CN115583906B - Treatment method and recycling method of m-diisopropylbenzene oxidation liquid and production method of resorcinol - Google Patents
Treatment method and recycling method of m-diisopropylbenzene oxidation liquid and production method of resorcinol Download PDFInfo
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- diisopropylbenzene
- propyl
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- benzene
- oxidation
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 194
- 230000003647 oxidation Effects 0.000 title claims abstract description 164
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 111
- 239000007788 liquid Substances 0.000 title claims abstract description 93
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 145
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000012452 mother liquor Substances 0.000 claims abstract description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000003377 acid catalyst Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- UGPWRRVOLLMHSC-UHFFFAOYSA-N 2-[3-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=CC(C(C)(C)O)=C1 UGPWRRVOLLMHSC-UHFFFAOYSA-N 0.000 claims description 60
- 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 description 44
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 230000001590 oxidative effect Effects 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- -1 m-isopropyl dimethyl benzyl Chemical group 0.000 claims description 18
- 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 claims description 14
- 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 claims description 13
- 238000004821 distillation Methods 0.000 claims description 13
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 12
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 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 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims 2
- 229940078552 o-xylene Drugs 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 10
- 239000012071 phase Substances 0.000 description 61
- 239000002994 raw material Substances 0.000 description 29
- 229960002163 hydrogen peroxide Drugs 0.000 description 27
- 239000006227 byproduct Substances 0.000 description 26
- 239000012535 impurity Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000009825 accumulation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- HEOVGVNITGAUKL-UHFFFAOYSA-N 3-Methyl-1-phenyl-1-butanone Chemical compound CC(C)CC(=O)C1=CC=CC=C1 HEOVGVNITGAUKL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SBUBPFHJZHQNNT-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene hydrogen peroxide Chemical compound OO.OO.CC(C)C1=CC=CC=C1C(C)C SBUBPFHJZHQNNT-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- SXBWYXYGEHOVPU-UHFFFAOYSA-N 2-hydroxy-3-methyl-1-phenylbutan-1-one Chemical compound CC(C)C(O)C(=O)C1=CC=CC=C1 SXBWYXYGEHOVPU-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- 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
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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 production, and discloses a treatment method and a recycling method of m-diisopropylbenzene oxidation liquid and a resorcinol production method, wherein the treatment method comprises the following steps: under the reaction condition that the hydroxylate is converted into the peroxidized hydroxylate, the m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in the presence of an acid catalyst and an organic solvent; removing the water phase in the mixed solution obtained after the reaction to obtain a first oil phase; performing first extraction on the first oil phase by using alkali liquor to obtain a first extracted water phase and a second oil phase, performing back extraction on the first extracted water phase by using a back extraction solvent, and removing the back extraction solvent in the third oil phase to obtain DHP; and removing the organic solvent in the second oil phase to obtain the recycled m-diisopropylbenzene oxidation liquid. The treatment method can remove DC and HHP and extract DHP, and has the advantages of high DHP yield and high purity.
Description
Technical Field
The invention relates to the field of resorcinol production, in particular to a treatment method and a recycling method of m-diisopropylbenzene oxidation liquid and a resorcinol production method.
Background
Resorcinol is commonly known as resorcinol, and has the chemical name of 1, 3-benzenediol, which is an important organic chemical raw material. The application of the resorcinol is very wide, and the resorcinol is used for preparing insect repellents and antituberculosis medicaments in the pharmaceutical industry; in agriculture, synthetic pesticides and herbicides; in addition, the method can be used for preparing dyes, flame retardants, plastic additives and the like. The resorcinol production process mainly comprises a benzene sulfonation alkali fusion method, a m-phenylenediamine hydrolysis method and a m-diisopropylbenzene oxidation method. The m-diisopropylbenzene oxidation method is the middle 80s of the 20 th century, is successfully developed by the Stanford university for the first time, has small process pollution, low cost and short flow, has high total yield of production and simultaneously produces acetone as a byproduct. The method for producing resorcinol by Sumitomo and Mitsui chemical company solves the environmental problem which can not be solved by the traditional process, and is the main direction of resorcinol production development in the future.
The resorcinol preparation method disclosed in patent application US4849549 is to perform oxidation reaction by introducing air under a certain temperature and pressure in the presence of a m-diisopropylbenzene oxidation solution initiator to obtain an oxidation solution mainly containing m-diisopropylbenzene, m-isopropylcumene hydroperoxide (MHP) and 1, 3-di (2-hydroperoxy-2-propyl) benzene (i.e. m-DHP) and 3- (2-hydroxy-2-propyl) cumene hydroperoxide (HHP), then extract DHP and HHP in the oxidation solution into alkali solution by sodium hydroxide solution, then strip the reaction solution by methyl isobutyl ketone (MIBK) at a low temperature and a high temperature, separate the reaction solution to obtain m-DHP with higher purity, and perform acidolysis reaction in the presence of a concentrated sulfuric acid catalyst to obtain resorcinol and byproduct acetone.
The schematic of the reaction path of the m-diisopropylbenzene oxidation reaction for preparing DHP is shown in FIG. 1. As is clear from the above reaction formula, in the oxidation process of m-diisopropylbenzene, by-products such as m-isopropyl dimethylbenzyl alcohol (MC) and 1, 3-bis (2-hydroxy-2-propyl) benzene (DC) are produced in addition to MHP, DHP and HHP.
The research result shows that the content of MC, HHP and DC in the oxidized liquid increases with the increase of the recycling times of the recycled oxidized liquid, if impurity removal treatment is not carried out on the recycled oxidized liquid, the byproducts influence the oxidation reaction of the recycled oxidized liquid with the increase of the content of MC, DC and HHP, and the byproducts are extremely easy to precipitate after the content of DC is more than 4.2%, so that the measurement of a sensing probe is influenced by the blockage of a pipeline. In order to increase the oxidation reaction rate of the recycled oxidizing solution, by-product impurities affecting the oxidation reaction must be removed.
U.S. patent application US3950431 discloses a method for removing accumulated oxidation byproducts from an oxidation solution from which DHP has been separated by alkali extraction, wherein an alkaline aqueous solution (alcohol-alkali-water mixed extractant) containing 10% to 80% of methanol or ethanol is used for extracting and recycling diisopropylbenzene oxidation solution to remove alcohols such as MC, HHP and DC, and byproducts affecting oxidation reaction such as ketones and olefins such as isopropyl acetophenone (MK) and hydroxy isopropyl acetophenone (KC). The method selects alcohol-alkali-water mixed extractant to extract and recycle oxidizing solution to remove oxidation reaction byproducts, however, the process has contradiction between the removal rate and the oil-water phase layering effect. In order to improve the removal rate, the content of the solvent alcohol must be improved, and because the alcohol and the water are mutually soluble, the oil-water phase layering effect is poor, the extracted oxidation liquid contains a large amount of methanol or ethanol, the removal process must be complicated by distillation, and the methanol and the ethanol are dissolved in the oxidation liquid to bring new impurities influencing the oxidation reaction, so that the potential safety hazard is high. Similarly, in order to improve the layering effect of the extracted oil phase and the water phase, the proportion of the added alcohol must be reduced, and the impurity removal efficiency of the oxidation liquid is low. Because the polarity of MHP is not different from that of MC, a certain amount of MHP can not enter into alcohol water solution, so that the loss of useful components is caused, the cost of raw materials is increased, and the amount of wastewater is increased.
U.S. patent applications US4088699 and US3993696 also disclose methods for removing oxidation-affecting impurities from an oxidizing solution from which DHP has been removed. The difference is that patent application US4088699 adopts a falling film evaporator under the vacuum degree of 110mmHg, adopts steam heating at 154 ℃, and distills the diisopropylbenzene and MHP in the recycled oxidizing liquid at 132 ℃, and the recovery rate of MHP is 82.5%. Patent application US3993696 uses the mixed diisopropylbenzene oxidation liquid of meta-para position with removed DHP to make steam distillation under neutral and weak alkaline condition (pH is 6-9), under the condition of reduced pressure and vacuum degree of 20-300 mmHg, then uses the diisopropylbenzene and diisopropylbenzene monohydrogen peroxide MHP to make distillation together with water, and uses the oil-water delamination to obtain diisopropylbenzene and MHP, and the recovery rate of MHP is up to 91%. Because the boiling point of MC is lower than that of MHP, MC in the oxidizing solution is distilled out together with MHP, and DC is also carried out, the method for removing impurities in the oxidizing solution by steam distillation under reduced pressure cannot obtain satisfactory effect, and the oxidizing solution is heated for a long time at 105-110 ℃, so that thermal decomposition of MHP is easily caused, and the method has great potential safety hazard and is not suitable for industrial production.
In summary, the treatment process for recovering the oxidizing liquid in the prior art has the following disadvantages: because the boiling point of MC is lower than that of MHP, MC in the oxidizing liquid is distilled out together with MHP, and DC is also carried out, under high temperature, MHP and residual DHP are decomposed by heating to generate MC and KC respectively, and MC and DC are dehydrated at high temperature to generate olefin byproducts. Moreover, distillation of organic peroxides at high temperatures presents a great safety hazard; the treatment method does not effectively utilize MC, DC and HHP, has large discharge amount of waste liquid, and is not beneficial to energy conservation and consumption reduction; the impurities in the oxidation reaction cannot be effectively removed, and the accumulation of the impurities in the oxidation liquid can affect the cyclic oxidation of the oxidation liquid.
Disclosure of Invention
The invention aims to solve the problems that peroxides of hydroxyl byproducts MC and DC are easy to decompose, potential safety hazards exist and the recovery rate of DHP is low in the process of treating m-diisopropylbenzene oxidation mother liquor in the prior art, and provides a treatment method and a recycling method of m-diisopropylbenzene oxidation liquor and a production method of resorcinol, wherein the treatment method of m-diisopropylbenzene oxidation liquor can convert the hydroxyl byproducts MC into useful intermediate products MHP, so that the reaction efficiency of recycling the m-diisopropylbenzene oxidation mother liquor in the subsequent oxidation process is improved, and the yield of the subsequent DHP is improved; meanwhile, the treatment method can convert DC and HHP into target products DHP, can avoid the accumulation of DC and the adverse effect of HHP on subsequent oxidation reaction, can extract DHP, has the advantages of high DHP yield and purity, and has the advantages of mild reaction conditions, less three wastes, cleanness, environmental protection and easy industrialization.
In order to achieve the above object, a first aspect of the present invention provides a method for treating a meta-diisopropylbenzene oxidation solution, comprising the steps of: (1) Under the reaction condition that the hydroxylate is converted into the peroxidized hydroxylate, the m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in the presence of an acid catalyst and an organic solvent; (2) Removing the water phase in the mixed solution obtained after the reaction to obtain a first oil phase; (3) Performing first extraction on the first oil phase by using alkali liquor to obtain a first extracted water phase and a second oil phase, performing back extraction on the first extracted water phase by using a back extraction solvent to obtain a third oil phase containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene, and removing the back extraction solvent in the third oil phase to obtain 1, 3-bis (2-hydroperoxy-2-propyl) benzene (DHP); (4) Removing the organic solvent in the second oil phase to obtain recycled m-diisopropylbenzene oxidation liquid; wherein the m-diisopropylbenzene oxidation mother liquor contains m-Diisopropylbenzene (DIPB), m-isopropyldimethylbenzyl alcohol (MC), m-isopropylcumene hydroperoxide (MHP) and 1, 3-bis (2-hydroxy-2-propyl) benzene (DC).
The second aspect of the invention provides a recycling method of m-diisopropylbenzene oxidation liquid, comprising the treatment method of the m-diisopropylbenzene oxidation liquid in the first aspect; the method also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene by adopting an oxidation method from the obtained recycled m-diisopropylbenzene oxidation solution.
In a third aspect, the present invention provides a method for producing resorcinol, comprising: 1) Oxidizing m-diisopropylbenzene to react under the condition of oxidizing to generate 1, 3-di (2-hydroperoxy-2-propyl) benzene to obtain m-diisopropylbenzene oxidation mother liquor containing 1, 3-di (2-hydroperoxy-2-propyl) benzene; 2) Obtaining 1, 3-bis (2-hydroperoxy-2-propyl) benzene and recycling m-diisopropylbenzene oxidation liquid from m-diisopropylbenzene oxidation mother liquor according to the treatment method of m-diisopropylbenzene oxidation liquid in the first aspect; 3) Returning the recycled m-diisopropylbenzene oxidation liquid obtained in the step 2) to the step 1); 4) And (3) carrying out acidolysis reaction on the 1, 3-di (2-hydroperoxy-2-propyl) benzene obtained in the step (2) in the presence of concentrated sulfuric acid to obtain resorcinol.
In the technical scheme, the m-diisopropylbenzene oxidation mother liquor is contacted and reacted with hydrogen peroxide in an organic solvent in the presence of an acid catalyst under the reaction condition of converting the hydroxylate into the peroxidized hydroxylate, so that the hydroxyl-containing byproduct MC can be converted into a useful intermediate product MHP, the reaction efficiency of the recycled m-diisopropylbenzene oxidation mother liquor in the subsequent oxidation process is improved, and the subsequent yield of DHP is improved; meanwhile, by applying the treatment method disclosed by the invention, DC and HHP can be converted into target products DHP, and the accumulation of DC and the adverse effect of HHP on subsequent oxidation reaction can be avoided. In addition, the treatment method can extract the DHP, and has the advantages of high DHP yield and high DHP purity. The recycled m-diisopropylbenzene oxidizing solution obtained by the method has few impurities, eliminates the influence of accumulation of MC, DC and HHP on the preparation of DHP by m-diisopropylbenzene oxidation reaction, avoids the blockage of DC precipitation on equipment pipelines, reduces waste liquid discharge, reduces cost, has mild reaction conditions, is easy to control reaction, has few reaction steps, generates little three wastes, is clean and environment-friendly, and is more suitable for industrialization.
According to the recycling method of the m-diisopropylbenzene oxidation liquid, the recycled m-diisopropylbenzene oxidation liquid obtained by the treatment method is used as a raw material, the content of MHP in the recycled raw material is increased, the conversion of the recycled m-diisopropylbenzene oxidation liquid into DHP in the oxidation process can be promoted, and the reaction efficiency and the yield of the DHP are improved; the recycled raw materials have low DC and HHP contents, so that the negative influence of the recycled raw materials on the subsequent oxidation reaction can be reduced, and the reaction efficiency is improved.
According to the resorcinol production method, m-diisopropylbenzene is used as a raw material, through oxidization and the treatment method, impurities in m-diisopropylbenzene oxidation mother liquor can be converted into raw materials which are favorable for recycling, and the recycled m-diisopropylbenzene oxidation liquid is returned to an oxidization stage, so that the utilization rate of the raw materials and the yield of DHP can be improved; while impurity treatment and conversion are carried out, the treatment method can extract the DHP without extracting the DHP in the mother liquor before treatment, has the advantages of high DHP yield and high purity, and can save the process flow. The DHP is used as an intermediate raw material for preparing resorcinol, so the resorcinol production method has the advantages of high raw material utilization rate, high product yield and flow saving.
Drawings
FIG. 1 is a schematic diagram of the reaction path of a m-diisopropylbenzene oxidation reaction to produce DHP;
FIG. 2 is a schematic diagram of the reaction path of the components in the m-diisopropylbenzene oxidation mother liquor with hydrogen peroxide.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for treating m-diisopropylbenzene oxidation liquid, which comprises the following steps: (1) Under the reaction condition that the hydroxylate is converted into the peroxidized hydroxylate, the m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in the presence of an acid catalyst and an organic solvent; (2) Removing the water phase in the mixed solution obtained after the reaction to obtain a first oil phase; (3) Performing first extraction on the first oil phase by using alkali liquor to obtain a first extracted water phase and a second oil phase, performing back extraction on the first extracted water phase by using a back extraction solvent to obtain a third oil phase containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene, and removing the back extraction solvent in the third oil phase to obtain 1, 3-bis (2-hydroperoxy-2-propyl) benzene (DHP); (4) Removing the organic solvent in the second oil phase to obtain recycled m-diisopropylbenzene oxidation liquid; wherein the m-diisopropylbenzene oxidation mother liquor contains m-Diisopropylbenzene (DIPB), m-isopropyldimethylbenzyl alcohol (MC), m-isopropylcumene hydroperoxide (MHP) and 1, 3-bis (2-hydroxy-2-propyl) benzene (DC).
The recycled m-diisopropylbenzene oxidation liquid obtained by the method has few impurities, eliminates the influence of accumulation of MC, DC and HHP on the preparation of DHP by m-diisopropylbenzene oxidation reaction, avoids the blockage of DC precipitation on equipment pipelines, reduces waste liquid discharge, reduces cost, has mild reaction conditions, is easy to control reaction, has few reaction steps, generates little three wastes, is clean and environment-friendly, and is suitable for industrialization.
The schematic diagram of the reaction path of the components in the m-diisopropylbenzene oxidation mother liquor and hydrogen peroxide is shown in figure 2. It can be seen that the treatment according to the invention is capable of converting MC into useful intermediate product MHP; can convert DC and HHP into target products DHP. As can be seen from FIG. 1, MHP is an intermediate raw material for producing DHP, and the MHP content increases, which tends to improve the reaction efficiency and the utilization of the raw material in the oxidation reaction at the subsequent recycling stage.
In the present invention, the source of the m-diisopropylbenzene oxidation mother liquor is not limited, and the m-diisopropylbenzene oxidation mother liquor can be prepared by a conventional method, for example, the method described in US4849549, that is, the m-diisopropylbenzene oxidation mother liquor is used as a raw material, and the m-diisopropylbenzene oxidation mother liquor is obtained by an air oxidation reaction.
The composition of the m-diisopropylbenzene oxidation mother liquor is not limited in the present invention, so long as the m-diisopropylbenzene oxidation mother liquor contains m-diisopropylbenzene, m-isopropyldimethylbenzyl alcohol, m-isopropylcumene hydroperoxide and 1, 3-bis (2-hydroxy-2-propyl) benzene, all of which can be treated by the method of the present invention. In general, the industrially obtained mother liquor for the oxidation of m-diisopropylbenzene contains some impurities such as MC, HHP, DC, etc., in addition to the reaction raw materials and the product DHP.
According to the invention, the m-diisopropylbenzene oxidation mother liquor can be used for extracting DHP first, then the m-diisopropylbenzene oxidation mother liquor is further treated according to the method of the invention, and the DHP can be also reserved in the m-diisopropylbenzene oxidation mother liquor. In order to save the treatment cost and reduce the treatment flow, preferably, the mixed liquor of the m-diisopropylbenzene oxidation reaction can be directly treated without extracting the DHP before the treatment. In this case, the m-diisopropylbenzene oxidation mother liquor further contains 1, 3-bis (2-hydroperoxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide.
According to the present invention, preferably, the content of diisopropylbenzene in the intermediate of the m-diisopropylbenzene oxidation mother liquor is 10% -50%, the content of m-isopropyl dimethyl benzyl alcohol is 1% -30%, the content of 1, 3-bis (2-hydroxy-2-propyl) benzene is 1% -10%, the content of 3- (2-hydroxy-2-propyl) cumene hydroperoxide is 0-10%, the content of m-isopropylcumene hydroperoxide is 30% -60%, and the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 0% -15%, based on the total mass of the m-diisopropylbenzene oxidation mother liquor.
According to the present invention, preferably, the content of diisopropylbenzene in the intermediate of the m-diisopropylbenzene oxidation mother liquor is 20% -40%, the content of m-isopropyl dimethyl benzyl alcohol is 5% -20%, the content of 1, 3-bis (2-hydroxy-2-propyl) benzene is 1% -10%, the content of 3- (2-hydroxy-2-propyl) cumene hydroperoxide is 0.5% -5%, the content of m-isopropyl cumene hydroperoxide is 35% -50%, and the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 3% -15%, based on the total mass of the m-diisopropylbenzene oxidation mother liquor.
According to the invention, the dosage of the hydrogen peroxide is wide in optional range, preferably, the molar ratio of the total molar amount of the 1, 3-di (2-hydroxy-2-propyl) benzene, m-isopropyl dimethyl benzyl alcohol and the optionally contained 3- (2-hydroxy-2-propyl) isopropylbenzene hydrogen peroxide to the hydrogen peroxide is 1:2-10, preferably 1:3-5. Under the preferred scheme, the conversion of MC into MHP and the conversion of DC and HHP into DHP are facilitated to be improved, the conversion rate and selectivity of MC and HHP are improved, and the generation of byproducts is reduced.
According to the invention, the concentration of the hydrogen peroxide is wide in optional range, and in order to facilitate the reaction, and reduce the generation of byproducts, the mass concentration of the hydrogen peroxide is preferably 10% -30%.
According to the present invention, the molar ratio of the total molar amount of the alcoholic hydroxyl groups in the 1, 3-bis (2-hydroxy-2-propyl) benzene and the optionally contained 1, 3-bis (2-hydroperoxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide to the hydrogen peroxide is preferably 1:2-10, preferably 1:3-5, and may be, for example, a ratio of 1 to 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8 and 5, or a ratio of any value between 1 and 3 and 5 to any interval.
According to the invention, the amount of the organic solvent used is selected in a wide range, so long as the diisopropylbenzene oxidizing solution is dissolved as much as possible and is in reaction contact. Preferably, the mass ratio of the organic solvent to the m-diisopropylbenzene oxidation mother liquor is 0.5-5:1, preferably 1-2:1.
According to the present invention, the organic solvent is selected from a wide range, preferably, the organic solvent is a hydrocarbon-substituted aromatic hydrocarbon having 7 to 12 carbon atoms and having 1 to 6 carbon atoms; preferably, the organic solvent is selected from at least one of toluene, para-xylene, ortho-xylene, meta-xylene, ethylbenzene and cumene.
According to the invention, the amount of the acid catalyst is wide, so that the conversion of MC into MHP, the conversion of DC and HHP into DHP and the conversion rate and selectivity of MC and HHP are further improved, and the generation of byproducts is further reduced. Preferably, the mass ratio of the acid catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01-0.1:1, a step of; preferably 0.01-0.05:1.
According to the present invention, preferably, the mass ratio of the acidic catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01 to 0.1:1, a step of; preferably 0.01-0.05:1 may be, for example, a ratio of 0.01, 0.02, 0.03, 0.04, or 0.05 to 1, or a ratio of any value between 0.01 and 0.05 and any interval to 1.
According to the present invention, the acidic catalyst is selected from a wide range, and in order to further promote the reaction while reducing the formation of by-products, it is preferable that the acidic catalyst is at least one selected from sulfuric acid, perchloric acid, nitric acid, phosphoric acid and benzenesulfonic acid.
According to the present invention, the concentration of the acid catalyst is selected to be wide in order to further facilitate the progress of the reaction while reducing the formation of by-products and reducing the emission of three wastes, preferably, the mass concentration of the acid catalyst is not less than 20%. This may be selected to be at different concentrations for different acidic catalysts, for example, the mass concentration of sulfuric acid may be 70% -98%, benzenesulfonic acid may be directly added, and the mass concentration of perchloric acid may be 20% -70%.
According to the invention, the conditions of the reaction are selected in a wide range, preferably the reaction temperature is 30-70 ℃, preferably 40-60 ℃; under the preferred scheme, the reaction is more favorable for carrying out, the conversion of MC into MHP and the conversion of DC and HHP into DHP are more favorable for improving the conversion rate and selectivity of MC and HHP and reducing the generation of byproducts.
In the present invention, the manner of controlling the temperature of the oxidation reaction is not limited, and for example, the temperature may be controlled by heating in a water bath.
According to the present invention, the pressure of the reaction can be selected within a wide range, preferably, in the present invention, the reaction pressure in the reaction process is a negative pressure, preferably, the vacuum degree is (-0.095) MPa- (-0.04) MPa, and more preferably (-0.085) MPa- (-0.07) MPa.
According to the invention, the time for the reaction is chosen within a wide range, preferably from 1 to 6 hours, preferably from 2 to 3 hours.
In the invention, the reaction time refers to the total reaction time from the time when the oxydol and the acid catalyst serving as the raw materials of the oxidation target liquid are added to the time when the reaction is stopped.
According to the present invention, the order of addition of the mixture in the reaction system is not particularly limited, and in order to reduce the occurrence of side reactions, increase the yield of DHP and the content of MHP in the recycled raw material, preferably, the m-diisopropylbenzene oxidation mother liquor is mixed with the organic solvent and hydrogen peroxide to obtain a mixed solution, and then an acidic catalyst is added to obtain a reaction mixed solution.
In a preferred embodiment of the present invention, the reaction conditions include: the temperature is 30-70deg.C, preferably 40-60deg.C; vacuum degree is (-0.095) to (-0.04) MPa, preferably (-0.085) - (-0.07) MPa; the time is 1-4 hours, preferably 2-3 hours. More beneficial to improving the conversion of MC into MHP, DC and HHP into DHP, improving the conversion rate and selectivity of MC and HHP and reducing the generation of byproducts.
In the present invention, preferably, the reaction is carried out under mixing conditions, and the mixing mode can be flexibly adjusted, such as stirring, shaking, etc.
According to the present invention, preferably, the reaction is carried out under reflux conditions such that part of water in the reaction system is separated from the reaction system and the oil phase is returned to the reaction system. Preferably in a reaction apparatus with a condenser.
According to the present invention, when the contents of 1, 3-bis (2-hydroxy-2-propyl) (DC) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide (HHP) in the oil phase mixture are each 1 mass% or less based on the total mass of the oil phase mixture, stopping the reaction; wherein the mass of the organic solvent does not account for the total mass of the oil phase mixture; the end point of the reaction is controlled under such conditions, that is, the present invention can be achieved. Preferably, the reaction is stopped when the conversion of 3-isopropyldimethylbenzyl alcohol MC is greater than 50%, preferably when the conversion of MC is 50% -70%. In this preferred embodiment, it is further advantageous to increase the conversion of MC to MHP, DC and HHP to DHP, to increase the conversion and selectivity of both, and to reduce the formation of by-products. The above technical effect is obtained because, as a result of studies, the inventors of the present invention have found that when the MC conversion rate is too low to be less than 50%, the oxidation reaction is incomplete, DC and HHP are not sufficiently oxidized, and the DHP yield is not high; when the MC conversion rate is over 70%, the oxidation reaction process is not easy to control, the reaction condition is demanding, the oxidation reaction is easy to be over-head, acidolysis side reaction is generated, even if the water in the system is too little in the reaction process, severe reaction can be caused, potential safety hazards exist, and when the conversion rate of the 3-isopropyl dimethyl benzyl alcohol MC is over 50%, the reaction is stopped when the MC conversion rate is preferably 50% -70%, so that the reaction process is easy to control, and the impurity removal rate is high.
The invention adopts gas chromatography to track and detect the MC content in the reaction system, calculates the MC content in the reaction raw material and the MC content in the reaction mixed liquid detected in real time, and calculates the MC conversion rate. In the present invention, the lower the amount of MC present in the reaction product, the higher the reaction conversion. In the present invention, the MC content in the reaction raw materials and products is measured by gas chromatography.
According to the present invention, it is preferable that the content of 1, 3-bis (2-hydroxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the recycled meta-diisopropylbenzene oxidation liquid is 1% by mass or less based on the total mass of the recycled meta-diisopropylbenzene oxidation liquid.
According to the present invention, the method of removing the aqueous phase in the mixed solution obtained after the reaction in the step (2) is liquid-liquid separation, and preferably, the liquid-liquid separation is performed after cooling the mixture obtained by the reaction to room temperature.
According to the invention, the first extraction of the first oil phase with the lye in step (3) is carried out in order to extract 1, 3-bis (2-hydroperoxy-2-propyl) benzene (DHP) into the lye in which the DHP is present in the form of the disodium salt. Preferably, the process of extracting DHP comprises: contacting the first oil phase with an alkali liquor for multiple times, combining the first extraction aqueous phase to obtain a first extraction aqueous phase containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene (DHP), performing back extraction on the first extraction aqueous phase by using a back extraction solvent to obtain a third oil phase containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene and a raffinate phase, and removing the back extraction solvent in the third oil phase to obtain 1, 3-bis (2-hydroperoxy-2-propyl) benzene.
In the invention, the raffinate phase of the third oil phase can be recycled to the alkali liquor extraction system. The conditions of the alkali liquor extraction and the back extraction solvent back extraction are not limited, so long as the corresponding purpose can be achieved.
According to the invention, preferably, the lye is an aqueous solution of sodium hydroxide and/or potassium hydroxide. The alkali liquor has a wide optional range of mass concentration, preferably the alkali liquor has a mass concentration of 1% -15%, preferably 5% -10%.
According to the invention, the stripping solvent has a plurality of optional types, and the invention can be realized as long as DHP can be stripped from alkali liquor. In order to further facilitate the removal of the stripping solvent on the basis of stripping the DHP from the lye, so that the DHP is obtained in a simpler manner, it is preferred that the stripping solvent is at least one selected from the group consisting of methyl isobutyl ketone, methyl isopropyl ketone, methyl ethyl ketone, diethyl ether, diisopropyl ether, butanol and amyl alcohol.
The method further comprises the steps of: the mode of oil-water phase separation of the mixed solution obtained by the reaction can be selected by a person skilled in the art, preferably, the liquid phase is firstly subjected to standing delamination, and the water layer containing excessive hydrogen peroxide and acid catalyst is separated to obtain the first oil phase. The water layer containing excessive hydrogen peroxide and the acid catalyst can be directly returned to the step (1), or can be returned to the step (1) after being concentrated for recycling.
The first oil phase may be directly contacted with the alkali solution, and in order to reduce consumption of the alkali solution and remove water-soluble impurities, preferably, the first oil phase is washed with water and then contacted with the alkali solution.
According to the present invention, the manner of removing the organic solvent in the second oil phase may be variously selected, and it is preferable to remove the organic solvent in the second oil phase by distillation under reduced pressure in the step (4). The conditions for reduced pressure distillation are widely selected. In order to facilitate the removal of the organic solvent while reducing the formation of by-products, preferably, the conditions of the reduced pressure distillation include: the temperature is 30-70deg.C, the vacuum degree is (-0.05) MPa- (-0.098) MPa, and more preferably, the temperature is 40-60deg.C, and the vacuum degree is (-0.07) MPa- (-0.085) MPa.
In a more preferred embodiment of the present invention, the reaction is stopped when the conversion of the 3-isopropyldimethylbenzyl alcohol MC is greater than 50%; step (4) removing the organic solvent in the second oil phase by reduced pressure distillation. In the preferred embodiment, the diisopropylbenzene oxidation liquid obtained by the treatment of the method not only improves the content of MHP and DHP, but also reduces the content of byproduct MC to be less than 1% by more than 50%, and hydrogen peroxide can be recycled by layering, thereby avoiding the damage of the traditional impurity removal technology to MC and DC, converting MC into useful MHP, converting HHP and DC into target product DHP, improving the yield and purity of DHP, avoiding secondary oxidation of crude DHP, and obtaining DHP with higher purity by removing organic solvent by reduced pressure distillation at lower temperature. Compared with the operation of separating peroxide MHP by carrying out reduced pressure distillation on water vapor of US3993696 or carrying out high-temperature distillation on a falling film of US4088699, the method has the advantages of mild reaction conditions, easy control of reaction and high safety; the reaction steps are few; the three wastes are generated in a small amount, clean and environment-friendly, and suitable for industrialization.
The second aspect of the invention provides a recycling method of m-diisopropylbenzene oxidation liquid, comprising the treatment method of the m-diisopropylbenzene oxidation liquid in the first aspect; the method also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene by adopting an oxidation method from the obtained recycled m-diisopropylbenzene oxidation solution.
According to the recycling method of the m-diisopropylbenzene oxidation liquid, the recycled m-diisopropylbenzene oxidation liquid obtained by the treatment method is used as a raw material, the content of MHP in the recycled raw material is increased, the conversion of the recycled m-diisopropylbenzene oxidation liquid into DHP in the oxidation process can be promoted, and the reaction efficiency and the yield of the DHP are improved; the recycled raw materials have low DC and HHP contents, and the negative influence of the recycled raw materials on the subsequent oxidation reaction can be reduced.
For the condition of preparing 1, 3-di (2-hydroperoxy-2-propyl) benzene by using an oxidation method for recycling m-diisopropylbenzene oxidation liquid, the condition of preparing 1, 3-di (2-hydroperoxy-2-propyl) benzene by using an intermediate diisopropylbenzene oxidation method in the prior art, such as a method described in US4849549, is not described herein.
In a third aspect, the present invention provides a method for producing resorcinol, comprising: 1) Oxidizing m-diisopropylbenzene to react under the condition of oxidizing to generate 1, 3-di (2-hydroperoxy-2-propyl) benzene to obtain m-diisopropylbenzene oxidation mother liquor containing 1, 3-di (2-hydroperoxy-2-propyl) benzene; 2) Obtaining 1, 3-bis (2-hydroperoxy-2-propyl) benzene and recycling m-diisopropylbenzene oxidation liquid from m-diisopropylbenzene oxidation mother liquor according to the treatment method of m-diisopropylbenzene oxidation liquid in the first aspect; 3) Returning the recycled m-diisopropylbenzene oxidation liquid obtained in the step 2) to the step 1); 4) And (3) carrying out acidolysis reaction on the 1, 3-di (2-hydroperoxy-2-propyl) benzene obtained in the step (2) in the presence of concentrated sulfuric acid to obtain resorcinol.
According to the resorcinol production method, m-diisopropylbenzene is used as a raw material, through oxidization and the treatment method, impurities in m-diisopropylbenzene oxidation mother liquor can be converted into raw materials which are favorable for recycling, and the recycled m-diisopropylbenzene oxidation liquid is returned to an oxidization stage, so that the utilization rate of the raw materials and the yield of DHP can be improved; while impurity treatment and conversion are carried out, the treatment method can extract the DHP without extracting the DHP in the mother liquor before treatment, has the advantages of high DHP yield and high purity, and can save the process flow. The DHP is used as an intermediate raw material for preparing resorcinol, so the resorcinol production method has the advantages of high raw material utilization rate, high product yield and flow saving.
For the condition of preparing 1, 3-bis (2-hydroperoxy-2-propyl) benzene by the oxidation method for recycling the m-diisopropylbenzene oxidation liquid in the step 1), the condition of preparing 1, 3-bis (2-hydroperoxy-2-propyl) benzene by the prior art intermediate diisopropylbenzene oxidation method can be adopted, for example, the method described in US4849549 is not repeated here.
For the manner of carrying out acidolysis reaction on the 1, 3-bis (2-hydroperoxy-2-propyl) benzene obtained in the step 2) in the presence of concentrated sulfuric acid in the step 4) to obtain resorcinol, the condition of preparing resorcinol from the 1, 3-bis (2-hydroperoxy-2-propyl) benzene in the prior art, for example, the method described in US4849549, is not described here again.
The present invention will be described in detail by examples. In the following examples:
and detecting the compositions of the m-diisopropylbenzene oxidation mother liquor and the recycled m-diisopropylbenzene oxidation liquid and the purity of DHP by adopting a gas chromatography method.
And tracking and detecting the content of MC in the reaction system by a gas chromatography method, and calculating the content of MC in the reaction raw material and the content of MC in the mixed solution in real-time reaction to obtain the consumed content of MC, wherein the percentage of the consumed content of MC to the content of MC in the reaction raw material is the conversion rate of MC.
In the following examples, the DHP yield was calculated by:
In the formula, W DHP Mother liquor of oxidizing solution 、WDC Mother liquor of oxidizing solution 、WHHP Mother liquor of oxidizing solution corresponds to the mass of DHP, DC, HHP in the oxidation mother liquor, and W DHP Obtaining the amount refers to the mass of DHP extracted.
Unless otherwise indicated, all reagents used were commercially available.
Example 1
(1) Into a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and an oil-water separator, 100 g of m-diisopropylbenzene oxidation mother liquor (its composition is shown in Table 1), 100 g of toluene solvent, 30% by mass of hydrogen peroxide, and a total hydroxyl molar ratio of hydrogen peroxide to MC, DC and HHP of 4:1, a step of; 70 mass% sulfuric acid was added, and the weight ratio of sulfuric acid (water content is not counted) to the oxidizing liquid was 0.025:1, a step of; stirring is started, vacuum pumping is carried out through a water pump under the condition of heating in a water bath at 45 ℃ to carry out reduced pressure reflux reaction, and the reaction is carried out under the condition that the vacuum degree is (-0.085) MPa; under the azeotropic state, water and toluene are cooled and enter an oil-water separator, wherein the toluene returns to the three-mouth bottle, and the water is sunk into the oil-water separator for collection; during the reaction, gas chromatography is adopted for detection and tracking, when the reaction is carried out for 2.5 hours, the total mass of the oil phase mixed solution is taken as a reference, the mass of the organic solvent is not counted into the total mass of the oil phase mixed solution, the MC content is 4.4 mass percent, and the reaction is stopped;
(2) And (3) cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing a lower water phase after layering.
(3) The first oil phase was washed with water, then extracted three times with 5 mass% sodium hydroxide solution, the alkaline extracts combined, and the DHP therein was back extracted with methyl isobutyl ketone (MIBK) solvent, and the MIBK solvent was distilled off to give 12.0 g of DHP as a white solid with a purity of 95.8%.
(4) And (3) distilling the second oil phase extracted by the alkali liquor under reduced pressure at 50 ℃ and vacuum degree (-0.08) MPa to remove toluene solvent, so as to obtain recycled m-diisopropylbenzene oxidation liquid which consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the recycled m-diisopropylbenzene oxidation liquid contains 37.0% of DIPB,4.4% of MC, and the contents of MHP, DHP, DC and HHP are shown in Table 2 in percentage by mass.
Example 2
(1) Into a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and an oil-water separator, 100 g of m-diisopropylbenzene oxidation mother liquor (its composition is shown in Table 1), 100 g of toluene, 30% by mass of hydrogen peroxide, and a total hydroxyl molar ratio of hydrogen peroxide to MC, DC and HHP of 2:1, a step of; 20 mass% perchloric acid was added, and the weight ratio of perchloric acid (water content is not counted) to the oxidizing solution was 0.01:1, a step of; stirring is started, vacuum pumping is carried out through a water pump under the condition of heating in a water bath at 50 ℃ for carrying out reduced pressure reflux reaction, and the reaction is carried out under the condition that the vacuum degree is (-0.075 MPa); under the azeotropic state, water and toluene are cooled and enter an oil-water separator, wherein the toluene returns to the three-mouth bottle, and the water is sunk into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, stopping the reaction when the MC content is 5.1% in 2 hours of the reaction;
(2) And (3) cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing a lower water phase after layering.
(3) The first oil phase was washed with water, then extracted four times with 5 mass% sodium hydroxide solution, the alkaline extracts were combined, and the DHP therein was back-extracted with MIBK solvent, which was distilled off to obtain 11.6 g DHP with a purity of 93.2%.
(4) The second oil phase after alkali liquor extraction is subjected to vacuum degree (-0.08) MPa at 50 ℃ to obtain recycled m-diisopropylbenzene oxidation liquid which consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the recycled m-diisopropylbenzene oxidation liquid contains 36.6% of DIPB and 5.1% of MC, and the contents of MHP, DHP, DC and HHP are shown in Table 2 in percentage by mass.
Example 3
(1) Into a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and an oil-water separator, 100 g of m-diisopropylbenzene oxidation mother liquor (its composition is shown in Table 1), 100 g of ethylbenzene solvent, 30% by mass of hydrogen peroxide, and a molar ratio of hydrogen peroxide to hydroxyl groups of MC, DC and HHP of 5:1, a step of; 98 mass% sulfuric acid was added, and the weight ratio of sulfuric acid (water content is not counted) to the oxidizing liquid was 0.05:1, a step of; stirring is started, vacuum pumping is carried out through a water pump under the condition of heating in a water bath at 60 ℃ to carry out reduced pressure reflux reaction, and the reaction is carried out under the condition that the vacuum degree is (-0.075) MPa; under the azeotropic state, water and ethylbenzene enter an oil-water separator after being cooled, wherein the ethylbenzene returns to the three-mouth bottle, and the water is sunk into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, stopping the reaction when the MC content is 4.3% after the reaction is carried out for 4.5 hours;
(2) And (3) cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing a lower water phase after layering.
(3) The first oil phase was washed with water, then extracted three times with 5 mass% sodium hydroxide solution, the alkaline extracts were combined, and DHP was back-extracted with MIBK solvent, which was distilled off to give 12.2 g of DHP as a white solid with a purity of 94.6%.
(4) And (3) distilling the second oil phase extracted by the alkali liquor under reduced pressure at 50 ℃ and vacuum degree (-0.08) MPa to remove the ethylbenzene solvent, so as to obtain recycled m-diisopropylbenzene oxidation liquid which consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the recycled m-diisopropylbenzene oxidation liquid contains 32.6% of DIPB and 4.3% of MC, and the contents of MHP, DHP, DC and HHP are shown in Table 2 in percentage by mass.
Example 4
(1) To a 500 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and an oil-water separator, 100g of m-diisopropylbenzene oxidation mother liquor (its composition is shown in Table 1), 100g of cumene solvent, 30% by mass of hydrogen peroxide, and a molar ratio of hydrogen peroxide to the total hydroxyl group content in MC, DC and HHP of 10:1, a step of; adding benzenesulfonic acid, wherein the weight ratio of benzenesulfonic acid to oxidizing solution is 0.1:1, a step of; stirring is started, vacuum pumping is carried out through a water pump under the condition of heating in a water bath at 65 ℃ for carrying out reduced pressure reflux reaction, and the reaction is carried out under the condition that the vacuum degree is (-0.04) MPa; under the azeotropic state, water and isopropylbenzene are cooled and enter an oil-water separator, wherein the isopropylbenzene returns to a three-mouth bottle, and the water is immersed into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, stopping the reaction when the MC content is 3.8% in the reaction for 5 hours;
(2) And (3) cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing a lower water phase after layering.
(3) The first oil phase was washed with water, then extracted four times with 5 mass% sodium hydroxide solution, the alkaline extracts combined, and the DHP therein back extracted with MIBK solvent, and the MIBK solvent was distilled off to give 12.9 g of DHP as a white solid with a purity of 95.6%.
(4) And (3) distilling the second oil phase extracted by the alkali liquor under reduced pressure at 50 ℃ and a vacuum degree of-0.08 MPa to remove the isopropylbenzene solvent, so as to obtain recycled m-diisopropylbenzene oxidation liquid, wherein the recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, and the contents of MHP, DHP, DC and HHP in the recycled m-diisopropylbenzene oxidation liquid are shown in a table 2 in percentage by mass.
Example 5
The same m-diisopropylbenzene oxidation mother liquor was treated in the same manner as in example 1 except that the weight ratio of sulfuric acid (not counting the water content) to the oxidation liquid in step (1) was 0.12:1, a step of; the molar ratio of hydrogen peroxide to the total hydroxyl groups of MC, DC and HHP is 1.5:1 the end point of the reaction was controlled by the conversion of MC as in example 1. After work-up 9.9 g of DHP as a white solid were obtained with a purity of 90.3%. The obtained recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the contents of MHP, DHP, DC and HHP in the recycled m-diisopropylbenzene oxidation liquid are shown in Table 2 in percentage by mass.
Example 6
The same m-diisopropylbenzene oxidation mother liquor was treated in the same manner as in example 1, except that the molar ratio of hydrogen peroxide to the total hydroxyl groups of MC, DC and HHP was 12:1 the end point of the reaction was controlled by the conversion of MC as in example 1. After work-up 11.0 g of DHP as a white solid were obtained with a purity of 92.7%. The obtained recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the contents of MHP, DHP, DC and HHP in the recycled m-diisopropylbenzene oxidation liquid are shown in Table 2 in percentage by mass.
Example 7
The same m-diisopropylbenzene oxidation mother liquor was treated in the same manner as in example 1, except that the MC conversion was monitored to 40% in step (1), and the reaction was stopped. After work-up 9.5 g of DHP as a white solid were obtained with a purity of 88.5%. The obtained recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the contents of MHP, DHP, DC and HHP in the recycled m-diisopropylbenzene oxidation liquid are shown in Table 2 in percentage by mass.
Comparative example 1
The m-diisopropylbenzene oxidation solution in example 1 is not subjected to hydrogen peroxide secondary oxidation reaction, the oxidation solution is directly subjected to alkali liquor extraction and MIBK back extraction, only 4.8 g of DHP is obtained, the purity is 85%, a small amount of white precipitate is precipitated in the obtained oxidation solution because of containing DC, the MC and DC contents are higher and higher along with the increase of the recycling times of the oxidation solution, the recycling oxidation reaction speed of the recycled oxidation solution is slower and slower, the byproduct HHP and DC are generated more and more due to the accumulation of MC content, and the generation efficiency and purity of the target product DHP are poorer and worse, and the pipeline is blocked due to the DC precipitate, so that the normal production is seriously influenced.
The obtained recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the recycled m-diisopropylbenzene oxidation liquid contains 38.3% of DIPB and 14% of MC, and the contents of MHP, DHP, DC and HHP are shown in Table 2 in percentage by mass.
Comparative example 2
The same m-diisopropylbenzene oxidation mother liquor was treated in the same manner as in example 1, except that sodium peroxide was used instead of hydrogen peroxide.
The obtained recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, wherein the recycled m-diisopropylbenzene oxidation liquid contains 36.3% of DIPB and 13.8% of MC, and the contents of MHP, DHP, DC and HHP are shown in Table 2 in percentage by mass.
TABLE 1
TABLE 2
As can be seen from the above examples and comparative examples, the specific method of the present invention can obtain high yield and high selectivity diisopropylbenzene dihydroperoxide DHP, the content of MHP in the recycled meta-diisopropylbenzene oxidation liquid obtained after treatment is increased, the contents of byproducts MC, DC and HHP are reduced, the problem of accumulation of byproducts in oxidation reaction is solved, the oxidation speed can be increased after recycling the meta-diisopropylbenzene oxidation liquid to an oxidation system, and further the DHP yield can be further increased.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (28)
1. The method for treating the m-diisopropylbenzene oxidizing solution is characterized by comprising the following steps of:
(1) Under the reaction condition that the hydroxylate is converted into the peroxidized hydroxylate, the m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in the presence of an acid catalyst and an organic solvent;
(2) Removing the water phase in the mixed solution obtained after the reaction to obtain a first oil phase;
(3) Performing first extraction on the first oil phase by using alkali liquor to obtain a first extracted water phase and a second oil phase, performing back extraction on the first extracted water phase by using a back extraction solvent to obtain a third oil phase containing 1, 3-bis (2-hydroperoxy-2-propyl) benzene, and removing the back extraction solvent in the third oil phase to obtain 1, 3-bis (2-hydroperoxy-2-propyl) benzene;
(4) Removing the organic solvent in the second oil phase to obtain recycled m-diisopropylbenzene oxidation liquid;
wherein the m-diisopropylbenzene oxidation mother liquor contains m-diisopropylbenzene, m-isopropyl dimethyl benzyl alcohol, m-isopropyl cumene hydroperoxide and 1, 3-di (2-hydroxy-2-propyl) benzene.
2. The process according to claim 1, wherein the m-diisopropylbenzene oxidation mother liquor further contains 1, 3-bis (2-hydroperoxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide.
3. The process according to claim 2, wherein,
Based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the content of diisopropylbenzene in the m-diisopropylbenzene oxidation mother liquor is 10% -50%, the content of m-isopropyldimethylbenzyl alcohol is 1% -30%, the content of 1, 3-bis (2-hydroxy-2-propyl) benzene is 1% -10%, the content of 3- (2-hydroxy-2-propyl) isopropylbenzene hydroperoxide is 0% -10%, the content of m-isopropylbenzene hydroperoxide is 30% -60%, and the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 0% -15%.
4. A process according to claim 3, wherein,
Based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the content of the intermediate diisopropylbenzene in the m-diisopropylbenzene oxidation mother liquor is 20% -40%, the content of m-isopropyldimethylbenzyl alcohol is 5% -20%, the content of 1, 3-bis (2-hydroxy-2-propyl) benzene is 1% -10%, the content of 3- (2-hydroxy-2-propyl) isopropylbenzene hydroperoxide is 0.5% -5%, the content of m-isopropylbenzene hydroperoxide is 35% -50%, and the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 3% -15%.
5. The method according to claim 2, wherein the molar ratio of the total molar amount of the alcoholic hydroxyl groups in the 1, 3-bis (2-hydroxy-2-propyl) benzene, m-isopropyl dimethylbenzyl alcohol and the optionally contained 3- (2-hydroxy-2-propyl) cumene hydroperoxide to the hydrogen peroxide is 1:2-10.
6. A treatment method according to claim 5, wherein the molar ratio of the total molar amount of alcoholic hydroxyl groups in the 1, 3-bis (2-hydroxy-2-propyl) benzene, m-isopropyl dimethylbenzyl alcohol and optionally 3- (2-hydroxy-2-propyl) cumene hydroperoxide to the hydrogen peroxide is 1:3-5.
7. The treatment method according to any one of claims 1 to 6, wherein a mass ratio of the organic solvent to the m-diisopropylbenzene oxidation mother liquor is 0.5 to 5:1.
8. The process according to claim 7, wherein the mass ratio of the organic solvent to the m-diisopropylbenzene oxidation mother liquor is 1-2:1.
9. A process according to any one of claims 1 to 6, wherein,
The organic solvent is hydrocarbon-substituted aromatic hydrocarbon with carbon number of 7-12 and carbon number of 1-6.
10. The process according to claim 9, wherein,
The organic solvent is selected from at least one of toluene, paraxylene, o-xylene, m-xylene, ethylbenzene and cumene.
11. The treatment method according to any one of claims 1 to 6, wherein a mass ratio of the acidic catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01 to 0.1:1.
12. The treatment method according to claim 11, wherein a mass ratio of the acidic catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01-0.05:1.
13. A process according to any one of claims 1 to 6, wherein,
The acidic catalyst is selected from at least one of sulfuric acid, perchloric acid, nitric acid, phosphoric acid and benzenesulfonic acid.
14. The process of any one of claims 1-6, wherein the reaction conditions comprise: the temperature is 30-70 ℃; and/or, the vacuum degree is (-0.095) MPa- (-0.04) MPa; and/or the reaction time is 1-6h.
15. The process of claim 14, wherein the reaction conditions comprise: the temperature is 40-60 ℃; and/or, the vacuum degree is (-0.085) MPa- (-0.07) MPa; and/or the reaction time is 2-3h.
16. A process according to any one of claims 1 to 6, wherein,
The reaction is carried out under the condition of reflux, so that part of water in the reaction system is separated from the reaction system, and the oil phase returns to the reaction system.
17. The process of any of claims 1-6, wherein the reaction is stopped when the conversion of 3-isopropyldimethylbenzyl alcohol is greater than 50%.
18. The process of claim 17, wherein the reaction is stopped when the conversion of 3-isopropyldimethylbenzyl alcohol is 50% -70%.
19. A process according to any one of claims 1 to 6, wherein,
The content of 1, 3-di (2-hydroxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the reclaimed meta-diisopropylbenzene oxidation liquid is below 1 mass percent based on the total mass of the reclaimed meta-diisopropylbenzene oxidation liquid.
20. The process according to any one of claims 1 to 6, wherein the lye is an aqueous solution of sodium hydroxide and/or potassium hydroxide.
21. A process according to any one of claims 1 to 6, wherein,
The mass concentration of the alkali liquor is 1% -15%.
22. The process according to claim 21, wherein,
The mass concentration of the alkali liquor is 5% -10%.
23. A process according to any one of claims 1 to 6, wherein,
The back extraction solvent is at least one selected from methyl isobutyl ketone, methyl isopropyl ketone, methyl ethyl ketone, diethyl ether, diisopropyl ether, butanol and amyl alcohol.
24. The process according to any one of claims 1 to 6, wherein the organic solvent in the second oil phase is removed by distillation under reduced pressure in step (4).
25. The process of claim 24, wherein,
Conditions for the reduced pressure distillation include: the temperature is 30-70 ℃, and the vacuum degree is (-0.05) MPa- (-0.098) MPa.
26. The process of claim 25, wherein,
Conditions for the reduced pressure distillation include: the temperature is 40-60 ℃, and the vacuum degree is (-0.07) MPa- (-0.085) MPa.
27. A method for recycling m-diisopropylbenzene oxidation liquid, comprising the method for treating m-diisopropylbenzene oxidation liquid according to any one of claims 1-26;
the method also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene by adopting an oxidation method from the obtained recycled m-diisopropylbenzene oxidation solution.
28. A method for producing resorcinol, comprising:
1) Oxidizing m-diisopropylbenzene to react under the condition of oxidizing to generate 1, 3-di (2-hydroperoxy-2-propyl) benzene to obtain m-diisopropylbenzene oxidation mother liquor containing 1, 3-di (2-hydroperoxy-2-propyl) benzene;
2) Obtaining 1, 3-bis (2-hydroperoxy-2-propyl) benzene and recycling m-diisopropylbenzene oxidation liquid from m-diisopropylbenzene oxidation mother liquor according to the treatment method of m-diisopropylbenzene oxidation liquid of any one of claims 1-26;
3) Returning the recycled m-diisopropylbenzene oxidation liquid obtained in the step 2) to the step 1);
4) And (3) carrying out acidolysis reaction on the 1, 3-di (2-hydroperoxy-2-propyl) benzene obtained in the step (2) in the presence of concentrated sulfuric acid to obtain resorcinol.
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| US3950431A (en) * | 1972-11-21 | 1976-04-13 | Sumitomo Chemical Company, Limited | Process for removing impurities in an oxidation mixture |
| CN112679403A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide |
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| JPS5852972B2 (en) * | 1976-08-18 | 1983-11-26 | 三井化学株式会社 | Method for producing divalent phenols |
| JPS6017783B2 (en) * | 1977-10-31 | 1985-05-07 | 三井化学株式会社 | Method for oxidizing m-diisopropylbenzene |
| JPS6024788B2 (en) * | 1978-10-17 | 1985-06-14 | 三井化学株式会社 | Method for producing aromatic hydroperoxide |
| US4849549A (en) * | 1987-12-22 | 1989-07-18 | Indspec Chemical Corporation | Process for preparation of resorcinol |
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| US3950431A (en) * | 1972-11-21 | 1976-04-13 | Sumitomo Chemical Company, Limited | Process for removing impurities in an oxidation mixture |
| CN112679403A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for preparing m-diisopropylbenzene hydroperoxide and p-diisopropylbenzene hydroperoxide |
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