CN116535302A - Green preparation method suitable for industrial production of 1, 3-cyclohexanedione - Google Patents
Green preparation method suitable for industrial production of 1, 3-cyclohexanedione Download PDFInfo
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- CN116535302A CN116535302A CN202210092077.0A CN202210092077A CN116535302A CN 116535302 A CN116535302 A CN 116535302A CN 202210092077 A CN202210092077 A CN 202210092077A CN 116535302 A CN116535302 A CN 116535302A
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- cyclohexanedione
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- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009776 industrial production Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 27
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims abstract description 19
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- KAVGXOKHWPNOAL-UHFFFAOYSA-N benzene-1,3-diol;sodium Chemical compound [Na].OC1=CC=CC(O)=C1 KAVGXOKHWPNOAL-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 enol sodium salt Chemical class 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- MWPIIMNHWGOFBL-UHFFFAOYSA-N dichloromethane;toluene Chemical compound ClCCl.CC1=CC=CC=C1 MWPIIMNHWGOFBL-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FELGMEQIXOGIFQ-CYBMUJFWSA-N (3r)-9-methyl-3-[(2-methylimidazol-1-yl)methyl]-2,3-dihydro-1h-carbazol-4-one Chemical compound CC1=NC=CN1C[C@@H]1C(=O)C(C=2C(=CC=CC=2)N2C)=C2CC1 FELGMEQIXOGIFQ-CYBMUJFWSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 239000005578 Mesotrione Substances 0.000 description 1
- 239000005618 Sulcotrione Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003474 anti-emetic effect Effects 0.000 description 1
- 239000002111 antiemetic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- NPAKNKYSJIDKMW-UHFFFAOYSA-N carvedilol Chemical compound COC1=CC=CC=C1OCCNCC(O)COC1=CC=CC2=NC3=CC=C[CH]C3=C12 NPAKNKYSJIDKMW-UHFFFAOYSA-N 0.000 description 1
- 229960004195 carvedilol Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960005343 ondansetron Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- PQTBTIFWAXVEPB-UHFFFAOYSA-N sulcotrione Chemical compound ClC1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O PQTBTIFWAXVEPB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A green preparation method suitable for industrialized production of 1, 3-cyclohexanedione comprises the steps of reacting resorcinol with liquid alkali to obtain resorcinol monosodium salt, carrying out catalytic hydrogenation to obtain enol sodium salt reaction liquid, filtering to remove a catalyst, acidifying and centrifuging filtrate to obtain a wet product of 1, 3-cyclohexanedione and an acidified mother liquor, and drying the wet product to obtain a finished product of 1, 3-cyclohexanedione; the method is characterized in that an organic solvent is used for extracting acidified mother liquor, then the 1, 3-cyclohexanedione in the acidified mother liquor is reversely extracted into an aqueous phase, the reversely extracted aqueous phase is used as washing water to wash a reaction kettle and a catalyst of the next batch reaction, the reaction kettle and the catalyst are separated out in the acid adjusting process of the next batch reaction, the yield is improved, the production of products with two specifications of primary materials and mother liquor materials is avoided, the production is simplified, the purity of the 1, 3-cyclohexanedione prepared by the method is good, the yield is high, the yield of the cyclohexanedione obtained in the single reaction of washing the reaction kettle and the catalyst by using the reversely extracted aqueous phase is not lower than 94%, the purity of the cyclohexanedione is not lower than 99%, and the method is green and environment-friendly and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical industry, and particularly relates to a green preparation method suitable for industrialized production of 1, 3-cyclohexanedione.
Background
1, 3-cyclohexanedione has an active beta-dicarbonyl structure, is widely used in organic synthesis, and is an important chemical intermediate. Can synthesize the specific medicine carvedilol and the antiemetic ondansetron for protecting cardiac and cerebral vessels and treating hypertension, and is also an important intermediate for synthesizing cosmetics, polymer additives, and excellent herbicides mesotrione and sulcotrione.
1, 3-cyclohexanedione may be prepared by catalytic hydrogenation of resorcinol. At present, resorcinol is hydrogenated in an alkali solution under the action of an excessive metal catalyst, and then is acidified, so that the resorcinol is the main production method of 1, 3-cyclohexanedione. The catalytic hydrogenation method for preparing the 1, 3-cyclohexanedione has the advantages of high product yield, easy control of reaction, easy separation of products and the like.
The nickel-based catalyst has the advantages of commercial and stable supply, repeated application, low price and the like, is the most commonly adopted catalyst in the preparation of 1, 3-cyclohexanedione by the current industrial resorcinol catalytic hydrogenation method, and has the following synthetic route:
in the catalytic hydrogenation process of cyclohexanedione, the procedures of salifying, hydrogenation, acidification, centrifugation and drying are relatively conventional operation, and the technical requirement is low, so that the cyclohexanedione has good water solubility, so that a large amount of product residues exist in the centrifugal mother liquor; in addition, cyclohexanedione has thermal instability, and the product can be dimerized, byproducts appear in the process of heating and desolventizing and crystallization after extraction, so that the product turns yellow, is sticky and is scrapped.
At present, few reports about the recovery of 1, 3-cyclohexanedione products from acidified mother liquor at home and abroad are presented, and the complexing with an organic amine complexing agent, the extraction with an organic solvent, the decomplexing with strong alkali and the acid-regulating crystallization process are reported in Chinese patent application CN111302909, but the process has complex operation, waste salt is produced in the acid-regulating and alkali-regulating working sections, thereby increasing the environmental protection treatment cost, and forming products with two specifications of one-time acid-regulating material and mother liquor acid-regulating material, which is unfavorable for unified packaging and sales.
Disclosure of Invention
The invention aims to provide a green preparation method suitable for industrial production of 1, 3-cyclohexanedione, and the prepared 1, 3-cyclohexanedione has good purity, high yield and environment friendliness, is suitable for industrial production, and solves the problem of recovery of 1, 3-cyclohexanedione in acidified mother liquor in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a green preparation method of 1, 3-cyclohexanedione, which comprises the following steps:
1) Hydrogenation and acidification
In the presence of water, resorcinol reacts with liquid alkali to obtain resorcinol monosodium salt, then hydrogenation is carried out under the action of nickel, palladium or platinum catalysts to obtain reaction liquid containing enol sodium salt, after the reaction is finished, the reaction liquid is filtered, the catalysts are filtered, a reaction kettle and the catalysts are washed by deionized water, the filtrates are combined, hydrochloric acid is added for acidification until PH=2-3, 1, 3-cyclohexanedione is separated out, centrifugation is carried out to obtain a wet product of 1, 3-cyclohexanedione and acidified mother liquor, and a cyclohexanedione finished product is obtained after drying;
the reaction formula is as follows:
2) Extraction and back extraction
Extracting an acidification mother liquor containing 1, 3-cyclohexanedione by adopting an alkyl halide or ether organic solvent to obtain an acidification water phase and an organic phase; desalting and biochemically degrading the acidified water phase; adding water into the organic phase for three times to strip the 1, 3-cyclohexanedione in the organic phase into the water phase to obtain a strip water phase and a secondary organic phase;
3) Repeating the steps 1) and 2), washing the reaction kettle and the catalyst by using a back extraction water phase obtained by back extraction when filtering the reaction liquid, dissolving the residual part of the product in water, combining with the filtrate, and acidifying to separate out;
4) Combining the secondary organic phases in the step 2) and the step 3), and rectifying to recover the solvent.
Further, in the step 1), when acid is added for acidification, 25% -35% hydrochloric acid is used for regulating the pH to 2-3, and the temperature is controlled to be 10-20 ℃.
And the dosage of the organic solvent is 25-35% of the acidified mother liquor.
Preferably, in the step 2), the ether solvent is selected from one or more of diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or 1, 4-dioxane, 1, 2-dimethoxyethane and anisole; the halogenated hydrocarbon solvent is selected from one or more of dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane and 1, 1-dichloroethane.
Further, in step 1 and step 3), the catalyst is a raney nickel catalyst.
In step 4), a high boiling point solvent containing no halogen and hetero atoms is added, wherein the high boiling point solvent is a hydrocarbon solvent or an aromatic hydrocarbon solvent with a boiling point of 90-120 ℃.
Preferably, in step 4), the high boiling point solvent is toluene or petroleum ether having a boiling range of 90-120 ℃.
And, in the step 4), the residue obtained after rectification is subjected to incineration treatment.
Further, in a single reaction of washing the reaction kettle and the catalyst by using a back extraction water phase, the yield of the obtained cyclohexanedione is not less than 94%, and the purity is not less than 99%.
The inventor researches on the stability of cyclohexanedioneIt was found that [ M+1 ] appears during heating] + Impurity of=207, cyclohexanedione dimer product, process as follows:
the invention filters the reaction liquid after the reaction is finished, acidizes the filtrate, separates out the 1, 3-cyclohexanedione product, uses the organic solvent to extract the acidized mother liquor, then uses the 1, 3-cyclohexanedione in the acidized mother liquor to back extract into the water phase, uses the back extract water phase as the washing water to wash the reaction kettle and the catalyst of the next batch reaction, separates out in the acid adjusting process of the next batch reaction, controls the post-treatment process below 40 ℃, avoids the formation of cyclohexanedione dimer, improves the yield of the 1, 3-cyclohexanedione, and simultaneously avoids the production of products with two specifications of primary materials and mother liquor materials.
In the invention, after the secondary organic phase is combined, the high-boiling point solvent which does not contain halogen and hetero atoms is added for bringing out the low-boiling point solvent in the kettle residue, and the solvent does not contain halogen and hetero atoms, does not contain halogen and nitrogen oxides during incineration, and has the advantages of simple environment-friendly treatment and low cost.
Compared with the prior art, the invention has the following beneficial effects:
the invention fully utilizes the acid mother liquor and the extraction solvent generated in the preparation of the 1, 3-cyclohexanedione, re-extracts the 1, 3-cyclohexanedione in the acid mother liquor into the water phase, uses the back extraction water phase as a washing water washing kettle and a catalyst, brings part of the previous batch of products into the next batch, and precipitates in the next acid adjusting process, thereby improving the yield, ensuring that the yield of the cyclohexanedione is not lower than 95 percent, ensuring that the purity is not lower than 99 percent, avoiding the production of products with two specifications of primary material and mother liquor material, and simplifying the production.
In the post-treatment, the post-treatment process is controlled below 40 ℃, the generation of cyclohexanedione dimer is avoided, the generated organic phases are combined, the high-boiling point solvent and the low-boiling point solvent are respectively obtained through distillation, the solvent can be used mechanically, the residue in the kettle is used for incineration, and the problem of three wastes is solved.
Detailed Description
The invention is further illustrated below with reference to specific examples and comparative examples.
Examples
Hydrogenation reaction: 150g (purity 99.5%, content: 99%) of resorcinol and liquid alkali (3995 g, 15%) are put into a kettle to prepare resorcinol monosodium salt solution, 10g of commercial Raney nickel catalyst (RTH 2100) is added, air and nitrogen are discharged according to hydrogenation program, the temperature is raised to 60-65 ℃ and hydrogen is pressurized to 5-6MPa, reaction liquid containing enol sodium salt is obtained through hydrogenation, suction filtration is carried out, deionized water is used for washing the reaction kettle and the catalyst, and the filtrate is combined to obtain hydrogenation reaction liquid.
Acidifying: the hydrogenation reaction liquid is subjected to acid adjustment by 137g (36%) of hydrochloric acid until the pH value is=2-3 to obtain an acidified mother liquid, the temperature is controlled to be 10-20 ℃, the acid adjustment is finished, the stirring is carried out for half an hour, the centrifugation is carried out, and 136g (content: 90%, purity: 99.5%) of cyclohexanedione wet product and 540g of the acidified mother liquid after the centrifugation are obtained. Drying the wet product to obtain 128.2g of finished 1, 3-cyclohexanedione with purity of 1 st batch: 99.2%, content 95.5%, yield: 80.7%.
Extraction and back extraction: 150g of dichloromethane is added into the acidified mother liquor after centrifugation for three times, stirred, separated, combined to obtain 155g of organic phase and 520g of acidified water phase, and the acidified water phase is subjected to desalting and biochemical degradation treatment. 150g of deionized water is taken, the extracted organic phase is added three times, the mixture is stirred and separated, 160g of back extraction aqueous phase and 140g of secondary organic phase are obtained by combining. 50g of toluene is added into the secondary organic phase, the temperature is raised, and a rectifying column is added for rectification to obtain 120g of methylene dichloride, 40g of toluene and 10g of kettle residue. And methylene dichloride toluene is used for the next extraction step, and the residue of the kettle is subjected to incineration treatment.
Hydrogenation reaction: 150g of resorcinol and 395g (15%) of liquid alkali are put into a kettle to prepare resorcinol monosodium salt solution, 10g of commercial Raney nickel catalyst (RTH 2100) is added, air and nitrogen are discharged according to a hydrogenation program, the temperature is raised to 60-65 ℃, hydrogen is used for pressurizing to 5-6MPa, a reaction mixture is obtained through hydrogenation, the reaction kettle and the catalyst are filtered, the back extraction water phase is used for washing, and the filtrate is combined to obtain a hydrogenation reaction liquid.
Acidifying: the hydrogenation reaction liquid is subjected to acid adjustment by 137g (36%) of hydrochloric acid until the pH value is=2-3 to obtain an acidified mother liquid, the temperature is controlled to be 10-20 ℃, the acid adjustment is finished, the stirring is carried out for half an hour, the centrifugation is carried out, and 160g (content: 90%, purity: 99.4%) of cyclohexanedione wet product and 675g of the acidified mother liquid after the centrifugation are obtained. Drying the wet product to obtain 149.5g of finished 1, 3-cyclohexanedione with purity of 96.0% in batch 2: 99.5%, yield: 94.6%.
Extraction and back extraction: 150g of dichloromethane is added into the acidified mother liquor after centrifugation for three times, stirring is carried out, the organic phase 157g and the acidified water phase 655g are obtained after liquid separation, and the acidified water phase is desalted and biochemically degraded. 150g of deionized water is taken, the extracted organic phase is added, and the mixture is stirred and separated to obtain 166g of back extraction aqueous phase and 135g of secondary organic phase. 50g of toluene is added into the secondary organic phase, the temperature is raised, and a rectifying column is added for rectification to obtain 110g of methylene dichloride, 35g of toluene and 12g of kettle residue. And methylene dichloride toluene is used for the next extraction step, and the residue of the kettle is subjected to incineration treatment.
And continuing to repeat the hydrogenation reaction, acidification, extraction and back extraction processes to obtain the 3 rd batch to the 6 th batch of 1,3 rd cyclohexanedione.
According to the above experiments, a plurality of batches of experiments were performed and the yield data are shown in table 1.
TABLE 1
| Batch of | Cyclohexanedione purity | Cyclohexanedione content | Yield is good |
| 1 | 99.2％ | 95.5％ | 80.7％ |
| 2 | 99.5％ | 96.0％ | 94.6％ |
| 3 | 99.5％ | 95.6％ | 95.3％ |
| 4 | 99.3％ | 96.5％ | 95.7％ |
| 5 | 99.6％ | 96.1％ | 95.8％ |
| 6 | 99.4％ | 95.8％ | 95.0％ |
As can be seen from Table 1, the mother liquor was not recovered in the first reaction, the yield was low, only 80.7%, the yield was increased to 94.6% in the second reaction due to the addition of the previous batch of recovered material in the form of a stripping aqueous phase, and the yield was also about 95% in the subsequent batch due to the addition of the recovered material. After repeating for 5 times, the total reaction yield can reach 92.85 percent, the yield of the cyclohexanedione preparation process is greatly improved, and the product with the yield and quality meeting the requirements is obtained.
Claims (9)
1. A green preparation method suitable for industrialized production of 1, 3-cyclohexanedione comprises the following steps:
1) Hydrogenation and acidification
In the presence of water, resorcinol reacts with liquid alkali to obtain resorcinol monosodium salt, then hydrogenation is carried out under the action of nickel, palladium or platinum catalysts to obtain reaction liquid containing enol sodium salt, after the reaction is finished, the reaction liquid is filtered, the catalysts are filtered, a reaction kettle and the catalysts are washed by deionized water, the filtrates are combined, hydrochloric acid is added for acidification until PH=2-3, 1, 3-cyclohexanedione is separated out, centrifugation is carried out to obtain a wet product of 1, 3-cyclohexanedione and acidified mother liquor, and a cyclohexanedione finished product is obtained after drying;
the reaction formula is as follows:
2) Extraction and back extraction
Extracting an acidification mother liquor containing 1, 3-cyclohexanedione by adopting an alkyl halide or ether organic solvent to obtain an acidification water phase and an organic phase; desalting and biochemically degrading the acidified water phase; adding water into the organic phase for three times to strip the 1, 3-cyclohexanedione in the organic phase into the water phase to obtain a strip water phase and a secondary organic phase;
3) Repeating the steps 1) and 2), washing the reaction kettle and the catalyst by using a back extraction water phase obtained by back extraction when filtering the reaction liquid, dissolving the residual part of the product in water, combining with the filtrate, and acidifying to separate out;
4) Combining the secondary organic phases in the step 2) and the step 3), and rectifying to recover the solvent.
2. The green process for the preparation of 1, 3-cyclohexanedione according to claim 1, characterized in that in step 1), the pH is adjusted to 2-3 with 25% -35% hydrochloric acid and the temperature is controlled to 10-20 ℃ during acidification with acid.
3. The green process for the preparation of 1, 3-cyclohexanedione according to claim 1, characterized in that in step 2) the organic solvent is used in an amount of 25 to 35% of the acidified mother liquor.
4. The green production method suitable for industrial production of 1, 3-cyclohexanedione according to claim 1, wherein in step 2), the ether-based solvent is one or more selected from the group consisting of diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane, 1, 2-dimethoxyethane and anisole; the halogenated hydrocarbon solvent is selected from one or more of dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane and 1, 1-dichloroethane.
5. The green process for the preparation of 1, 3-cyclohexanedione according to claim 1, characterized in that in step 1 and step 3) the nickel catalyst is a raney nickel catalyst.
6. The green process for the preparation of 1, 3-cyclohexanedione according to claim 1, characterized in that in step 4) a high boiling solvent free of halogen and heteroatoms is added, said high boiling solvent being a hydrocarbon solvent or an aromatic hydrocarbon solvent having a boiling point of 90-120 ℃.
7. The green process for the preparation of 1, 3-cyclohexanedione according to claim 6, characterized in that in step 4) the high boiling solvent is toluene or petroleum ether having a boiling range of 90-120 ℃.
8. The green process for producing 1, 3-cyclohexanedione according to claim 1, wherein the residue obtained after the rectification in step 4) is subjected to incineration.
9. The green process for preparing 1, 3-cyclohexanedione according to any one of claims 1 to 8, wherein the yield of cyclohexanedione obtained in a single reaction with a stripping aqueous phase washing reaction vessel and catalyst is not less than 94% and the purity is not less than 99%.
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