CN115894193B - Method for decomposing hydroperoxide acid - Google Patents
Method for decomposing hydroperoxide acid Download PDFInfo
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- CN115894193B CN115894193B CN202111156683.6A CN202111156683A CN115894193B CN 115894193 B CN115894193 B CN 115894193B CN 202111156683 A CN202111156683 A CN 202111156683A CN 115894193 B CN115894193 B CN 115894193B
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- cation exchange
- exchange resin
- hydrogen type
- type cation
- hydrogen
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- 238000000034 method Methods 0.000 title claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 150000001768 cations Chemical class 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000005342 ion exchange Methods 0.000 claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 34
- -1 alkaline earth metal cations Chemical class 0.000 claims description 24
- 238000010306 acid treatment Methods 0.000 claims description 17
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical group OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-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
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001422 barium ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000008961 swelling Effects 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical group 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a process for the acid decomposition of a hydroperoxide, comprising: (1) Ion exchange is carried out on the hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and the exchange conditions are controlled to ensure that the hydrogen ion exchange rate is 10% -60%; (2) The hydroperoxide is contacted with the resin catalyst in the presence of an optional solvent. The invention can effectively improve the swelling resistance and the temperature resistance of the resin catalyst, thereby improving the acidolysis reaction efficiency of the hydroperoxide and having good application prospect.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a method for decomposing hydroperoxide acid.
Background
Phenol and cyclohexanone are important basic chemical raw materials, and the application is very wide. Phenol is an important intermediate of synthetic plastics, medicines, pesticides, bactericides and the like, is particularly used for manufacturing synthetic materials such as polycarbonate, epoxy resin, phenolic resin and the like in the industries such as electronics, automobiles, appliances and the like, and is required to be increased rapidly, and the increase rate of the phenol is kept to be 7-10% in the next few years. The cyclohexanone is mainly used for producing important monomer raw materials of caprolactam and adipic acid of high polymer materials such as nylon, polyurethane and the like, and simultaneously, the cyclohexanone is also an important industrial solvent and has large dosage.
The production of phenol ketone involves the oxidation process of hydrocarbon, wherein phenol is mainly produced by adopting a cumene method, and the process mainly comprises three reaction processes of benzene and propylene alkylation to prepare cumene, cumene oxidation to prepare cumene hydroperoxide, decomposition of cumene hydroperoxide acid to prepare phenol and co-production of acetone. The existing industrial phenol production technology has the following problems: (1) The co-production of acetone has the problem of surplus and the added value of the product is low; (2) The acid decomposition process uses concentrated sulfuric acid as a catalyst, which not only causes equipment corrosion, but also generates a large amount of phenol-containing wastewater to cause environmental pollution. The main flow production process of cyclohexanone adopts a cyclohexane liquid phase oxidation method, which comprises four reaction processes of preparing cyclohexane by benzene hydrogenation, preparing cyclohexane hydroperoxide by cyclohexane oxidation, preparing cyclohexanone by decomposing cyclohexane hydroperoxide and preparing cyclohexanol by dehydrogenating cyclohexanol, and has the advantages of long flow, low conversion rate (only 3% -5%) in the oxidation process, poor product selectivity, higher energy consumption and material consumption, high cost, large amount of salt-containing and organic matter-containing waste water generated in the production process, large discharge amount of three wastes and outstanding environmental protection problem. The traditional industrial production technology of phenol and cyclohexanone has the outstanding problems of environmental protection, high energy consumption, low added value of the co-products and the like, and has lower production benefit. Along with the requirements of the industry in China for structural transformation of high-quality and high-end products and the severe requirements of the country for environmental protection, the development of the green phenol ketone technology with energy conservation, environmental protection and high added value has become a great subject of the green chemical industry.
The acidic resin can catalyze the acid decomposition of hydroperoxides, such as cyclohexylbenzene hydroperoxide. However, due to the limitation of physical and chemical properties of the resin, the resin is easy to swell in the reaction process, has poor thermal stability and mechanical properties, is easy to crush, directly influences the reaction efficiency, and has an application effect to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, one of the technical problems to be solved by the invention is to overcome the defects of easy swelling, poor thermal stability and low acid decomposition efficiency of the resin catalyst in the reaction process in the prior acid decomposition technology.
The present invention provides a process for the acid decomposition of a hydroperoxide, comprising:
(1) Ion exchange is carried out on the hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and the exchange conditions are controlled to ensure that the hydrogen ion exchange rate is 10% -60%;
(2) The hydroperoxide is contacted with the resin catalyst in the presence of an optional solvent.
The invention can effectively improve the swelling resistance and the temperature resistance of the resin catalyst, thereby improving the acidolysis reaction efficiency of the hydroperoxide and having good application prospect.
According to the technical scheme provided by the invention, the resin catalyst can be applied to common reactor forms such as a reaction kettle, a fixed bed and the like, is simple to operate and is easy to popularize.
According to the technical scheme provided by the invention, the swelling of the resin in a reaction system can be effectively reduced, the thermal stability is improved, the acid decomposition reaction of the hydroperoxide can be carried out at a higher temperature, and the acidolysis reaction efficiency is improved.
Compared with the prior art, the method for improving the resin matrix to solve the swelling resistance and the temperature resistance is simple and easy to obtain, and has good industrial application prospect.
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 following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art as the invention suggests, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
It is specifically noted that two or more aspects (or embodiments) disclosed in the context of this specification may be arbitrarily combined with each other, and the resulting solution (such as a method or system) is part of the original disclosure of this specification, while also falling within the scope of the invention.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
The present invention provides a process for the acid decomposition of a hydroperoxide, comprising:
(1) Ion exchange is carried out on the hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and the exchange conditions are controlled to ensure that the hydrogen ion exchange rate is 10% -60%; (2) The hydroperoxide is contacted with the resin catalyst in the presence of an optional solvent.
The invention can improve the acidolysis reaction efficiency of the hydroperoxide and has good application prospect.
According to the present invention, the divalent cations are selected from a wide range of species, such as alkaline earth metal cations and divalent transition metal cations, and for the present invention, it is preferable that the divalent cations are one or more of magnesium ions, calcium ions, copper ions, zinc ions and barium ions. The preferable divalent cations are selected, so that the method has the advantages of stable property, convenience, availability and the like.
According to the invention, the trivalent cations may be selected from a wide range of species, such as trivalent cobalt ions, aluminum ions, iron ions, chromium ions, vanadium ions, etc., and for the purposes of the invention, it is preferred that the trivalent cations be aluminum ions and/or iron ions. The preferable trivalent cations are selected, so that the method has the advantages of stable property, convenience, availability and the like.
According to the present invention, there is no particular requirement on the kind of the salt, and for the present invention, it is preferable that the salt of divalent cation and/or trivalent cation is chloride salt and/or nitrate salt. The preferred salt is selected, and has the advantages of high commercialization degree, easy purchase and the like.
According to the present invention, the type of the hydrogen type cation exchange resin is wide in optional range, and resins commonly used in the field can be used in the present invention, and for the present invention, it is preferable that the hydrogen type cation exchange resin is a hydrogen type monovalent cation exchange resin; preferably, the hydrogen cation exchange resin is one or more selected from DL-1H hydrogen cation exchange resin, 122 hydrogen cation exchange resin, 001 x 7 sodium cation exchange resin fully exchanged to hydrogen form after hydrochloric acid treatment, 001 x 14 sodium cation exchange resin fully exchanged to hydrogen form after hydrochloric acid treatment, DL12 sodium cation exchange resin fully exchanged to hydrogen form after hydrochloric acid treatment, and D001 sodium cation exchange resin fully exchanged to hydrogen form after hydrochloric acid treatment.
According to the present invention, the hydrochloric acid treatment is preferably carried out at a concentration of 5% to 37%.
According to the invention, reasonable hydrogen ion exchange conditions are adopted, so that the strength of the resin acid can be effectively controlled, the selectivity of acidolysis reaction is improved, the resin is modified, and the swelling resistance of the body is improved.
According to a preferred embodiment of the present invention, the conditions for ion exchange include: the exchange temperature is 5-90 ℃, preferably 20-60 ℃.
According to the invention, the ion exchange time is 0.5 to 24 hours.
According to a preferred embodiment of the present invention, step (1) comprises: the hydrogen type cation exchange resin is soaked in a salt solution containing divalent cations and/or trivalent cations for ion exchange, and partial ion exchange is carried out under the condition of stirring, so that partial hydrogen ions are replaced, and the resin catalyst is obtained.
The present invention is particularly suitable for use in the acid decomposition reaction of hydroperoxides, which are commonly used in the present invention, and for the present invention it is preferred that the hydroperoxide is a tertiary alkyl substituted benzene hydroperoxide, more preferably cyclohexylbenzene hydroperoxide.
According to a preferred embodiment of the present invention, the conditions of contact are selected from a wide range, and acid decomposition conditions commonly used in the art can be used in the present invention, and for the present invention, the preferred conditions of contact include: the addition amount of the resin catalyst is 0.1-50% of the mass of the hydroperoxide, and is preferably 1-20%. Thereby, the yield of the target product can be improved.
According to a preferred embodiment of the present invention, the conditions of the contacting include: the temperature is 40-150 ℃.
According to a preferred embodiment of the present invention, the conditions of the contacting include: the time is 0.5 to 24 hours.
According to a preferred embodiment of the invention, the solvent is an aromatic compound and/or a ketone compound.
According to a preferred embodiment of the present invention, the aromatic compound is represented by the general formula B:
Wherein R is one of C 1～C8 alkyl; m is an integer of 0 to 6; preferably one or more of benzene, toluene and para-xylene.
According to a preferred embodiment of the present invention, the ketone compound is a ketone compound having 3 to 6 carbon atoms, preferably acetone and/or cyclohexanone.
In the present invention,
Preparing hydrogen type cation exchange resin:
100g of 001 x 7 sodium type cation exchange resin is added into 150g of 10 wt% hydrochloric acid, stirred for 12 hours at room temperature, filtered, and the resin is washed with deionized water until the filtrate is neutral, thus obtaining the 001 x 7 hydrogen type cation exchange resin with completely exchanged ions.
Preparation example 1
9.5G of magnesium chloride is dissolved in 200 ml of water to prepare an ion exchange solution, 100g of 001 x 7 hydrogen type cation exchange resin is added into the solution, the mixture is stirred for 8 hours at the room temperature of 20 ℃, and the magnesium ion cross-linked modified resin A with the ion exchange rate of 10% is obtained after filtration and drying.
Preparation example 2
20.8G of barium chloride is dissolved in 300 ml of water to prepare an ion exchange solution, 100g of DL-1H hydrogen type cation exchange resin is added into the solution, the solution is stirred for 15 hours at the room temperature of 30 ℃, and the barium ion crosslinking modified resin B is obtained after filtration and drying, wherein the ion exchange rate is 60 percent.
Preparation example 3
15G of aluminum chloride is dissolved in 300 ml of water to prepare an ion exchange solution, 100g of D001 hydrogen type cation exchange resin is added into the solution, the solution is stirred for 12 hours at the room temperature of 35 ℃, and the resin C modified by aluminum ion crosslinking is obtained after filtration and drying, wherein the ion exchange rate is 55%.
Preparation example 4
16.4G of calcium nitrate is dissolved in 200 ml of water to prepare an ion exchange solution, 100g of 001 x 7 hydrogen type cation exchange resin is added into the solution, the mixture is stirred for 12 hours at 40 ℃, and the calcium ion crosslinking modified resin D with the ion exchange rate of 40% is obtained after filtration and drying.
Preparation example 5
17.6G of ferric nitrate is dissolved in 200 ml of water to prepare an ion exchange solution, 100g of 122 hydrogen type cation exchange resin is added into the solution, the mixture is stirred for 12 hours at 40 ℃, and the calcium ion crosslinking modified resin E with the ion exchange rate of 42% is obtained after filtration and drying.
Preparation example 6
Resin F was obtained by the same method as in preparation example 3, except that vanadium chloride was used, and the ion exchange rate was 55%.
Resin swelling experiments: 20g of the test resin sample was added to 100mL of cyclohexanone and soaked for 48 hours, and the sample was taken out to measure the swelling property, and the test results are shown in Table 1:
table 1 comparative swelling properties of resin samples in cyclohexanone
As can be seen from the data in Table 1, the resin catalyst treated by the method of the invention has obviously better swelling resistance than the commercial sodium/hydrogen cation exchange resin, and can be better applied to the acid decomposition reaction of cyclohexylbenzene hydroperoxide.
Example 1
10G of resin A catalyst was charged in a fixed bed reactor, and a cyclohexylbenzene oxidizing solution (main composition: cyclohexylbenzene hydroperoxide, cyclohexylbenzene, cyclohexanone and phenylcyclohexanol, the rest of examples were the same) containing 30% by weight of cyclohexylbenzene hydroperoxide was added at 1.0ml/min at 60℃and reacted continuously for 24 hours, with a cyclohexylbenzene hydroperoxide conversion of 98%, a phenol selectivity of 91% and a cyclohexanone selectivity of 87%.
Example 2
10G of resin B catalyst was charged in a fixed bed reactor, and a cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was added at 50℃and 2.0ml/min, followed by continuous reaction for 24 hours, with a cyclohexylbenzene hydroperoxide conversion of 96.5%, a phenol selectivity of 92% and a cyclohexanone selectivity of 90%.
Example 3
10G of resin A catalyst was charged in a fixed bed reactor, and a cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was added at 80℃at 1.0ml/min, followed by continuous reaction for 24 hours, with a cyclohexylbenzene hydroperoxide conversion of 99%, a phenol selectivity of 89% and a cyclohexanone selectivity of 85%.
Examples 4 to 7
The procedure of example 2 was followed except that the catalysts used were resin C, resin D, resin E, resin F, and the results are shown in Table 2.
Comparative example 1
10G of a 001X 7 sodium cation exchange resin was charged in a fixed bed reactor and cyclohexylbenzene oxidation liquor containing 30% wt cyclohexylbenzene hydroperoxide was added at 60℃at 1.0ml/min with a cyclohexylbenzene hydroperoxide conversion of 55%, a phenol selectivity of 75% and a cyclohexanone selectivity of 70%.
Comparative example 2
10G of 001 x 7 hydrogen cation exchange resin was charged in a fixed bed reactor and cyclohexylbenzene oxidation liquor containing 25% wt cyclohexylbenzene hydroperoxide was added at 80℃at 1.0ml/min with a cyclohexylbenzene hydroperoxide conversion of 79%, a phenol selectivity of 60% and a cyclohexanone selectivity of 53%.
Comparative example 3
The procedure of example 2 was followed except that DL-1H hydrogen type cation exchange resin was used as a catalyst, and the reaction results are shown in Table 2.
Comparative example 4
The procedure of example 4 was followed except that a D001 hydrogen type cation exchange resin was used as a catalyst, and the reaction results are shown in Table 2.
Comparative example 5
The procedure of example 6 was followed except that 122 hydrogen type cation exchange resin was used as a catalyst, and the reaction results are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the catalyst conversion and selectivity of the present invention have significant advantages, indicating that the catalyst of the present invention has high acid decomposition efficiency, which in the present invention refers to the resin catalyzed peroxide reaction efficiency.
The following table 3 shows the long-term reaction data for each catalyst, see in particular table 3.
TABLE 3 (reaction 100h, the remaining conditions are the same)
As can be seen from the data in Table 3, the catalyst of the present invention has excellent stability, and can maintain high conversion and selectivity after long-term reaction for 100 hours.
As can be seen from the experimental results of examples and comparative examples, the resin catalyst prepared by adopting the technical scheme of the invention can more stably catalyze the acid decomposition reaction of cyclohexylbenzene hydroperoxide, can still effectively maintain the catalytic performance of the resin even at a higher temperature, and can obtain phenol and cyclohexanone products with excellent conversion rate and selectivity.
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 (24)
1. A method of acid decomposition of a hydroperoxide, the method comprising:
(1) Ion exchange is carried out on hydrogen type cation exchange resin and salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, the exchange condition is controlled to ensure that the hydrogen ion exchange rate is 10-60%, the divalent cations are alkaline earth metal cations and/or divalent transition metal cations, and the trivalent cations are one or more of cobalt ions, aluminum ions, iron ions, chromium ions and vanadium ions;
(2) Contacting a hydroperoxide, which is a tertiary alkyl substituted benzene hydroperoxide, with the resin catalyst, optionally in the presence of a solvent.
2. The method according to claim 1, wherein in the step (1),
The divalent cations are one or more of magnesium ions, calcium ions, copper ions, zinc ions and barium ions.
3. The method according to claim 1 or 2, wherein in step (1),
The trivalent cations are aluminum ions and/or iron ions.
4. The method according to claim 1, wherein in the step (1),
The salts of divalent cations and/or trivalent cations are chloride salts and/or nitrate salts.
5. The method according to claim 2, wherein in step (1),
The salts of divalent cations and/or trivalent cations are chloride salts and/or nitrate salts.
6. A method according to claim 3, wherein in step (1),
The salts of divalent cations and/or trivalent cations are chloride salts and/or nitrate salts.
7. The method according to claim 1, wherein in the step (1),
The hydrogen type cation exchange resin is hydrogen type monovalent cation exchange resin.
8. The method according to claim 7, wherein in the step (1),
The hydrogen type cation exchange resin is selected from one or more of DL-1H hydrogen type cation exchange resin, 122 hydrogen type cation exchange resin, 001 x 7 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, 001 x 14 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, DL12 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment and D001 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment.
9. The method of claim 8, wherein the concentration of hydrochloric acid is 5% to 37%.
10. The method according to claim 2, wherein in step (1),
The hydrogen type cation exchange resin is hydrogen type monovalent cation exchange resin.
11. The method of claim 10, wherein in step (1),
The hydrogen type cation exchange resin is selected from one or more of DL-1H hydrogen type cation exchange resin, 122 hydrogen type cation exchange resin, 001 x 7 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, 001 x 14 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, DL12 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment and D001 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment.
12. The method of claim 11, wherein the concentration of hydrochloric acid is 5% to 37%.
13. A method according to claim 3, wherein in step (1),
The hydrogen type cation exchange resin is hydrogen type monovalent cation exchange resin.
14. The method of claim 13, wherein in step (1),
The hydrogen type cation exchange resin is selected from one or more of DL-1H hydrogen type cation exchange resin, 122 hydrogen type cation exchange resin, 001 x 7 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, 001 x 14 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment, DL12 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment and D001 sodium type cation exchange resin which is completely exchanged into hydrogen type after hydrochloric acid treatment.
15. The method of claim 14, wherein the concentration of hydrochloric acid is 5% to 37%.
16. The method according to claim 1, wherein in the step (1),
The conditions for ion exchange included: the exchange temperature is 5-90 ℃; and/or the exchange time is 0.5 to 24 hours.
17. The method of claim 16, wherein in step (1),
The conditions for ion exchange included: the exchange temperature is 20-60 ℃.
18. The method of claim 1, wherein step (1) comprises: the hydrogen type cation exchange resin is soaked in a salt solution containing divalent cations and/or trivalent cations for ion exchange, and partial ion exchange is carried out under the condition of stirring, so that partial hydrogen ions are replaced, and the resin catalyst is obtained.
19. The process of claim 1, wherein step (2) the hydroperoxide is cyclohexylbenzene hydroperoxide.
20. The method of claim 1, wherein step (2),
The conditions of contact include:
The temperature is 40-150 ℃; and/or
The time is 0.5 to 24 hours.
21. The method of claim 20, wherein step (2),
The conditions of contact include: the temperature is 50-80 ℃.
22. The method of claim 1, wherein the solvent of step (2) is an aromatic compound and/or a ketone compound.
23. The method of claim 22, wherein step (2),
The aromatic compound is represented by the general formula B:
Wherein R is one of C 1～C8 alkyl; m is an integer of 0 to 6;
the ketone compound is a ketone compound with 3-6 carbon atoms.
24. The method of claim 23, wherein in step (2), the aromatic compound is one or more of benzene, toluene, and para-xylene;
the ketone compound is acetone and/or cyclohexanone.
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