CN115583906A - 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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- oxidation
- benzene
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 197
- 230000003647 oxidation Effects 0.000 title claims abstract description 174
- 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 167
- 238000000034 method Methods 0.000 title claims abstract description 94
- 239000007788 liquid Substances 0.000 title claims abstract description 90
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000012452 mother liquor Substances 0.000 claims abstract description 59
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 150000002978 peroxides Chemical class 0.000 claims abstract description 7
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 21
- -1 m-isopropyldimethylbenzyl alcohol Chemical compound 0.000 claims description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 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 13
- 230000002378 acidificating effect Effects 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 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
- 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 9
- 238000004821 distillation Methods 0.000 claims description 9
- 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
- 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
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 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 28
- 229960002163 hydrogen peroxide Drugs 0.000 description 27
- 239000006227 byproduct Substances 0.000 description 24
- 239000012535 impurity Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 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 9
- 230000000694 effects Effects 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000009825 accumulation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 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
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- 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 2
- 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
- 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
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940072185 drug for treatment of tuberculosis Drugs 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
- 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
- 239000013067 intermediate product 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
- 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
- 239000000575 pesticide Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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-
- 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 production method of resorcinol, wherein the treatment method comprises the following steps: under the reaction condition that hydroxylates are converted into peroxide hydroxylates, m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in the presence of an acid catalyst and an organic solvent; removing a water phase in the mixed solution obtained after the reaction to obtain a first oil phase; carrying out first extraction on the first oil phase by using alkali liquor to obtain a first extracted water phase and a second oil phase, carrying out 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; 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 DHP purity.
Description
Technical Field
The invention relates to the field of resorcinol production, and particularly relates to a treatment method and a recycling method of m-diisopropylbenzene oxidation liquid and a production method of 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 production process of resorcinol mainly comprises benzene sulfonation alkali fusion method, m-phenylenediamine hydrolysis method and m-diisopropylbenzene oxidation method. The m-diisopropylbenzene oxidation method is developed and successfully developed by Stanford university in the middle of the 20 th century and the 80 th generation 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 producing resorcinol for Sumitomo and Mitsui chemical company in Japan solves the environmental problem which can not be solved by the traditional process, and is the main direction of resorcinol production development in future.
The patent application US4849549 discloses a method for preparing resorcinol, which comprises the steps of taking m-diisopropylbenzene as a raw material, carrying out an oxidation reaction by introducing air in the presence of an m-diisopropylbenzene oxidation liquid initiator at a certain temperature and under a certain pressure to obtain an oxidation liquid mainly containing m-diisopropylbenzene, m-isopropylcumene hydroperoxide (MHP), 1, 3-bis (2-hydroperoxy-2-propyl) benzene (m-DHP) and 3- (2-hydroxy-2-propyl) cumene hydroperoxide (HHP), extracting the DHP and the HHP in the oxidation liquid into an alkali liquor by using a sodium hydroxide solution, carrying out low-temperature and high-temperature back extraction on methyl isobutyl ketone (MIBK) to separate m-DHP with higher purity, taking m-DHP as a raw material, and carrying out an acidolysis reaction in the presence of a concentrated sulfuric acid catalyst to obtain resorcinol and simultaneously obtain acetone as a byproduct.
A schematic diagram of the reaction pathway for the preparation of DHP by the m-diisopropylbenzene oxidation reaction is shown in FIG. 1. As is clear from the above reaction formula, in addition to MHP, DHP and HHP, by-products such as m-isopropyldimethylbenzyl alcohol (MC) and 1, 3-bis (2-hydroxy-2-propyl) benzene (DC) are produced in the oxidation process of m-diisopropylbenzene.
According to research results, the content of MC, HHP and DC in the oxidation liquid is increased along with the increase of the recycling times of the recycled oxidation liquid, if impurity removal treatment is not carried out on the recycled oxidation liquid, the oxidation reaction of the recycled oxidation liquid is influenced by the byproducts along with the increase of the content of MC, DC and HHP, and the byproducts are easy to precipitate out after the content of DC is more than 4.2%, so that a pipeline is blocked, and the measurement of a sensing probe is influenced. In order to increase the oxidation reaction rate of the recycled oxidation liquid, impurities that are byproducts of the oxidation reaction must be removed.
US patent application US3950431 discloses a method for removing accumulated oxidation by-products from an oxidation liquid from which DHP has been separated by alkaline extraction, wherein alcohols such as MC, HHP and DC, and ketones and olefins such as isopropylacetophenone (MK) and hydroxyisopropylacetophenone (KC) affecting the oxidation reaction are removed by extracting with an alkaline aqueous solution (alcohol-base-water mixed extractant) containing 10% to 80% methanol or ethanol for reuse in the diisopropylbenzene oxidation liquid. The method has the defects that an alcohol-alkali-water mixed extractant is selected for extracting and recycling the oxidation liquid to remove oxidation reaction byproducts, but the contradiction between the removal rate and the oil-water phase layering effect exists in the process. In order to improve the removal rate, the content of solvent alcohol must be increased, because the alcohol is mutually soluble with water, the oil-water phase layering effect is poor, the oxidation liquid after extraction contains a large amount of methanol or ethanol, the methanol or ethanol must be removed by distillation, the removal process is complex, and the methanol or ethanol is dissolved in the oxidation liquid to bring new impurities which influence the oxidation reaction, so that great potential safety hazard exists. Similarly, in order to improve the layering effect of the extraction oil phase and the water phase, the proportion of the added alcohol needs to be reduced, and the impurity removal efficiency of the oxidation liquid is low. As the polarity difference between MHP and MC is not large, a certain amount of MHP inevitably enters into the alcohol-water solution, so that the loss of useful components is caused, the raw material cost is increased, and the wastewater amount is increased.
US patent applications US4088699 and US3993696 likewise disclose methods for removing oxidation affecting impurities from an oxidation liquor from which DHP has been removed. The difference is that the patent application US4088699 adopts a falling film evaporator under the vacuum degree of 110mmHg, steam heating at 154 ℃ is adopted, the kettle temperature is 132 ℃, diisopropylbenzene and MHP in the recycled oxidation liquid are distilled out, and the recovery rate of the MHP is 82.5%. Patent application US3993696 adopts the method that under the conditions of neutrality and alkalescence (pH is 6 to 9) and under the condition of reduced pressure, the vacuum degree is 20 to 300mmHg, the m-p mixed diisopropylbenzene oxidizing solution without DHP is subjected to steam distillation, diisopropylbenzene and diisopropylbenzene hydroperoxide MHP are distilled out together with water, diisopropylbenzene and MHP are obtained through oil-water separation, and the recovery rate of MHP is 91 percent at most. Because the boiling point of MC is lower than MHP, MC in the oxidation liquid is inevitably distilled out together with MHP, and DC is also brought out, so the method for removing impurities in the oxidation liquid by steam distillation under reduced pressure cannot obtain satisfactory effect, and heating the oxidation liquid for a long time at 105-110 ℃ easily causes thermal decomposition of MHP, has great safety hazard, and is not suitable for industrial production.
In conclusion, the treatment process for recovering the oxidation liquid in the prior art has the following defects: because the boiling point of MC is lower than MHP, MC in the oxidation liquid must be distilled out together with MHP, and DC is also brought out, MHP and residual DHP are heated and decomposed at high temperature to respectively generate MC and KC, and MC and DC are also 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 waste liquid discharge amount, and is not beneficial to energy conservation and consumption reduction; impurities in the oxidation reaction cannot be effectively removed, and the accumulation of the impurities in the oxidation liquid can influence the circular oxidation of the oxidation liquid.
Disclosure of Invention
The invention aims to solve the problems that peroxide of hydroxyl by-products MC and DC is easy to decompose, potential safety hazard exists 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; meanwhile, the treatment method can convert DC and HHP into target products DHP, can avoid accumulation of DC and adverse effects of HHP on subsequent oxidation reaction, can extract DHP, and has the advantages of high DHP yield and purity, and the method has the advantages of mild reaction conditions, less three-waste generation, cleanness, environmental protection and easiness in industrialization.
In order to achieve the above object, a first aspect of the present invention provides a method for treating m-diisopropylbenzene oxidizing solution, comprising the steps of: (1) Under the reaction condition that hydroxylates are converted into peroxide hydroxylates, 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 extraction water phase and a second oil phase, performing back extraction on the first extraction 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 invention provides a recycling method of m-diisopropylbenzene oxidation liquid in a second aspect, which comprises the treatment method of the m-diisopropylbenzene oxidation liquid in the first aspect; also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene from the obtained recycled m-diisopropylbenzene oxidation liquid by an oxidation method.
The third aspect of the present invention provides a method for producing resorcinol, which comprises: 1) Carrying out m-diisopropylbenzene oxidation 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) The m-diisopropylbenzene oxidation mother liquor is treated according to the method for treating the m-diisopropylbenzene oxidation liquor of the first aspect to obtain 1, 3-di (2-hydroperoxy-2-propyl) benzene and recycled m-diisopropylbenzene oxidation liquor; 3) Returning the recycled m-diisopropylbenzene oxidation liquid obtained in the step 2) to the step 1); 4) 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, under the reaction condition of converting hydroxylate into peroxide hydroxylate, m-diisopropylbenzene oxidation mother liquor is in contact reaction with hydrogen peroxide in an organic solvent in the presence of an acid catalyst, so that a 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 DHP yield is improved; meanwhile, the treatment method can convert DC and HHP into the target product DHP, and can avoid the accumulation of DC and the adverse effect of HHP on the subsequent oxidation reaction. 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 oxidation liquid obtained by the method has few impurities, eliminates the influence of the accumulation of MC, DC and HHP on the preparation of DHP through m-diisopropylbenzene oxidation reaction, avoids the blockage of DC precipitate on equipment pipelines, reduces the discharge of waste liquid and reduces the cost.
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 the raw material, the content of MHP in the recycled raw material is increased, the recycled m-diisopropylbenzene oxidation liquid can be promoted to be converted into DHP in the oxidation process, and the reaction efficiency and the yield of the DHP are improved; the contents of DC and HHP in the recycled raw materials are low, so that the negative effects of the DC and the HHP 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, DHP is not required to be extracted in advance through the oxidation and the treatment method, impurities in m-diisopropylbenzene oxidation mother liquor can be converted into the raw material which is beneficial to recycling, the recycled m-diisopropylbenzene oxidation liquid returns to an oxidation stage, and the utilization rate of the raw material and the yield of the DHP can be improved; while the impurities are treated and converted, the treatment method can extract DHP without extracting DHP in the mother liquor before treatment, has the advantages of high DHP yield and high purity, and can save process flows. DHP is used as an intermediate raw material for preparing resorcinol, so the production method of resorcinol has the advantages of high utilization rate of raw materials, high product yield and process saving.
Drawings
FIG. 1 is a schematic diagram of the reaction pathway for the preparation of DHP by the m-diisopropylbenzene oxidation;
FIG. 2 is a schematic diagram of the reaction path of the reaction of the components in the m-diisopropylbenzene oxidation mother liquor and hydrogen peroxide.
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.
The invention provides a method for treating m-diisopropylbenzene oxidizing solution, which comprises the following steps: (1) Under the reaction condition of converting hydroxylate into peroxide hydroxylate, in the presence of an acidic catalyst and an organic solvent, carrying out contact reaction on m-diisopropylbenzene oxidation mother liquor and hydrogen peroxide; (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 extraction water phase and a second oil phase, performing back extraction on the first extraction 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 the accumulation of MC, DC and HHP on the preparation of DHP through m-diisopropylbenzene oxidation reaction, avoids the blockage of DC precipitate on equipment pipelines, reduces the discharge of waste liquid and reduces the cost.
The reaction path schematic diagram of the reaction of the components in the m-diisopropylbenzene oxidation mother liquor and hydrogen peroxide is shown in figure 2. It can be seen that according to the treatment process of the present invention, MC can be converted into useful intermediate MHP; can convert DC and HHP into target product DHP. As can be seen from FIG. 1, MHP as an intermediate raw material for producing DHP increases the content of MHP, and in the subsequent oxidation reaction in the recycling stage, the reaction efficiency and the utilization rate of the raw material must be improved.
In the present invention, the m-diisopropylbenzene oxidation mother liquor is not limited in its source and can be prepared by a conventional method, for example, a method described in US4849549, which is a method of producing m-diisopropylbenzene from m-diisopropylbenzene by an air oxidation reaction.
The composition of the m-diisopropylbenzene oxidation mother liquor is not limited in the invention, and the m-diisopropylbenzene oxidation mother liquor can be treated by the method provided by the invention as 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. In general, the industrially obtained m-diisopropylbenzene oxidation mother liquor contains impurities such as MC, HHP, DC and the like in addition to the reaction raw material and the product DHP.
According to the invention, the m-diisopropylbenzene oxidation mother liquor can extract DHP firstly, and then the m-diisopropylbenzene oxidation mother liquor is further treated according to the method of the invention, and the DHP can also be retained in the m-diisopropylbenzene oxidation mother liquor. In order to save the treatment cost and reduce the treatment flow, the DHP may preferably not be extracted before the treatment, but the mixed solution of the m-diisopropylbenzene oxidation reaction may be directly treated. 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, based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the m-diisopropylbenzene content of the m-diisopropylbenzene oxidation mother liquor is 10% to 50%, the m-isopropyldimethylbenzyl alcohol content is 1% to 30%, the 1, 3-bis (2-hydroxy-2-propyl) benzene content is 1% to 10%, the 3- (2-hydroxy-2-propyl) cumene hydroperoxide content is 0% to 10%, the m-isopropylcumene hydroperoxide content is 30% to 60%, and the 1, 3-bis (2-hydroperoxy-2-propyl) benzene content is 0% to 15%.
According to the present invention, preferably, based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the m-diisopropylbenzene content of the m-diisopropylbenzene oxidation mother liquor is 20% to 40%, the m-isopropyldimethylbenzyl alcohol content is 5% to 20%, the 1, 3-bis (2-hydroxy-2-propyl) benzene content is 1% to 10%, the 3- (2-hydroxy-2-propyl) cumene hydroperoxide content is 0.5% to 5%, the m-isopropylcumene hydroperoxide content is 35% to 50%, and the 1, 3-bis (2-hydroperoxy-2-propyl) benzene content is 3% to 15%.
According to the invention, the dosage of the hydrogen peroxide is wide in selection range, preferably, the molar ratio of the total molar amount of the 1, 3-bis (2-hydroxy-2-propyl) benzene, the m-isopropyl dimethyl benzyl alcohol and the optionally contained 3- (2-hydroxy-2-propyl) cumene hydroperoxide to the alcoholic hydroxyl group in the hydrogen peroxide is 1. Under the preferable scheme, the conversion rate and selectivity of MC to MHP and the conversion rate and selectivity of DC and HHP to DHP are improved, and the generation of by-products is reduced.
According to the invention, the concentration of the hydrogen peroxide is wide in the 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 invention, preferably, the molar ratio of the total molar amount of the 1, 3-bis (2-hydroxy-2-propyl) benzene and the optional 1, 3-bis (2-hydroperoxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide to the hydrogen peroxide is 1.
According to the invention, the dosage of the organic solvent can be selected from a wide range, so long as the diisopropylbenzene oxidation liquid is dissolved as much as possible and is in contact with the reaction. Preferably, the mass ratio of the organic solvent to the m-diisopropylbenzene oxidation mother liquor is 0.5-5:1, preferably 1-2.
According to the invention, the selection range of the organic solvent is wide, and preferably, the organic solvent is C7-12 arene substituted by C1-6 alkyl; preferably, the organic solvent is selected from at least one of toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and cumene.
According to the invention, the amount of the acidic catalyst is wide, and in order to further improve the conversion of MC to MHP, the conversion of DC and HHP to DHP, and further improve the conversion rate and selectivity of the MC and the HHP, the formation of by-products is further reduced. Preferably, the mass ratio of the acidic catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01-0.1:1; preferably 0.01 to 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; preferably 0.01 to 0.05:1 may be, for example, 0.01, 0.02, 0.03, 0.04, a ratio of 0.05 to 1, or any value between 0.01 and 0.05 and a ratio of any interval to 1.
According to the present invention, the acid catalyst is selected from a wide range, and in order to further promote the reaction while reducing the production of by-products, it is preferable that the acid catalyst is selected from at least one of sulfuric acid, perchloric acid, nitric acid, phosphoric acid, and benzenesulfonic acid.
According to the invention, the concentration of the acidic catalyst is selected in a wide range, so as to further facilitate the reaction, reduce the generation of byproducts and reduce the emission of three wastes, and preferably, the mass concentration of the acidic catalyst is not less than 20%. This can be done by selecting different concentrations for different acidic catalysts, for example, the mass concentration of sulfuric acid can be 70% to 98%, benzenesulfonic acid can be added directly, and the mass concentration of perchloric acid can be 20% to 70%.
According to the invention, the reaction conditions can be selected in a wide range, and the reaction temperature is preferably 30-70 ℃, preferably 40-60 ℃; under the preferable scheme, the reaction is more favorably carried out, the conversion of MC to MHP, the conversion of DC and HHP to DHP are more favorably improved, the conversion rate and the selectivity of the MC to MHP and the DC and the HHP to DHP are improved, and the generation of by-products is reduced.
In the present invention, the temperature of the oxidation reaction is not limited, and may be controlled by heating in a water bath, for example.
According to the invention, the pressure for the reaction can be selected in a wide range, and preferably, in the invention, the reaction pressure in the reaction process is 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 reaction time can be selected 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 of adding the oxydol and the acid catalyst serving as the raw materials of the oxidizing target solution to the time of stopping the reaction.
According to the present invention, the order of adding the mixture in the reaction system is not particularly limited, and in order to reduce the occurrence of side reactions and to increase the yield of DHP and the content of MHP in the recycled raw material, it is preferable to first mix the m-diisopropylbenzene oxidation mother liquor with the organic solvent and hydrogen peroxide to obtain a mixed solution, and then add the acidic catalyst to obtain a reaction mixed solution.
In a preferred embodiment of the present invention, the reaction conditions include: the temperature is 30-70 ℃, preferably 40-60 ℃; the vacuum degree is (-0.095) to (-0.04) MPa, preferably (-0.085) - (-0.07) MPa; the time is 1-4h, preferably 2-3h. Is more beneficial to improving the conversion of MC into MHP, the conversion of 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, the reaction is preferably carried out under a mixing condition, and the mixing manner 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 the water in the reaction system is removed 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 both 1 mass% or less based on the total mass of the oil-phase mixture, the reaction is stopped; wherein the mass of the organic solvent is not counted into the total mass of the oil phase mixed solution; the invention can be realized by controlling the end point of the reaction under the condition. Preferably, the reaction is stopped when the conversion of said 3-isopropyldimethylbenzyl alcohol MC is more than 50%, preferably the conversion of MC is 50% -70%. In this preferred embodiment, it is more 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-mentioned technical effects are obtained because, as a result of the studies by the present inventors, it was found that when the conversion of MC 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 conversion rate of the MC is higher than 50%, preferably 50-70%, the reaction is stopped, so that the method has high impurity removal rate and the reaction process is easy to control.
The method for measuring the conversion rate of the MC adopts the gas chromatography, namely the content of the MC in a reaction system is tracked and detected through the gas chromatography, and the conversion rate of the MC is calculated through calculating the content of the MC in reaction raw materials and the content of the MC in a reaction mixed solution detected in real time. In the present invention, the lower the content 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 determined by gas chromatography.
According to the present invention, it is preferable that the contents of 1, 3-bis (2-hydroxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the recycled m-diisopropylbenzene oxidation liquid are both 1 mass% or less based on the total mass of the recycled m-diisopropylbenzene oxidation liquid.
According to the present invention, the step (2) of removing the aqueous phase from the mixed solution obtained after the reaction is liquid-liquid separation, and preferably, the mixture obtained after the reaction is cooled to room temperature before the liquid-liquid separation.
According to the invention, the first extraction of the first oil phase with 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 DHP is present in the form of the disodium salt. Preferably, the process of extracting DHP comprises: contacting the first oil phase with 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), carrying out 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 of the back extraction solvent are not limited, so long as the corresponding purposes can be realized.
According to the invention, the lye is preferably an aqueous solution of sodium hydroxide and/or potassium hydroxide. The selectable range of the mass concentration of the alkali liquor is wide, preferably, the mass concentration of the alkali liquor is 1% -15%, preferably 5% -10%.
According to the invention, the stripping solvent can be selected from a wide variety, and the invention can be realized as long as DHP can be stripped from the alkali liquor. In order to further facilitate the removal of the stripping solvent on the basis of the stripping of DHP out of the alkaline liquor, such that DHP is obtained in a simpler manner, preferably the stripping solvent is selected from at least one of methyl isobutyl ketone, methyl isopropyl ketone, methyl ethyl ketone, diethyl ether, diisopropyl ether, butanol and pentanol.
The method further comprises the following steps: the way of separating the mixed liquid obtained from the reaction into oil and water phases can be chosen by those skilled in the art, and preferably, the liquid phase is first subjected to standing for layering, and the water layer containing the excess hydrogen peroxide and the acidic catalyst is removed to obtain the first oil phase. Wherein, the water layer containing the excess hydrogen peroxide and the acidic catalyst can be directly returned to the step (1), or can be returned to the step (1) after concentration for recycling.
The first oil phase may be directly contacted with the lye, and in order to reduce the consumption of the lye and simultaneously remove the water-soluble impurities, the first oil phase is preferably washed with water and then contacted with the lye.
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 that the organic solvent in the second oil phase is removed by distillation under reduced pressure in the step (4). The selection range of the conditions for the reduced pressure distillation is wide. In order to facilitate the removal of the organic solvent and reduce the formation of byproducts, the conditions of the reduced pressure distillation preferably include: the temperature is 30-70 deg.C, and the vacuum degree is (-0.05) MPa- (-0.098) MPa, more preferably, the temperature is 40-60 deg.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 more than 50%; and (4) removing the organic solvent in the second oil phase by means of reduced pressure distillation. In the preferred embodiment, the diisopropylbenzene oxidation solution obtained by the method disclosed by the invention is treated, the contents of MHP and DHP are increased, the byproduct MC can be reduced by more than 50%, the contents of DC and HHP are reduced to less than 1%, hydrogen peroxide can be recycled by layering and recycling, the damage of the existing impurity removal process to MC and DC is avoided, MC is converted into useful MHP, HHP and DC are converted into target products DHP, the yield and purity of DHP are increased, secondary oxidation of crude DHP products is avoided, and DHP with higher purity can be obtained only by removing an organic solvent through reduced pressure distillation at a lower temperature. Compared with the operation of distilling water vapor under reduced pressure or distilling falling film at high temperature to separate peroxide MHP in US3993696 or US4088699, the method has the advantages of mild reaction conditions, easy control of the reaction and high safety; the reaction steps are few; the production of three wastes is less, clean and environment-friendly, and is suitable for industrialization.
The second aspect of the invention provides a recycling method of m-diisopropylbenzene oxidation liquid, which comprises the treatment method of the m-diisopropylbenzene oxidation liquid in the first aspect; also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene from the obtained reclaimed m-diisopropylbenzene oxidation solution by an oxidation method.
According to the recycling method of the m-diisopropylbenzene oxidizing solution, the recycled m-diisopropylbenzene oxidizing solution obtained by the treatment method is used as the raw material, the content of MHP in the recycled raw material is increased, the recycled m-diisopropylbenzene oxidizing solution can be promoted to be converted into DHP in the oxidation process, 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 effects of the DC and the HHP on the subsequent oxidation reaction can be reduced.
As for the condition for preparing 1, 3-bis (2-hydroperoxy-2-propyl) benzene by using an oxidation method for recycling m-diisopropylbenzene oxidation liquid, the condition for preparing 1, 3-bis (2-hydroperoxy-2-propyl) benzene by using a prior art intermediate diisopropylbenzene oxidation method, such as the method described in U.S. Pat. No. 4,4849549, can be adopted, and details are not repeated.
The third aspect of the present invention provides a method for producing resorcinol, which comprises: 1) Carrying out m-diisopropylbenzene oxidation 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) The m-diisopropylbenzene oxidation mother liquor is treated according to the method for treating the m-diisopropylbenzene oxidation liquor of the first aspect to obtain 1, 3-di (2-hydroperoxy-2-propyl) benzene and recycled m-diisopropylbenzene oxidation liquor; 3) Returning the recycled m-diisopropylbenzene oxidizing solution obtained in the step 2) to the step 1); 4) 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.
The production method of the resorcinol takes the m-diisopropylbenzene as the raw material, and through the oxidation and the treatment method, DHP does not need to be extracted in advance, impurities in m-diisopropylbenzene oxidation mother liquor can be converted into the raw material which is beneficial to recycling, the recycled m-diisopropylbenzene oxidation liquor returns to an oxidation stage, and the utilization rate of the raw material and the yield of the DHP can be improved; while the impurities are treated and converted, the treatment method can extract DHP without extracting DHP in the mother liquor before treatment, has the advantages of high DHP yield and high purity, and can save process flows. DHP is used as an intermediate raw material for preparing resorcinol, so the production method of resorcinol has the advantages of high utilization rate of raw materials, high product yield and process saving.
For the condition of preparing 1, 3-di (2-hydroperoxy-2-propyl) benzene by using an oxidation method for the m-diisopropylbenzene oxidation liquid recycled in the step 1), the condition of preparing 1, 3-di (2-hydroperoxy-2-propyl) benzene by using an intermediate diisopropylbenzene oxidation method in the prior art can be adopted, for example, the method described in U.S. Pat. No. 4,4849549, and details are not repeated.
As for the manner in which the 1, 3-bis (2-hydroperoxy-2-propyl) benzene obtained in step 2) is subjected to acidolysis in the presence of concentrated sulfuric acid in step 4) to obtain resorcinol, the prior art conditions for preparing resorcinol from 1, 3-bis (2-hydroperoxy-2-propyl) benzene, such as the method described in U.S. Pat. No. 4,4849549, may be adopted and will not be described in detail.
The present invention will be described in detail below by way of examples. The following examples:
detecting the composition of m-diisopropylbenzene oxidation mother liquor and recycled m-diisopropylbenzene oxidation liquor and the purity of DHP by adopting a gas chromatography.
Tracking and detecting the content of MC in the reaction system by gas chromatography, calculating the content of MC in the reaction raw materials and the content of MC in the mixed solution in real-time reaction to obtain the content of consumed MC, wherein the percentage of the content of consumed MC to the content of MC in the reaction raw materials is the conversion rate of MC.
In the following examples, the DHP yield was calculated as follows:
in the formula, W Mother liquor of DHP oxidation liquid 、W DC oxidation mother liquor 、W HHP oxidation liquid mother liquor Respectively corresponding to the mass of DHP, DC, HHP in the oxidation mother liquor, W DHP yield Refers to the quality of the extracted DHP.
All reagents used are commercially available unless otherwise specified.
Example 1
(1) In 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 (the composition is shown in table 1), 100 g of a toluene solvent, 30 mass% of hydrogen peroxide, and a molar ratio of hydrogen peroxide to the total hydroxyl groups of MC, DC and HHP of 4:1; adding 70 mass percent of sulfuric acid, wherein the weight ratio of the sulfuric acid (the content of water is not counted) to the oxidizing solution is 0.025:1; starting stirring, heating in a water bath at 45 ℃, vacuumizing by a water pump to perform reduced pressure reflux reaction, and performing reaction under the vacuum degree of (-0.085) MPa; under the azeotropic state, cooling water and toluene, and feeding the water and the toluene into an oil-water separator, wherein the toluene returns to the three-neck bottle, and the water is deposited into the oil-water separator for collection; detecting and tracking by using gas chromatography in the reaction process, and stopping the reaction when the reaction is carried out for 2.5 hours by taking the total mass of the oil-phase mixed solution as a reference, not counting the mass of the organic solvent into the total mass of the oil-phase mixed solution, and keeping the MC content at 4.4 mass%;
(2) Cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing the 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, then DHP therein was back-extracted with methyl isobutyl ketone (MIBK) solvent, and the MIBK solvent was distilled off to give 12.0 g 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 the vacuum degree of (-0.08) MPa to remove the toluene solvent 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 recycled m-diisopropylbenzene oxidation liquid contains 37.0% of DIPB and 4.4% of MC by mass percent, and the contents of MHP, DHP, DC and HHP are shown in Table 2.
Example 2
(1) 100 g of m-diisopropylbenzene oxidation mother liquor (the composition is shown in table 1), 100 g of toluene and 30 mass% of hydrogen peroxide are added into a 500 ml three-necked flask provided with a stirrer, a thermometer, a reflux condenser and an oil-water separator, and the molar ratio of the hydrogen peroxide to the total hydroxyl groups of MC, DC and HHP is 2:1; adding 20 mass percent of perchloric acid, wherein the weight ratio of the perchloric acid (the content of water is not counted) to the oxidizing solution is 0.01:1; starting stirring, heating in a water bath at 50 ℃, vacuumizing by a water pump to perform reduced pressure reflux reaction, and reacting under the vacuum degree of (-0.075 MPa); under the azeotropic state, cooling water and toluene, and feeding the water and the toluene into an oil-water separator, wherein the toluene returns to the three-neck bottle, and the water is deposited into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, and stopping the reaction when the MC content is 5.1% after the reaction is carried out for 2 hours;
(2) Cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing the lower water phase after layering.
(3) The first oil phase was washed with water, then extracted four times with 5% by mass sodium hydroxide solution, the alkaline extracts were combined, then the DHP was back-extracted with MIBK solvent, which was distilled off to give 11.6 g DHP with a purity of 93.2%.
(4) And (3) obtaining recycled m-diisopropylbenzene oxidation liquid at 50 ℃ and the vacuum degree of (-0.08) MPa, wherein the recycled m-diisopropylbenzene oxidation liquid comprises DIPB, MC, MHP, DHP, DC and HHP, and the recycled m-diisopropylbenzene oxidation liquid contains 36.6% of DIPB and 5.1% of MC by mass percent, and the contents of MHP, DHP, DC and HHP are shown in a table 2.
Example 3
(1) In 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 (the composition is shown in table 1), 100 g of ethylbenzene solvent, 30 mass% hydrogen peroxide, and a hydroxyl group molar ratio of hydrogen peroxide to MC, DC and HHP of 5:1; adding 98 mass percent of sulfuric acid, wherein the weight ratio of the sulfuric acid (the content of water is not counted) to the oxidizing solution is 0.05:1; starting stirring, heating in water bath at 60 deg.C, vacuumizing by water pump to perform reduced pressure reflux reaction, and reacting under vacuum degree (-0.075) MPa; under the azeotropic state, cooling water and ethylbenzene, and feeding the cooled water and ethylbenzene into an oil-water separator, wherein the ethylbenzene returns to a three-neck bottle, and the water sinks into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, and stopping the reaction when the MC content is 4.3% after the reaction is carried out for 4.5 hours;
(2) Cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing the lower water phase after layering.
(3) The first oil phase was washed with water and then extracted three times with 5% by mass sodium hydroxide solution, the alkaline extracts were combined and then stripped of DHP with MIBK solvent, which was distilled off to give 12.2 g DHP as a white solid with a purity of 94.6%.
(4) And distilling the second oil phase extracted by the alkali liquor under reduced pressure at 50 ℃ and the vacuum degree of (-0.08) MPa to remove the ethylbenzene solvent to obtain a recycled m-diisopropylbenzene oxidation liquid, wherein the recycled m-diisopropylbenzene oxidation liquid consists of DIPB, MC, MHP, DHP, DC and HHP, and 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 in percentage by mass are shown in a table 2.
Example 4
(1) In 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 (the composition is shown in table 1), 100 g of cumene solvent, 30 mass% hydrogen peroxide, and the molar ratio of hydrogen peroxide to the total hydroxyl content in MC, DC and HHP was 10:1; adding benzene sulfonic acid, wherein the weight ratio of the benzene sulfonic acid to the oxidizing solution is 0.1:1; starting stirring, heating in 65 deg.C water bath, vacuumizing by water pump, performing reflux reaction under reduced pressure, and reacting under vacuum degree (-0.04) MPa; under the azeotropic state, water and isopropyl benzene are cooled and enter an oil-water separator, wherein the isopropyl benzene returns to a three-mouth bottle, and the water sinks into the oil-water separator for collection; detecting and tracking by adopting gas chromatography in the reaction process, and stopping the reaction when the MC content is 3.8% after the reaction is carried out for 5 hours;
(2) Cooling the kettle liquid to room temperature (25 ℃), performing liquid-liquid separation to obtain a first oil phase and a water phase, and removing the lower water phase after layering.
(3) The first oil phase was washed with water, then extracted four times with 5% by mass sodium hydroxide solution, the alkaline extracts were combined, then DHP was back-extracted with MIBK solvent, which was distilled off to give 12.9 g 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 the vacuum degree of-0.08 MPa to remove the isopropylbenzene solvent to obtain a 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 the 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 (excluding water content) to the oxidation liquid in step (1) was 0.12:1; 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 same conversion rate of MC as in example 1. After work-up 9.9 g DHP were obtained as a white solid 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 a 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 same conversion rate of MC as in example 1. After work-up 11.0 g DHP were obtained as a white solid 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 the 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 conversion of MC was monitored to be 40% in step (1), and the reaction was stopped. After work-up, 9.5 g of DHP are obtained as a white solid 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 a table 2 in percentage by mass.
Comparative example 1
The m-diisopropylbenzene oxidation solution of example 1 is not subjected to secondary oxidation reaction of hydrogen peroxide, and the oxidation solution is directly subjected to alkali liquor extraction and MIBK back extraction, so that only 4.8 g of DHP is obtained, the purity is 85%, a small amount of white precipitate is separated out due to the DC contained in the obtained oxidation solution, along with the increase of the recycling times of the oxidation solution, the content of MC and DC is higher and higher, the speed of the recycling oxidation reaction of the recycled oxidation solution is lower and lower, due to the accumulation of the content of MC, the generation of byproducts HHP and DC is higher and higher, the generation efficiency and purity of the target product DHP are lower and lower, and the DC precipitate can block pipelines and seriously affect the normal production.
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 by mass percent, and the contents of MHP, DHP, DC and HHP are shown in Table 2.
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 percent of DIPB and 13.8 percent of MC by mass percent, and the contents of MHP, DHP, DC and HHP are shown in Table 2.
TABLE 1
TABLE 2
The embodiment and the comparative example show that the specific method can obtain the diisopropylbenzene dihydroperoxide DHP with high yield and high selectivity, the content of MHP in the recycled m-diisopropylbenzene oxidizing solution obtained after treatment is improved, the contents of byproducts MC, DC and HHP are reduced, the problem of accumulation of the byproducts in the oxidation reaction is solved, the oxidation speed can be improved after the recycled m-diisopropylbenzene oxidizing solution returns to an oxidation system, and the yield of DHP can be further improved.
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 (11)
1. The method for treating the m-diisopropylbenzene oxidizing solution is characterized by comprising the following steps of:
(1) Under the reaction condition that hydroxylates are converted into peroxide hydroxylates, 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) Carrying out first extraction on the first oil phase by using alkali liquor to obtain a first extraction water phase and a second oil phase, carrying out back extraction on the first extraction 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-isopropyldimethylbenzyl alcohol, m-isopropylcumene hydroperoxide and 1, 3-di (2-hydroxy-2-propyl) benzene.
2. The treatment method 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;
preferably, based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the content of m-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) 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%;
preferably, based on the total mass of the m-diisopropylbenzene oxidation mother liquor, the content of m-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) cumene hydroperoxide is 0.5-5%, the content of m-isopropylcumene hydroperoxide is 35-50%, and the content of 1, 3-bis (2-hydroperoxy-2-propyl) benzene is 3-15%.
3. The treatment method according to claim 1 or 2, wherein the molar ratio of the total molar amount of alcoholic hydroxyl groups in the 1, 3-bis (2-hydroxy-2-propyl) benzene, m-isopropyldimethylbenzyl alcohol and optionally 3- (2-hydroxy-2-propyl) cumene hydroperoxide to hydrogen peroxide is 1.
4. The treatment process according to claim 1, 2 or 3, wherein the mass ratio of the organic solvent to the m-diisopropylbenzene oxidation mother liquor is from 0.5 to 5:1, preferably 1-2;
preferably, the organic solvent is an aromatic hydrocarbon with 7-12 carbon atoms substituted by a hydrocarbon group with 1-6 carbon atoms;
preferably, the organic solvent is selected from at least one of toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and cumene.
5. The treatment method according to any one of claims 1 to 4, wherein the mass ratio of the acidic catalyst to the m-diisopropylbenzene oxidation mother liquor is 0.01-0.1:1; preferably 0.01 to 0.05:1;
preferably, the acidic catalyst is selected from at least one of sulfuric acid, perchloric acid, nitric acid, phosphoric acid and benzenesulfonic acid.
6. The process of any one of claims 1 to 5, wherein the reaction conditions include: the temperature is 30-70 ℃, preferably 40-60 ℃; and/or the vacuum degree is (-0.095) MPa- (-0.04) MPa, preferably (-0.085) MPa- (-0.07) MPa; and/or the reaction time is 1-6h, preferably 2-3h;
preferably, the reaction is carried out under reflux conditions such that a portion of the water in the reaction system is removed from the reaction system and the oil phase is returned to the reaction system.
7. The process according to any one of claims 1 to 6, wherein the reaction is stopped when the conversion of 3-isopropyldimethylbenzyl alcohol is more than 50%, preferably the conversion of 3-isopropyldimethylbenzyl alcohol is 50% to 70%;
preferably, the content of 1, 3-bis (2-hydroxy-2-propyl) benzene and 3- (2-hydroxy-2-propyl) cumene hydroperoxide in the recycled m-diisopropylbenzene oxidizing solution is less than 1 mass percent based on the total mass of the recycled m-diisopropylbenzene oxidizing solution.
8. The process of any one of claims 1 to 7, wherein the lye is an aqueous solution of sodium hydroxide and/or potassium hydroxide;
preferably, the mass concentration of the alkali liquor is 1% -15%, preferably 5% -10%;
preferably, the stripping solvent is selected from at least one of methyl isobutyl ketone, methyl isopropyl ketone, methyl ethyl ketone, diethyl ether, diisopropyl ether, butanol and pentanol.
9. The process according to any one of claims 1 to 8, wherein the organic solvent in the second oil phase is removed by distillation under reduced pressure in step (4);
preferably, the conditions of the reduced pressure distillation include: the temperature is 30-70 ℃, and the vacuum degree is (-0.05) MPa- (-0.098) MPa;
further preferably, the temperature is 40-60 ℃ and the vacuum degree is (-0.07) MPa- (-0.085) MPa.
10. A recycling method of m-diisopropylbenzene oxidation liquid, which is characterized by comprising the treatment method of m-diisopropylbenzene oxidation liquid of any one of claims 1 to 9;
also comprises the step of preparing the 1, 3-di (2-hydroperoxy-2-propyl) benzene from the obtained reclaimed m-diisopropylbenzene oxidation solution by an oxidation method.
11. A method for producing resorcinol, comprising:
1) Carrying out m-diisopropylbenzene oxidation 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) The m-diisopropylbenzene oxidation mother liquor is treated according to the method for treating the m-diisopropylbenzene oxidation liquid of any one of claims 1-9 to obtain 1, 3-bis (2-hydroperoxy-2-propyl) benzene and recycled m-diisopropylbenzene oxidation liquid;
3) Returning the recycled m-diisopropylbenzene oxidizing solution obtained in the step 2) to the step 1);
4) 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 |
| US4237319A (en) * | 1977-10-31 | 1980-12-02 | Mitsui Petrochemical Industries Ltd. | Process for liquid-phase oxidation of m-diisopropylbenzene |
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| US4283570A (en) * | 1976-08-18 | 1981-08-11 | Mitsui Petrochemical Industries Ltd. | Process for preparing resorcinol |
| US4849549A (en) * | 1987-12-22 | 1989-07-18 | Indspec Chemical Corporation | Process for preparation of resorcinol |
| 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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| US3950431A (en) * | 1972-11-21 | 1976-04-13 | Sumitomo Chemical Company, Limited | Process for removing impurities in an oxidation mixture |
| US4283570A (en) * | 1976-08-18 | 1981-08-11 | Mitsui Petrochemical Industries Ltd. | Process for preparing resorcinol |
| US4237319A (en) * | 1977-10-31 | 1980-12-02 | Mitsui Petrochemical Industries Ltd. | Process for liquid-phase oxidation of m-diisopropylbenzene |
| US4267387A (en) * | 1978-10-17 | 1981-05-12 | Mitsui Petrochemical Industries Ltd. | Process for preparation of aromatic hydroperoxides |
| US4849549A (en) * | 1987-12-22 | 1989-07-18 | Indspec Chemical Corporation | Process for preparation of resorcinol |
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