CN114507122A - Method for recycling 3- (4-methylbenzylidene) -camphor synthesis by-product - Google Patents
Method for recycling 3- (4-methylbenzylidene) -camphor synthesis by-product Download PDFInfo
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- CN114507122A CN114507122A CN202210109099.3A CN202210109099A CN114507122A CN 114507122 A CN114507122 A CN 114507122A CN 202210109099 A CN202210109099 A CN 202210109099A CN 114507122 A CN114507122 A CN 114507122A
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- camphor
- methylbenzylidene
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- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000006227 byproduct Substances 0.000 title claims abstract description 11
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012141 concentrate Substances 0.000 claims abstract description 13
- 239000008096 xylene Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 4
- 241000723346 Cinnamomum camphora Species 0.000 claims description 4
- 229960000846 camphor Drugs 0.000 claims description 4
- 229930008380 camphor Natural products 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical group [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007306 turnover Effects 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a recycling method of a 3- (4-methylbenzylidene) -camphor synthesis byproduct, which comprises the following steps: s1, adding the 3- (4-methylbenzylidene) -camphor refined mother liquor concentrate containing cis-3- (4-methylbenzylidene) -camphor, a solvent, a catalyst and a cocatalyst into a reactor, and reacting at 50-90 ℃ for 0.5-8 hours; s2, adding water for cleaning after reaction, and recovering xylene and a crude product of 3- (4-methylbenzylidene) -camphor by reduced pressure distillation; and recrystallizing the S3 and the 3- (4-methylbenzylidene) -camphor crude product by using ethanol to obtain a refined product. The method can turn over and reuse the by-product in the production process of the 3- (4-methylbenzylidene) -camphor, and the cis-form 3- (4-methylbenzylidene) -camphor is converted into the 3- (4-methylbenzylidene) -camphor (trans form) again and is recovered, so that the production cost is reduced, the yield of the target product is improved, the purity of the product is improved to more than 99.5 percent, and the product quality is ensured.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a recycling method of a 3- (4-methylbenzylidene) -camphor synthesis byproduct.
Background
3- (4-methylbenzylidene) -camphor is an ultraviolet absorber widely used in the cosmetic field. At present, the main production method for synthesizing 3- (4-methylbenzylidene) -camphor takes p-tolualdehyde and camphor as raw materials, and synthesizes the 3- (4-methylbenzylidene) -camphor through a claisen Schmidt reaction, wherein the reaction can generate cis-trans isomers, the trans isomers are target products, the cis isomers are byproducts, have unpleasant characteristic odor, are close to the properties of the trans isomers, cannot be separated through rectification, and can only be separated from a system through a recrystallization method, so a large amount of cis-3- (4-methylbenzylidene) -camphor is enriched in refined mother liquor, and after the refined mother liquor is distilled to recover a solvent, the cis-3- (4-methylbenzylidene) -camphor is enriched in a refined mother liquor concentrate, the refined mother liquor concentrate is treated as solid waste, and a method for recycling cis-3- (4-methylbenzylidene) -camphor is needed in order to improve the total yield and reduce the production cost.
Disclosure of Invention
The invention provides a recycling method of a 3- (4-methylbenzylidene) -camphor (also called 4-MBC) synthesis byproduct, which can convert the byproduct cis 3- (4-methylbenzylidene) -camphor into 3- (4-methylbenzylidene) -camphor (trans) again and recycle, improve the yield of a target product and reduce the production cost. Unless otherwise stated, 3- (4-methylbenzylidene) -camphor is referred to herein as the trans isomer.
The technical scheme of the invention is that the method for recycling the 3- (4-methylbenzylidene) -camphor synthesis by-product is characterized by comprising the following steps:
s1, adding the 3- (4-methylbenzylidene) -camphor refined mother liquor concentrate containing cis-3- (4-methylbenzylidene) -camphor, a solvent, a catalyst and a cocatalyst into a reactor, and reacting at 50-90 ℃ for 0.5-8 hours;
s2, adding water for cleaning after reaction, and recovering xylene and a crude product of 3- (4-methylbenzylidene) -camphor by reduced pressure distillation;
and recrystallizing the S3 and the 3- (4-methylbenzylidene) -camphor crude product by using ethanol to obtain a refined product.
Further, the solvent is any one of toluene, xylene, mesitylene and cyclohexane.
Further, the catalyst is sodium benzene sulfinate.
Further, the amount of the catalyst is 5-20%, preferably 5-10% of the weight of the refined mother liquor concentrate.
Further, the cocatalyst is hydrochloric acid with the mass concentration of 35-38%.
Furthermore, the using amount of the cocatalyst is 60-80% of the mass of the catalyst.
Further, the reaction temperature in S1 is 70-80 ℃, and the reaction time is 2-3 hours.
And further, adding water into a reaction system in the S2, washing for 2-4 times, shaking for separation, collecting an organic phase, and distilling.
Further, in the distillation under reduced pressure in S2, xylene was collected by a water pump at 160 ℃ and camphor by an oil pump, and the crude product was collected by an oil pump at 190 ℃.
Further, in S3, ethanol and water are mixed according to the mass ratio of 1-3: 1 during recrystallization, the crude product is dissolved, crystallization is carried out at the temperature below 10 ℃, and the fine product is obtained by suction filtration.
The reaction principle of the invention is as follows:
the invention has the following beneficial effects:
cis 3- (4-methylbenzylidene) -camphor has higher energy than trans, 3- (4-methylbenzylidene) -camphor (trans) is more thermodynamically stable, and for many olefins, direct heating can change the cis form to the trans form, but for 4-MBC, the higher activation energy for the conversion of cis to trans form does not allow the reaction to occur. The invention uses sodium benzene sulfinate as a catalyst to catalyze the reaction under the acidic condition, so that the activation energy required by the reaction is reduced, and the reaction of converting a cis-form body into a trans-form body is smoothly carried out.
By adopting the method provided by the invention, the by-product in the production process of the 3- (4-methylbenzylidene) -camphor can be overturned for reuse, and the cis-form 3- (4-methylbenzylidene) -camphor is converted into the 3- (4-methylbenzylidene) -camphor (trans-form) again and is recovered, so that the production cost is reduced, the yield of the target product is improved, the purity of the product is improved to more than 99%, and the quality of the product is ensured.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The 3- (4-methylbenzylidene) -camphor purification mother liquor concentrates used in examples 1 to 3 were of the same batch and were examined by GC as follows, wherein the 3- (4-methylbenzylidene) -camphor content by mass was 62.49%, the cis 3- (4-methylbenzylidene) -camphor content was 22.42%, and the balance was unknown impurities.
Example 1
270kg of a concentrate of refined mother liquor of 3- (4-methylbenzylidene) -camphor, 430kg of xylene, 14kg of sodium sulfinate and 11.2kg of hydrochloric acid were charged into a reaction vessel, reacted at 75 ℃ for 5 hours, after completion of the reaction, the content of 3- (4-methylbenzylidene) -camphor was increased to 80.63%, the content of cis-3- (4-methylbenzylidene) -camphor was decreased to 2.28%, the reaction system was washed with 100kg of water, then the xylene and the crude product of 3- (4-methylbenzylidene) -camphor were distilled off by reduced pressure distillation, and the crude product of 3- (4-methylbenzylidene) -camphor recovered was recrystallized with 800kg of 75% ethanol to obtain 190kg of a refined product of 3- (4-methylbenzylidene) -camphor having a content of 99.2%.
Example 2
271kg of the concentrate of the refined mother liquor of 3- (4-methylbenzylidene) -camphor, 431kg of xylene, 25kg of sodium sulfinate and 20kg of hydrochloric acid were charged into a reaction vessel, and reacted at 75 ℃ for 3 hours, after completion of the reaction, the content of 3- (4-methylbenzylidene) -camphor was increased to 81.02%, the content of cis-3- (4-methylbenzylidene) -camphor was decreased to 1.56%, the reaction system was washed with 100kg of water, then the xylene and the crude product of 3- (4-methylbenzylidene) -camphor were distilled off by reduced pressure distillation, and the crude product of 3- (4-methylbenzylidene) -camphor recovered was recrystallized with 800kg of 75% ethanol to obtain 192kg of a refined product of 3- (4-methylbenzylidene) -camphor having a content of 99.5%.
Example 3
270kg of a concentrate of refined mother liquor of 3- (4-methylbenzylidene) -camphor, 430kg of toluene, 27kg of sodium sulfinate and 16.2kg of hydrochloric acid were charged into a reaction vessel, and reacted at 90 ℃ for 3 hours, after completion of the reaction, the content of 3- (4-methylbenzylidene) -camphor was increased to 80.89%, the content of cis-3- (4-methylbenzylidene) -camphor was decreased to 1.87%, the reaction system was washed with 100kg of water, then the toluene and the crude product of 3- (4-methylbenzylidene) -camphor were distilled off by reduced pressure distillation, and the crude product of 3- (4-methylbenzylidene) -camphor recovered was recrystallized with 800kg of 75% ethanol to obtain 189kg of a refined product of 3- (4-methylbenzylidene) -camphor having a content of 99.3%.
Example 4: 51.61g of mother liquor concentrate was taken, wherein the mass percentage of 3- (4-methylbenzylidene) -camphor was 62.49%, the cis 3- (4-methylbenzylidene) -camphor was 22.42%, and the balance was unknown impurities. The mother liquor concentrate was dissolved in 250g of xylene, transferred into a 500ml four-necked flask with mechanical stirring, and 10.3g of sodium benzenesulfonate and 6.2g of 36% concentrated hydrochloric acid were weighed and added to the four-necked flask, and subjected to oil bath reaction at 70 ℃ for 3 hours. After the reaction is finished, 200ml of water is added into the system, the pH value of the system is about 6 after shaking, liquid separation and water washing for four times, and an organic phase is collected, wherein the cis-3- (4-methylbenzylidene) -camphor content is 0.23 percent, and the 3- (4-methylbenzylidene) -camphor mass percent content is 81.70 percent. And (2) putting the organic phase into a 500ml single-mouth bottle, carrying out oil bath on a water pump at 160 ℃ to collect dimethylbenzene, collecting camphor by an oil pump, carrying out oil bath on an oil pump at 190 ℃ to collect a product, mixing ethanol and water according to the mass ratio of 2:1, dissolving the product in a mixed solution with the mass 4 times that of the product, crystallizing at the temperature below 10 ℃, and carrying out suction filtration to obtain a refined product with the purity of 99.6%.
Claims (10)
1. A method for recycling a by-product in the synthesis of 3- (4-methylbenzylidene) -camphor is characterized by comprising the following steps:
s1, adding the 3- (4-methylbenzylidene) -camphor refined mother liquor concentrate containing cis-3- (4-methylbenzylidene) -camphor, a solvent, a catalyst and a cocatalyst into a reactor, and reacting at 50-90 ℃ for 0.5-8 hours;
s2, adding water for cleaning after reaction, and recovering xylene and a crude product of 3- (4-methylbenzylidene) -camphor by reduced pressure distillation;
and recrystallizing the S3 and the 3- (4-methylbenzylidene) -camphor crude product by using ethanol to obtain a refined product.
2. The method of claim 1, wherein: the solvent is any one of toluene, xylene, mesitylene and cyclohexane.
3. The method of claim 1, wherein: the catalyst is sodium benzene sulfinate.
4. The method of claim 3, wherein: the amount of the catalyst is 5-20%, preferably 5-10% of the weight of the refined mother liquor concentrate.
5. The method of claim 1, wherein: the cocatalyst is hydrochloric acid with the mass concentration of 35-38%.
6. The method of claim 5, wherein: the using amount of the cocatalyst is 60-80% of the mass of the catalyst.
7. The method of claim 1, wherein: the reaction temperature in S1 is 70-80 ℃, and the reaction time is 2-3 hours.
8. The method of claim 1, wherein: and (4) adding water into a reaction system in the S2, washing for 2-4 times, shaking for separation, and collecting an organic phase for distillation.
9. The method of claim 1, wherein: and during reduced pressure distillation in S2, collecting xylene by a water pump at 160 ℃, collecting camphor by an oil pump, and collecting a crude product by the oil pump at 190 ℃.
10. The method of claim 1, wherein: and (3) during recrystallization in S3, mixing ethanol and water according to the mass ratio of 1-3: 1, dissolving the crude product, crystallizing at the temperature below 10 ℃, and performing suction filtration to obtain a refined product.
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