CN105481685B CN105481685B (en) | 2018-03-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403465A (en) * | 2022-05-20 | 2022-11-29 | 湖南工程学院 | Preparation method for synthesizing organic carboxylic ester from carbon dioxide and olefin |
| CN115806480A (en) * | 2022-12-02 | 2023-03-17 | 华夏碧水环保科技股份有限公司 | Salicylic acid production method by comprehensively utilizing wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996354A (en) * | 1988-09-21 | 1991-02-26 | Basf Aktiengesellschaft | Preparation of 2,4-dihydroxybenzoic acid |
| CN103012124A (en) * | 2012-12-26 | 2013-04-03 | 浙江大学 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
-
2014
- 2014-10-09 CN CN201410527330.6A patent/CN105481685B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996354A (en) * | 1988-09-21 | 1991-02-26 | Basf Aktiengesellschaft | Preparation of 2,4-dihydroxybenzoic acid |
| CN103012124A (en) * | 2012-12-26 | 2013-04-03 | 浙江大学 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
Non-Patent Citations (1)
| Title |
|---|
| TAKAYUKI IIJIMA AND TATSUAKI YAMAGUCHI: "K2CO3-catalyzed direct synthesis of salicylic acid from phenol and supercritical CO2", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403465A (en) * | 2022-05-20 | 2022-11-29 | 湖南工程学院 | Preparation method for synthesizing organic carboxylic ester from carbon dioxide and olefin |
| CN115403465B (en) * | 2022-05-20 | 2023-08-18 | 湖南工程学院 | A kind of preparation method of carbon dioxide and olefin synthetic organic carboxylate |
| CN115806480A (en) * | 2022-12-02 | 2023-03-17 | 华夏碧水环保科技股份有限公司 | Salicylic acid production method by comprehensively utilizing wastewater |
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| CN105481685B (en) | 2018-03-23 |
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