CN114426463A - Process for preparing resorcinol - Google Patents
Process for preparing resorcinol Download PDFInfo
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- CN114426463A CN114426463A CN202011092052.8A CN202011092052A CN114426463A CN 114426463 A CN114426463 A CN 114426463A CN 202011092052 A CN202011092052 A CN 202011092052A CN 114426463 A CN114426463 A CN 114426463A
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- Prior art keywords
- solvent
- resorcinol
- ketone
- reaction
- benzene
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000002904 solvent Substances 0.000 claims abstract description 68
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 42
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 42
- IROSBXFYXRIPRU-UHFFFAOYSA-N 1,3-bis(2-hydroperoxypropan-2-yl)benzene Chemical compound OOC(C)(C)C1=CC=CC(C(C)(C)OO)=C1 IROSBXFYXRIPRU-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 87
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 150000002576 ketones Chemical class 0.000 claims description 37
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 34
- 238000000605 extraction Methods 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 31
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 27
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000007790 solid phase Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 33
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000001914 filtration Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229940018564 m-phenylenediamine Drugs 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- ADNTWSHRSHPGHG-UHFFFAOYSA-N 1,3-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC(C(C)C)=C1 ADNTWSHRSHPGHG-UHFFFAOYSA-N 0.000 description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- UOUMSRHFISCLAL-UHFFFAOYSA-N hydrogen peroxide 2-(3-propan-2-ylphenyl)propan-2-ol Chemical compound OO.CC(C)C1=CC=CC(C(C)(C)O)=C1 UOUMSRHFISCLAL-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- GBTVWZMJUZJPBU-AWEZNQCLSA-N methyl (2s)-2-(hexanoylamino)-3-(4-hydroxyphenyl)propanoate Chemical compound CCCCCC(=O)N[C@H](C(=O)OC)CC1=CC=C(O)C=C1 GBTVWZMJUZJPBU-AWEZNQCLSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- -1 MIBK) Chemical compound 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940072185 drug for treatment of tuberculosis Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of resorcinol, and discloses a method for preparing resorcinol, which comprises the following steps: in the presence of a solvent, a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and sodium bisulfate are subjected to acidolysis reaction. The resorcinol obtained by the method has high yield, high selectivity and high purity, and the sodium bisulfate catalyst can be recycled by filtration, so that the corrosion of the existing strong acids such as concentrated sulfuric acid or sulfur trioxide on equipment when being used as the catalyst is avoided, the alkali treatment is not needed, and the discharge of three wastes is reduced; the method has the advantages of mild reaction conditions, easy control of the reaction, few reaction steps, little three wastes, cleanness, environmental protection and suitability for industrialization.
Description
Technical Field
The invention relates to the technical field of resorcinol, and particularly relates to a method for preparing resorcinol.
Background
Resorcinol is commonly called as reloccine, and the chemical name of resorcinol is 1, 3-benzenediol, which is an important organic chemical raw material. The application is very wide, and the resorcinol is used for preparing anthelmintic and anti-tuberculosis drugs in the pharmaceutical industry; in agriculture, pesticides and herbicides can be synthesized; in addition, the method can also be used for preparing dyes, flame retardants, plastic additives and the like. The resorcinol-formaldehyde adhesive is widely applied to the rubber industry, and the resorcinol is also applied to a plurality of fields of ultraviolet absorbers, dyes, medicines, pesticides and the like. The resorcinol-formaldehyde is used for dipping the tire cord fabric and bonding an automobile rubber tube and an adhesive tape, and the demand of the tire cord fabric is greatly increased along with the rapid development of the automobile industry in China, so that the increase of the demand of the resorcinol is driven. The adhesive prepared from resorcinol can also be used for bonding wood, plastics, building materials, paper products, ceramics, metals, textile materials and the like.
At present, the production process of resorcinol mainly comprises benzene sulfonation, m-phenylenediamine hydrolysis and m-diisopropylbenzene oxidation. The benzene sulfonation process produces a large amount of sodium sulfate and sodium sulfite as byproducts (4 tons of byproducts are produced in each ton of resorcinol, and 60 tons of wastewater) and the pollution is particularly serious. The catalytic hydrolysis method of m-phenylenediamine comprises the steps of firstly, reacting benzene with mixed acid to obtain m-dinitrobenzene, catalytically hydrogenating the m-dinitrobenzene to obtain m-phenylenediamine, and then catalytically hydrolyzing the m-phenylenediamine to obtain resorcinol. The reaction for preparing m-phenylenediamine by catalytic hydrogenation of m-dinitrobenzene is carried out in a nitrogen environment at high temperature and high pressure, ammonia gas is generated in the reaction, a large amount of sulfuric acid is used for neutralization, and the requirement on equipment is high due to excessive corrosion.
The m-diisopropylbenzene oxidation method is developed and developed successfully by Stanford university in the middle of the 80 th's 20 th century for the first time, and has the advantages of little process pollution, low cost, short flow, high total production yield and byproduct acetone. The method for chemically producing resorcinol for Sumitomo and Mitsui solves the environmental problem which cannot be solved by the traditional process, and is the main direction of resorcinol production development in the future.
The traditional resorcinol preparation method is characterized in that m-diisopropylbenzene is used as a raw material, an oxidation solution containing diisopropylbenzene, MHP and 1, 3-bis (2-hydroperoxy-2-propyl) benzene (namely m-DHP) is obtained through an air oxidation reaction, then m-DHP with higher purity is obtained through alkali liquor extraction and methyl isobutyl ketone (MIBK) back extraction, resorcinol is obtained through an acidolysis reaction in the presence of a concentrated sulfuric acid catalyst by using the m-DHP as the raw material, and simultaneously acetone is a byproduct, so that the reaction is violent, side reactions are more, and the reaction yield is low. The reaction process is as follows:
the synthesis method has the disadvantages of severe reaction, severe corrosion of concentrated sulfuric acid on equipment, need of using alkali to neutralize acid catalyst, generation of waste water containing salt and resorcinol, high treatment difficulty and great potential safety hazard.
US2789142A discloses a process for the preparation of resorcinol: continuously reacting a methyl isobutyl ketone (MIBK) solution of m-DHP with an acetone solution of concentrated sulfuric acid under reflux, wherein the reaction residence time is 6 to 8 minutes. After the reaction, the pH value is neutralized to 2.5 to 4.0 by 4 percent sodium hydroxide solution, and as can be seen from the examples, the relationship between the resorcinol reaction yield and the solvent composition and the pH value of the post-treatment is very large, the MIBK and acetone mixed solvent is adopted, the reaction yield is 82.1 to 91.7 percent, the methyl ethyl ketone and acetone mixed solvent is adopted, the reaction yield is 65.6 to 79.8 percent, and when the reaction solvent is acetone, the resorcinol yield is 64 to 83 percent, so that the reaction and the post-treatment are difficult to control by adopting concentrated sulfuric acid as a catalyst, and the resorcinol yield is not high.
GB819450A discloses that although resorcinol can be obtained in high yield by using an acetone solution of sulfur trioxide as a DHP acidolysis catalyst, the problems of acid neutralization and equipment corrosion also exist when sulfur trioxide gas is introduced into acetone.
US4847436A employs BF3The ether complex as catalyst for DHP acidolysis to prepare resorcinol, the comparative example of this patent application uses concentrated sulfuric acid twice as much as the acidolysis catalyst, the yield of resorcinol is only 61.1%, although the yield of resorcinol is higher in this patent application method, but BF exists3Has strong toxicity, is easy to hydrolyze and smoke in the air, is inconvenient to store and use, has high requirements on the water content of a solvent and a reaction system (the water content of the reaction system is required to be less than 0.1 percent), and determines the problems of high toxicity, smoke generation, high toxicity, high water content of the reaction system and the likeThe catalyst can only prepare resorcinol in a laboratory, and is not suitable for industrial production.
US4339613A describes the synthesis of resorcinol using a superacid, perfluoroalkyl (containing one to eighteen carbon atoms) sulfonic acid, as a catalyst for the acid hydrolysis of m-DHP, which is also a laboratory preparation of resorcinol.
The prior art has the following defects: 1. concentrated sulfuric acid (or sulfur trioxide) is used as a catalyst for the reaction, the reaction is too violent, so that the potential safety hazard is large, and the concentrated sulfuric acid (or sulfur trioxide) has strong corrosivity on equipment and is not suitable for large-scale production; 2. after the reaction is finished, alkali is used for neutralizing sulfuric acid (or sulfur trioxide) to generate salt-containing and resorcinol-containing wastewater, which is unfavorable for environmental protection and not suitable for industrial production; 3. the concentrated sulfuric acid (or sulfur trioxide) catalyst can catalyze the resorcinol product to further react with acetone to generate a resinous by-product, and the reaction conversion rate and the yield are not high, so that the method is not beneficial to industrialization.
Disclosure of Invention
The invention aims to overcome the defects that the yield of a method for preparing resorcinol by acidolysis of m-DHP by using concentrated sulfuric acid and/or sulfur trioxide as a catalyst in the prior art needs to be further improved, the method has strong corrosion to equipment, violent reaction and more side reactions, and the method for preparing resorcinol has the characteristics of high yield, high purity, less three-waste generation, cleanness, environmental protection, mild reaction conditions and easy industrialization.
In order to achieve the above object, the present invention provides a method for preparing resorcinol, comprising: in the presence of a solvent, a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and sodium bisulfate are subjected to acidolysis reaction.
Preferably, the solvent contains a ketone and an aromatic hydrocarbon.
Preferably, the ketone content in the solvent is from 10 to 80% by weight, preferably from 20 to 80% by weight; the aromatic hydrocarbon content is 20 to 90% by weight, preferably 20 to 80% by weight.
Preferably, the ketone content in the solvent is 20 to 45 wt%, and the aromatic hydrocarbon content is 55 to 80 wt%.
Preferably, the weight ratio of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene to the sodium bisulfate is 1 (0.01-1), more preferably 1 (0.02-0.5).
Preferably, the method further comprises: and washing the solid phase to obtain recovered sodium bisulfate, and recycling the recovered sodium bisulfate for the acidolysis reaction.
In the prior art, concentrated sulfuric acid and/or sulfur trioxide is generally used as a catalyst for acidolysis of m-DHP, and the selectivity of resorcinol is 60-70%, but the research of the inventor of the invention finds that when the industrially easily obtained m-DHP is used as a raw material and sodium bisulfate is used as a catalyst for acidolysis of m-DHP, the reaction can be carried out gently, the selectivity of resorcinol is more than 80%, preferably more than 85%, the obtained resorcinol has high yield and high purity, and the sodium bisulfate catalyst can be recovered by filtration and recycled, so that the corrosion of equipment when strong acid such as concentrated sulfuric acid or sulfur trioxide is used as a catalyst is avoided, alkali treatment is not needed, and the emission of three wastes is reduced; the method has the advantages of mild reaction conditions, easy control of the reaction, few reaction steps, little three wastes, cleanness, environmental protection and suitability for industrialization; while those skilled in the art generally consider that acid salts such as sodium bisulfate are not sufficient for the acidolysis reaction, in the prior art, acid salts such as sodium bisulfate are generally used as catalysts in the dehydration esterification reaction or polymerization reaction of acid alcohols.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the present invention provides a method for preparing resorcinol, which comprises: in the presence of a solvent, a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and sodium bisulfate are subjected to acidolysis reaction.
According to the invention, the amount of the solvent can be selected within a wide range, as long as it is advantageous to dissolve 1, 3-bis (2-hydroperoxy-2-propyl) benzene as much as possible; preferably, the solvent is used in an amount of 3 to 10 times, preferably 4 to 6 times, the weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene.
The solvent can be selected in a wider range, so long as the yield, the purity and the selectivity of the resorcinol are improved; preferably, the solvent is selected from ketones and/or aromatic hydrocarbons.
According to the present invention, preferably, the solvent is a mixed solvent; further preferably, the solvent contains a ketone and an aromatic hydrocarbon. The inventor of the invention further finds that the preferable scheme is more beneficial to improving the selectivity of the resorcinol; under the same other conditions, the single solvent can affect the selectivity of the resorcinol, and the selectivity can be relatively reduced by about 10%.
The invention has wider selectable range of the contents of ketone and aromatic hydrocarbon in the solvent; preferably, the ketone content in the solvent is from 10 to 80% by weight, preferably from 20 to 80% by weight; the aromatic hydrocarbon content is 20 to 90% by weight, preferably 20 to 80% by weight. Under the preferred scheme, the selectivity and the yield of the resorcinol are improved.
In a preferred embodiment of the invention, the ketone content of the solvent is less than the aromatic hydrocarbon content; preferably, the ketone content in the solvent is 20 to 45 wt%, and the aromatic hydrocarbon content is 55 to 80 wt%. The inventor further researches and finds that the preferable scheme is more favorable for improving the selectivity and the yield of the resorcinol; if the ketone content is higher than the aromatic hydrocarbon content under otherwise identical conditions, the resorcinol selectivity is reduced. In addition, acetone is generally adopted as a solvent in the prior art, the using amount of the acetone is large, and the recovery cost of the solvent is high; the content of the ketone adopted in the method is relatively low, and the solvent recovery cost is low.
According to the invention, the ketone can be selected in a wide range, so long as the selectivity and the yield of the resorcinol are favorably improved; preferably, the ketone is a ketone having 3 to 6 carbon atoms, and may be, for example, an aliphatic ketone and/or a cyclic ketone having 3 to 6 carbon atoms. Preferably, the ketone having 3 to 6 carbon atoms is at least one of acetone, methyl ethyl ketone, and methyl isobutyl ketone.
According to the invention, the aromatic hydrocarbon can be selected in a wider range, so long as the selectivity and the yield of the resorcinol are favorably improved; preferably, the aromatic hydrocarbon is an aromatic hydrocarbon having 6 to 10 carbon atoms, and the aromatic hydrocarbon having 6 to 10 carbon atoms is preferably at least one of benzene, toluene, xylene, ethylbenzene and cumene.
According to the present invention, preferably, the solvent is selected from at least one of acetone, methyl ethyl ketone, methyl isobutyl ketone (i.e., MIBK), toluene, xylene, ethylbenzene, and cumene.
According to the present invention, preferably, the solvents are acetone and toluene. Under the preferable scheme, the solubility of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene is further favorably improved, and the selectivity and the yield of the resorcinol are further favorably improved.
According to a preferred embodiment of the invention, the method comprises: at least part of ketone is mixed with sodium bisulfate to obtain a first mixed solution, then a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene is mixed with aromatic hydrocarbon and optionally the rest ketone to obtain a second mixed solution, and then the first mixed solution and the second mixed solution are mixed for the acidolysis reaction.
In the invention, the dosage proportion of the residual ketone and the aromatic hydrocarbon and the at least part of ketone in the solvent can be selected in a wide range, as long as sodium bisulfate and 1, 3-bis (2-hydroperoxy-2-propyl) benzene are dissolved as much as possible; preferably, the aromatic hydrocarbon is used in an amount of 3 to 10 parts by weight and the remaining ketone is used in an amount of 0 to 4 parts by weight, relative to 1 part by weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene.
More preferably, the aromatic hydrocarbon is used in an amount of 4 to 6 parts by weight and the remaining ketone is used in an amount of 2 to 3 parts by weight, relative to 1 part by weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene. Further research by the inventor shows that when the amount of the ketone is small, m-DHP is precipitated, thereby influencing the acidolysis reaction; in the preferred embodiment of the present invention, 1, 3-bis (2-hydroperoxy-2-propyl) benzene can be dissolved better, and the selectivity and yield of resorcinol can be further improved.
In the present invention, the manner of mixing the first mixed solution and the second mixed solution is not limited, and those skilled in the art can freely select the mixed solution, and it is preferable that the second mixed solution containing m-DHP is slowly added dropwise to the first mixed solution while maintaining the temperature of the acidolysis reaction within a desired temperature range in a condensing environment.
In the present invention, the source of the raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene is not limited, and may be commercially available, or may be prepared by a conventional method, for example, m-diisopropylbenzene is used as a raw material, an oxidation solution containing diisopropylbenzene, MHP, and 1, 3-bis (2-hydroperoxy-2-propyl) benzene (i.e., m-DHP) is obtained by an air oxidation reaction, 1, 3-bis (2-hydroperoxy-2-propyl) benzene in the oxidation solution is extracted with an alkali solution to obtain an extract phase and a raffinate phase, and the extract phase is back-extracted with MIBK to obtain m-DHP with higher purity.
The concentration of the raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene is not limited as long as the raw material contains 1, 3-bis (2-hydroperoxy-2-propyl) benzene and can perform the acidolysis reaction; generally, commercially available 1, 3-bis (2-hydroperoxy-2-propyl) benzene feeds will contain small amounts of impurities such as m-diisopropylbenzene monohydroperoxide and/or 3- (2-hydroxy-2-propyl) cumene hydroperoxide; preferably, the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene in the raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene is more than or equal to 90 wt%.
According to the invention, the amount of sodium bisulfate can be selected within a wide range, and the weight ratio of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene to the sodium bisulfate is preferably 1 (0.01-1), preferably 1 (0.02-0.5). Under the preferable scheme, the regulation and control effect of sodium bisulfate as a catalyst on resorcinol selectivity is better exerted.
The invention has wide optional range of the conditions of the acidolysis reaction, and preferably, the temperature of the acidolysis reaction is 30-70 ℃, preferably 40-60 ℃. Under the preferable scheme, the acidolysis reaction is more favorably carried out. In the present invention, the method of controlling the acid hydrolysis reaction temperature is not limited, and for example, the acid hydrolysis reaction temperature may be controlled to fall within the above range by heating in a water bath.
According to the invention, the acidolysis reaction is preferably carried out for a period of time of 0.4 to 6 hours, preferably 0.4 to 2 hours. In the present invention, the time of the acidolysis reaction is the total reaction time, and is from the time of adding the raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene to the time of stopping the reaction.
In the present invention, the reaction pressure during the acidolysis reaction is not limited, and is preferably carried out under normal pressure.
In the present invention, the acidolysis reaction is preferably carried out under stirring. In the present invention, the acidolysis reaction is an exothermic reaction, and therefore the acidolysis reaction is preferably carried out in a condensing environment, and may be carried out in a reaction apparatus equipped with a condenser, for example.
According to a preferred embodiment of the invention, the method further comprises: when the conversion of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 97% or more, the reaction is stopped. The method for measuring the conversion rate of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene is not limited, and generally, the content of m-DHP is measured by iodometry, and the reaction process is tracked, so that the conversion rate is obtained.
According to the present invention, preferably, the method further comprises: carrying out solid-liquid separation on the mixture obtained by the acidolysis reaction to obtain a solid phase and a liquid phase; the liquid phase is subjected to extraction. In the present invention, it is preferable that the mixture obtained by the acid hydrolysis reaction is cooled to room temperature, and then the solid-liquid separation is performed.
The extraction is not particularly limited as long as resorcinol can be obtained, and can be freely selected by a person skilled in the art according to actual requirements; preferably, the process of extraction comprises: the liquid phase is subjected to first distillation to remove the solvent (preferably ketone in the solvent), then first extraction is carried out, then the aqueous phase obtained by the first extraction is subjected to back extraction of resorcinol in the aqueous phase by using a back extraction solvent to obtain an extract phase and a raffinate phase, and the back extraction solvent is removed by second distillation to obtain crude resorcinol. In the invention, the raffinate phase can be directly discharged or recycled after distillation. The conditions of the first distillation and the second distillation are not limited in the present invention as long as the respective objects can be achieved.
According to the present invention, there is no limitation on the extractant used in the first extraction as long as resorcinol can be extracted, and those skilled in the art can freely select the extractant according to actual conditions; preferably, the extractant used for the first extraction is water (preferably distilled water).
According to the present invention, preferably, in the first extraction, the extraction phase volume ratio is 1: (0.3-1).
According to the present invention, the stripping solvent is not limited as long as it is advantageous to strip out resorcinol, and those skilled in the art can freely select it according to the actual situation; preferably, the stripping solvent is methyl isobutyl ketone.
According to the invention, the volume ratio of the back extraction phase is not limited as long as the resorcinol is favorably back extracted; preferably, in the back extraction, the volume ratio of the back extraction phase is (0.5-1) between A (aqueous phase)/O (organic phase): 1.
preferably, the stripping stage number is 1-3 stages, more preferably 3 stages (i.e., three stripping).
According to the present invention, preferably, the method further comprises: recrystallizing the crude resorcinol to obtain pure resorcinol.
According to the present invention, there is no limitation on the crystallization solvent used for the recrystallization as long as it is favorable to obtain pure resorcinol. Preferably, the crystallization solvent used for recrystallization is an aromatic hydrocarbon solvent.
Preferably, the aromatic hydrocarbon solvent is an aromatic hydrocarbon having 6 to 10 carbon atoms, more preferably at least one selected from the group consisting of toluene, xylene, ethylbenzene and cumene, and still more preferably toluene.
According to the present invention, the amount of the crystallization solvent for the recrystallization is not limited as long as it is advantageous to improve the yield; for example, the recrystallization may be carried out using a crystallization solvent in an amount of 3 to 10 times the weight of the crude resorcinol.
The recrystallization method is not limited, and is a conventional method in the field as long as pure resorcinol is obtained; for example, the method of recrystallization may include: the mixture of crude resorcinol and recrystallization crystallization solvent is heated to 60-70 ℃, and then cooled to 20-30 ℃ for recrystallization for 1-4h, so that resorcinol is precipitated.
In the present invention, the method further comprises: after the recrystallization, the pure resorcinol is obtained by optionally suction filtering, optionally washing and optionally drying. The conditions of the suction filtration, the washing and the drying are not limited at all, and can be freely selected by the person skilled in the art, so that the details are not repeated.
According to a preferred embodiment of the invention, the method further comprises: and washing the solid phase to obtain recovered sodium bisulfate, and recycling the recovered sodium bisulfate for the acidolysis reaction.
In the present invention, the washing conditions for washing the solid phase are not limited as long as they are favorable for removing impurities attached to sodium bisulfate generated by the acidolysis reaction; preferably, the weight ratio of the solid phase to the washing solvent is 1: 1-7.
In the invention, the catalyst used in the acidolysis reaction can be the recovered sodium bisulfate completely or partially, and the invention has no limitation on the method; when the recovered sodium bisulfate is partially adopted, high resorcinol selectivity and yield can be obtained.
According to the present invention, the cleaning agent for cleaning is preferably selected from ketones having 3 to 6 carbon atoms, more preferably at least one selected from acetone, methyl ethyl ketone and methyl isobutyl ketone, and still more preferably acetone.
According to a preferred embodiment of the present invention, the method for preparing resorcinol comprises:
in the presence of a solvent, carrying out acidolysis reaction on a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and sodium bisulfate, and stopping the reaction when the conversion rate of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene is more than 97%;
carrying out solid-liquid separation on the mixture obtained by the acidolysis reaction to obtain a solid phase and a liquid phase; carrying out first distillation on the liquid phase to remove the solvent, carrying out first extraction, carrying out back extraction on resorcinol in the water phase obtained by the first extraction by using a back extraction solvent to obtain an extract phase and a raffinate phase, and carrying out second distillation on the extract phase to remove the back extraction solvent to obtain crude resorcinol; recrystallizing the crude resorcinol to obtain pure resorcinol;
washing the solid phase to obtain recovered sodium bisulfate, and circularly using the recovered sodium bisulfate for the acidolysis reaction;
wherein the weight ratio of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene to the sodium bisulfate is 1 (0.01-1); the temperature of the acidolysis reaction is 30-70 ℃;
the dosage of the solvent is 3 to 10 times of the weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene; the solvent contains ketone and aromatic hydrocarbon, wherein the content of the ketone in the solvent is 20-45 wt%, and the content of the aromatic hydrocarbon in the solvent is 55-80 wt%;
in the raw material containing 1, 3-di (2-hydroperoxy-2-propyl) benzene, the content of 1, 3-di (2-hydroperoxy-2-propyl) benzene is more than or equal to 90 wt%.
The selectivity of the resorcinol prepared by the method is over 80 percent, preferably over 85 percent, the obtained resorcinol has high yield and high purity, and the sodium bisulfate catalyst can be recycled by filtration, so that the corrosion of the existing strong acid such as concentrated sulfuric acid or sulfur trioxide on equipment when being used as the catalyst is avoided, the alkali treatment is not needed, and the discharge of three wastes is reduced; the method has the advantages of mild reaction conditions, easy control of the reaction, few reaction steps, little three wastes, cleanness, environmental protection and suitability for industrialization.
The present invention will be described in detail below by way of examples. In the following examples, the starting materials were all commercially available except for the other descriptions, and the starting material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene contained 95 wt% of m-DHP, 0.8 wt% of m-diisopropylbenzene hydroperoxide, and 4.2 wt% of 3- (2-hydroxy-2-propyl) cumene hydroperoxide.
Example 1
Adding 10 g of acetone and 1 g of sodium bisulfate catalyst into a 100 ml three-mouth bottle provided with a stirrer, a thermometer and a reflux condenser to obtain a first mixed solution, starting stirring, slowly dropwise adding a second mixed solution obtained by dissolving a raw material containing m-DHP (containing 5g of m-DHP) into 25 g of toluene under the heating of water bath at 40 ℃, heating the reaction solution to 50 ℃ by the heat generated by reaction, adding the second mixed solution after about 17 minutes, continuing the reaction for 10 minutes, detecting and tracking the reaction process by adopting an iodometry method in the reaction process, stopping the reaction when the conversion rate of the m-DHP in the reaction solution reaches 98 percent, obtaining a reaction mixture, and carrying out acidolysis reaction for 30 minutes. Cooling the reaction mixture to room temperature, filtering to obtain a solid phase and a liquid phase, washing 0.95g of the solid phase by using 3 g of acetone to obtain a recovered sodium bisulfate catalyst, evaporating the liquid phase under reduced pressure to remove the acetone to obtain an organic phase, extracting resorcinol in the organic phase by using 15 ml of distilled water (O/A ═ 2: 1) to obtain an aqueous phase, back-extracting the resorcinol in the aqueous phase by using 30 ml of MIBK (A/O ═ 1: 2) for three times, combining MIBK solutions, distilling the solutions under reduced pressure at 40-60 ℃ to remove the MIBK solvent to obtain a distillation kettle liquid, filtering to obtain crude resorcinol, recrystallizing the crude resorcinol by using toluene with the weight of 4 times of the crude resorcinol, wherein the recrystallization method comprises the steps of firstly heating to 60-70 ℃, then cooling to 20-30 ℃, recrystallizing for 2 hours, carrying out suction filtration, washing and drying to obtain pure resorcinol, the melting point is 108-110 ℃, the yield is 85 percent, and the selectivity is 90 percent.
Example 2
Adding 10 g of acetone and 0.5 g of sodium bisulfate catalyst into a 100 ml three-mouth bottle provided with a stirrer, a thermometer and a reflux condenser to obtain a first mixed solution, starting stirring, slowly dropwise adding a second mixed solution obtained by dissolving a raw material containing m-DHP (containing 5g of m-DHP) into 25 g of toluene and 10 g of acetone under the heating of water bath at 40 ℃, heating the reaction solution to 45 ℃ by the heat generated by reaction, finishing adding the second mixed solution in about 15 minutes, continuing the reaction for 10 minutes, detecting and tracking the reaction process by using an iodometry method in the reaction process, stopping the reaction when the conversion rate of the m-DHP in the reaction solution reaches 98 percent, obtaining a reaction mixture, and carrying out acidolysis reaction for 30 minutes. Cooling the reaction mixture to room temperature, then filtering to obtain a solid phase and a liquid phase, washing 0.48g of the solid phase with 3 g of acetone to obtain a recovered sodium bisulfate catalyst, evaporating the liquid phase under reduced pressure to remove acetone to obtain an organic phase, extracting resorcinol in the organic phase with 15 ml of distilled water (O/A ═ 2: 1) to obtain an aqueous phase, back-extracting the resorcinol in the aqueous phase with 30 ml of MIBK (A/O ═ 1: 2) in three times, combining the MIBK solutions, the solution is subjected to reduced pressure distillation at 40-60 ℃ to remove MIBK solvent to obtain distillation kettle liquid, crude resorcinol is obtained through filtration, the crude resorcinol is recrystallized by toluene with 4 times of the weight of the crude resorcinol (the recrystallization method is the same as that of example 1), and pure resorcinol is obtained after suction filtration, washing and drying, wherein the melting point is 108-110 ℃, the yield is 87% and the selectivity is 92%.
Example 3
Adding 10 g of acetone and 0.1 g of sodium bisulfate catalyst into a 100 ml three-mouth bottle provided with a stirrer, a thermometer and a reflux condenser to obtain a first mixed solution, starting stirring, slowly dropwise adding a second mixed solution obtained by dissolving a raw material containing m-DHP (containing 5g of m-DHP) into 25 g of toluene and 10 g of acetone under the heating of 55 ℃ water bath, raising the temperature of a reaction solution to 60 ℃ by using the heat generated by reaction, finishing adding the second mixed solution in about 15 minutes, continuing the reaction for 45 minutes, detecting and tracking the reaction process by using an iodometry method in the reaction process, stopping the reaction when the conversion rate of the m-DHP in the reaction solution reaches 98 percent, obtaining a reaction mixture, and carrying out acidolysis reaction for 60 minutes. Cooling the reaction mixture to room temperature, then filtering to obtain a solid phase and a liquid phase, washing 0.9g of the solid phase with 3 g of acetone to obtain a recovered sodium bisulfate catalyst, evaporating the liquid phase under reduced pressure to remove acetone to obtain an organic phase, extracting resorcinol in the organic phase with 15 ml of distilled water (O/A ═ 2: 1) to obtain an aqueous phase, back-extracting the resorcinol in the aqueous phase with 30 ml of MIBK (A/O ═ 1: 2) in three times, combining the MIBK solutions, the solution is subjected to reduced pressure distillation at 40-60 ℃ to remove MIBK solvent to obtain distillation kettle liquid, crude resorcinol is obtained through filtration, the crude resorcinol is recrystallized by toluene with 4 times of the weight of the crude resorcinol (the recrystallization method is the same as that of example 1), and pure resorcinol is obtained after suction filtration, washing and drying, wherein the melting point is 108-110 ℃, the yield is 81% and the selectivity is 86%.
Example 4
Adding 10 g of acetone and 0.48g of the recovered sodium bisulfate catalyst obtained in the example 2 into a 100 ml three-neck flask provided with a stirrer, a thermometer and a reflux condenser to obtain a first mixed solution, starting stirring, slowly dropwise adding a second mixed solution obtained by dissolving a raw material containing m-DHP (containing 5g of m-DHP) in 25 g of toluene and 10 g of acetone under the heating of water bath at 40 ℃, heating the reaction solution to 44 ℃ by using the heat generated by the reaction, completely adding the second mixed solution within about 15 minutes, continuing the reaction for 15 minutes, detecting and tracking the reaction process by using an iodometric method in the reaction process, stopping the reaction when the m-DHP conversion rate in the reaction solution reaches 98%, obtaining a reaction mixture, and carrying out acidolysis reaction for 40 minutes. Cooling the reaction mixture to room temperature, then filtering to obtain a solid phase and a liquid phase, washing 0.46g of the solid phase with 3 g of acetone to obtain a recovered sodium bisulfate catalyst, evaporating the liquid phase under reduced pressure to remove acetone to obtain an organic phase, extracting resorcinol in the organic phase with 15 ml of distilled water (O/A ═ 2: 1) to obtain an aqueous phase, back-extracting the resorcinol in the aqueous phase with 30 ml of MIBK (A/O ═ 1: 2) in three times, combining the MIBK solutions, the solution is subjected to reduced pressure distillation at 40-60 ℃ to remove MIBK solvent to obtain distillation kettle liquid, crude resorcinol is obtained through filtration, the crude resorcinol is recrystallized by toluene with 4 times of the weight of the crude resorcinol (the recrystallization method is the same as that of example 1), and pure resorcinol is obtained after suction filtration, washing and drying, wherein the melting point is 108-110 ℃, the yield is 83% and the selectivity is 88%.
Example 5
The procedure of example 2 was followed except that the second mixed solution was prepared using a different solvent composition, specifically, without adding toluene, using a second mixed solution obtained by dissolving a raw material containing m-DHP (5 g of m-DHP) in 35 g of acetone; the rest is the same as in example 2.
The prepared pure resorcinol has melting point of 108-110 ℃, yield of 84% and selectivity of 89%.
Example 6
The procedure of example 2 was followed except that the amounts of acetone and toluene in the second mixed solution were varied, specifically, a second mixed solution was prepared by dissolving m-DHP-containing raw material (containing 5g of m-DHP) in 10 g of toluene and 25 g of acetone; the rest is the same as in example 2.
The prepared pure resorcinol has the melting point of 108-110 ℃, the yield of 82 percent and the selectivity of 85 percent.
Example 7
The procedure of example 2 was followed except that 10 g of acetone was not added to the second mixed solution, and a second mixed solution was obtained by dissolving the raw material containing m-DHP (containing 5g of m-DHP) in 25 g of toluene only; the rest is the same as in example 2.
The prepared pure resorcinol has melting point of 108-110 ℃, yield of 80% and selectivity of 81%.
Example 8
The procedure of example 2 was followed except that the raw materials, catalyst and solvent were mixed in different manners, specifically, acetone, sodium bisulfate catalyst, m-DHP-containing raw material, and toluene were directly mixed in the same amounts; the rest is the same as in example 2.
The prepared pure resorcinol has melting point of 108-110 ℃, yield of 76% and selectivity of 80%.
Example 9
The procedure is as in example 2, except that said acetone and toluene are replaced with methyl isobutyl ketone, which is used in the same amount as the total amount of said acetone and toluene; the rest is the same as in example 2.
The prepared pure resorcinol has melting point of 108-110 ℃, yield of 78% and selectivity of 83%.
Comparative example 1
The procedure of example 2 was followed, except that the sodium hydrogensulfate was replaced with the same amount of potassium hydrogensulfate, and the procedure of example 2 was repeated.
The prepared pure resorcinol has melting point of 108-110 ℃, yield of 50% and selectivity of 45%.
It can be seen from the above examples and comparative examples that resorcinol with high yield and high selectivity can be obtained by the specific method of the present invention, and the recovered sodium bisulfate catalyst obtained after the reaction can be recycled, and resorcinol with high yield and high selectivity can still be obtained when the catalyst is recycled.
In addition, the comparative example is not a prior art, is only set for comparison with the method of the present invention, and is not a limitation of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of making resorcinol, the method comprising: in the presence of a solvent, a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and sodium bisulfate are subjected to acidolysis reaction.
2. The process according to claim 1, wherein the solvent is used in an amount of 3 to 10 times, preferably 4 to 6 times, the weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene;
preferably, the solvent contains a ketone and/or an aromatic hydrocarbon;
preferably, the solvent contains a ketone and an aromatic hydrocarbon;
preferably, the ketone content in the solvent is from 10 to 80% by weight, preferably from 20 to 80% by weight; the content of aromatic hydrocarbons is 20 to 90 wt.%, preferably 20 to 80 wt.%;
preferably, the ketone content in the solvent is 20-45 wt%, and the aromatic hydrocarbon content is 55-80 wt%;
preferably, the ketone is a ketone with 3-6 carbon atoms;
preferably, the aromatic hydrocarbon is aromatic hydrocarbon with 6-10 carbon atoms;
preferably, the solvent is selected from at least one of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethylbenzene, and cumene;
preferably, the solvents are acetone and toluene.
3. The method of claim 2, wherein the method comprises: mixing at least part of ketone with sodium bisulfate to obtain a first mixed solution, mixing a raw material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene with aromatic hydrocarbon and optionally the rest ketone to obtain a second mixed solution, and mixing the first mixed solution and the second mixed solution to carry out acidolysis reaction;
preferably, the aromatic hydrocarbon is used in an amount of 3 to 10 parts by weight and the remaining ketone is used in an amount of 0 to 4 parts by weight, relative to 1 part by weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene;
more preferably, the aromatic hydrocarbon is used in an amount of 4 to 6 parts by weight and the remaining ketone is used in an amount of 2 to 3 parts by weight, relative to 1 part by weight of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene.
4. The method according to any one of claims 1 to 3, wherein the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene in the starting material containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene is not less than 90% by weight.
5. A process according to any one of claims 1 to 4, wherein the weight ratio of 1, 3-bis (2-hydroperoxy-2-propyl) benzene to sodium bisulfate is from 1 (0.01 to 1), preferably from 1 (0.02 to 0.5).
6. The process according to any one of claims 1 to 5, wherein the temperature of the acidolysis reaction is 30 to 70 ℃, preferably 40 to 60 ℃;
preferably, the acidolysis reaction time is 0.4-6h, preferably 0.4-2 h.
7. The method of any of claims 1-6, wherein the method further comprises: when the conversion of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 97% or more, the reaction is stopped.
8. The method of any of claims 1-7, wherein the method further comprises: carrying out solid-liquid separation on the mixture obtained by the acidolysis reaction to obtain a solid phase and a liquid phase; the liquid phase is subjected to extraction.
9. The method of claim 8, wherein the extracting comprises: firstly distilling the liquid phase for the first time to remove the solvent, then carrying out first extraction, carrying out back extraction on resorcinol in the water phase obtained by the first extraction by using a back extraction solvent to obtain an extract phase and a raffinate phase, and carrying out second distillation on the extract phase to remove the back extraction solvent to obtain crude resorcinol;
preferably, the extractant used in the first extraction is water;
preferably, in the first extraction, the volume ratio of the extraction phase is 1: (0.3-1);
preferably, the stripping solvent is methyl isobutyl ketone;
preferably, in the back extraction, the volume ratio of the back extraction phase is (0.5-1): 1;
preferably, the method further comprises: recrystallizing the crude resorcinol to obtain pure resorcinol;
preferably, the crystallization solvent used for recrystallization is an aromatic hydrocarbon solvent;
preferably, the aromatic hydrocarbon solvent is an aromatic hydrocarbon having 6 to 10 carbon atoms, and more preferably at least one selected from the group consisting of toluene, xylene, ethylbenzene and cumene.
10. The method of claim 8 or 9, wherein the method further comprises: washing the solid phase to obtain recovered sodium bisulfate, and circularly using the recovered sodium bisulfate for the acidolysis reaction;
preferably, the detergent for washing is selected from ketones having 3 to 6 carbon atoms, and more preferably at least one selected from acetone, methyl ethyl ketone, and methyl isobutyl ketone.
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| CN1036010A (en) * | 1988-02-04 | 1989-10-04 | 三井石油化学工业株式会社 | 3-(2-hydrogen peroxide-based-2-propyl group) phenol and use the method for this compound Resorcinol |
| CN1235952A (en) * | 1992-09-14 | 1999-11-24 | 通用电气公司 | Process for preparing phenol and acetone by cumene hydroperoxide intensified decomposition |
| JPH09143111A (en) * | 1995-11-20 | 1997-06-03 | Sumitomo Chem Co Ltd | Decomposition of hydroperoxide |
| US6350921B1 (en) * | 1998-02-24 | 2002-02-26 | Indspec Chemical Corporation | Process for the production of a dihydroxybenzene and dicarbinol from diisopropylbenzene |
| CN101024600A (en) * | 2006-02-22 | 2007-08-29 | 住友化学株式会社 | Process for producing phenols |
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