CN115894193A - Method for decomposing hydroperoxide acid - Google Patents
Method for decomposing hydroperoxide acid Download PDFInfo
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- CN115894193A CN115894193A CN202111156683.6A CN202111156683A CN115894193A CN 115894193 A CN115894193 A CN 115894193A CN 202111156683 A CN202111156683 A CN 202111156683A CN 115894193 A CN115894193 A CN 115894193A
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- resin
- hydrogen
- cation exchange
- ion
- exchange resin
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- 238000000034 method Methods 0.000 title claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 38
- 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 37
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001768 cations Chemical class 0.000 claims abstract description 24
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkaline earth metal cations Chemical class 0.000 claims description 22
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 claims description 16
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 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 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 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
- 230000008569 process Effects 0.000 claims description 5
- 150000003839 salts 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
- 150000001491 aromatic compounds Chemical group 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 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
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000003841 chloride salts Chemical class 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
- 150000002823 nitrates Chemical class 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 29
- 230000002579 anti-swelling effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000052 comparative effect 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
- 230000008961 swelling Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 239000000126 substance Substances 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
- 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
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 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
- DYQAZJQDLPPHNB-UHFFFAOYSA-N 1-phenyl-2-hexanone Chemical compound CCCCC(=O)CC1=CC=CC=C1 DYQAZJQDLPPHNB-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
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 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
- 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
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture 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
- 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
- 230000035484 reaction time Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention provides a method for decomposing hydroperoxide acid, which comprises the following steps: (1) Performing ion exchange on hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and controlling the exchange conditions to ensure that the hydrogen ion exchange rate is 10-60%; (2) Contacting a hydroperoxide with the resin catalyst in the presence of an optional solvent. The invention can effectively improve the anti-swelling performance 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 are widely applied. Phenol is an important intermediate for synthesizing 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, electric appliances and the like, and is demanded to be accelerated rapidly, and the acceleration is kept to be 7% -10% in the coming years. Cyclohexanone is mainly used for producing caprolactam and adipic acid which are important monomer raw materials of high polymer materials such as nylon, polyurethane and the like, and is also an important industrial solvent with large dosage.
The production of phenol ketone relates to the oxidation process of hydrocarbon, wherein phenol is mainly produced by a cumene method, and the process mainly comprises three reaction processes of cumene preparation by benzene and propylene alkylation, cumene hydroperoxide preparation by cumene oxidation, and phenol preparation by cumene hydroperoxide acid decomposition and acetone coproduction. The problems of the prior industrial phenol production technology are as follows: (1) The problem of excessive co-production of acetone is solved, and the added value of the product is low; (2) In the acid decomposition process, concentrated sulfuric acid is used as a catalyst, so that equipment corrosion is caused, and a large amount of phenol-containing wastewater is generated to cause environmental pollution. The mainstream production process of the cyclohexanone adopts a cyclohexane liquid-phase oxidation method, which comprises four reaction processes of preparing cyclohexane by benzene hydrogenation, preparing hydrogen peroxide by cyclohexane oxidation, preparing cyclohexanone by decomposing hydrogen peroxide and cyclohexanol, and preparing cyclohexanone by cyclohexanol dehydrogenation, wherein the flow is long, the conversion rate of the oxidation process is low (only 3% -5%), the product selectivity is poor, the energy consumption and material consumption are high, the cost is high, a large amount of waste water containing salt and organic matters is generated in the production process, the three-waste discharge amount is large, and the environmental protection problem is prominent. The traditional industrial production technology of phenol and cyclohexanone has the problems of outstanding environmental protection, high energy consumption, low added value co-products and the like, and the production benefit is low. With the requirement of the transformation of the industry to high-quality and high-end products in China and the strict requirement of the country on environmental protection, the development of an energy-saving, environment-friendly and high-added-value green phenolic ketone technology becomes a major topic of the green chemical industry.
The acidic resin is capable of catalyzing acid decomposition reactions of hydroperoxides, such as cyclohexylbenzene hydroperoxide. However, due to the limitation of the physicochemical properties of the resin, the resin is easy to swell in the reaction process, has poor thermal stability and poor mechanical properties, is easy to break, directly influences the reaction efficiency, and needs to be improved in application effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to overcome the defects of easy swelling, poor thermal stability and low acid decomposition efficiency of a resin catalyst in the reaction process in the prior acid decomposition technology.
The invention provides a method for decomposing hydroperoxide acid, which comprises the following steps:
(1) Performing ion exchange on hydrogen type cation exchange resin and salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and controlling the exchange conditions to ensure that the hydrogen ion exchange rate is 10-60%;
(2) Contacting a hydroperoxide with the resin catalyst in the presence of an optional solvent.
The invention can effectively improve the anti-swelling performance 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, and is simple to operate and 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 by solving the problems of swelling resistance and temperature resistance is simple and easy to obtain, and has good industrial application prospect.
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 following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the 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 same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time the disclosure was made, but also include those that are not currently used, but would become known in the art to be suitable for a similar purpose.
It should be expressly understood that two or more of the aspects (or embodiments) disclosed in the context of this specification can be combined with each other as desired, and that such combined aspects (e.g., methods or systems) are incorporated in and constitute a part of this original disclosure, while remaining within the scope of the present invention.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
The invention provides a method for decomposing hydroperoxide acid, which comprises the following steps:
(1) Performing ion exchange on hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and controlling the exchange conditions to ensure that the hydrogen ion exchange rate is 10-60%; (2) Contacting a hydroperoxide with the resin catalyst in the presence of an optional solvent.
The method can improve the acidolysis reaction efficiency of the hydroperoxide and has good application prospect.
According to the present invention, the species of the divalent cations are widely selectable, 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 have the advantages of stable property, convenience, easy obtaining and the like.
According to the invention, the trivalent cation 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 cation is aluminum and/or iron ions. The optimized trivalent cation has the advantages of stable property, convenience, easy obtaining and the like.
According to the invention, there is no particular requirement on the type of salt, and for the purposes of the invention it is preferred that the salt of the divalent cation and/or trivalent cation is a chloride salt and/or a nitrate salt. The selection of the preferred salt has the advantages of high commercialization degree, easy commercial availability, and the like.
According to the present invention, the kind of the hydrogen type cation exchange resin is widely selected, and any resin commonly used in the art 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-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 form after hydrochloric acid treatment, 001 x 14 sodium-type cation exchange resin which is completely exchanged into hydrogen form after hydrochloric acid treatment, DL12 sodium-type cation exchange resin which is completely exchanged into hydrogen form after hydrochloric acid treatment, and D001 sodium-type cation exchange resin which is completely exchanged into hydrogen form after hydrochloric acid treatment.
According to the present invention, the concentration of hydrochloric acid used in the hydrochloric acid treatment is preferably 5% to 37%.
According to the invention, reasonable hydrogen ion exchange conditions are adopted, so that the resin acid strength can be effectively controlled, the acidolysis reaction selectivity is improved, meanwhile, the resin is modified, and the bulk anti-swelling performance is improved.
According to a preferred embodiment of the present invention, the conditions of the ion exchange include: the exchange temperature is 5 to 90 ℃ and preferably 20 to 60 ℃.
According to the invention, the ion exchange time is between 0.5 and 24 hours.
According to a preferred embodiment of the present invention, the step (1) comprises: the resin catalyst is obtained by immersing a hydrogen type cation exchange resin in a salt solution containing divalent cations and/or trivalent cations for ion exchange, performing partial ion exchange under stirring, and displacing part of hydrogen ions.
The present invention is particularly suitable for acid decomposition reactions of hydroperoxides, and all conventional hydroperoxides can be used in the present invention, and for the present invention, the hydroperoxide is preferably tertiary alkyl substituted benzene hydroperoxide, more preferably cyclohexylbenzene hydroperoxide.
According to a preferred embodiment of the present invention, the conditions of the contacting can be selected from a wide range, and any acid decomposition conditions commonly used in the art can be used in the present invention, and for the present invention, preferred contacting conditions include: the addition amount of the resin catalyst is 0.1-50% of the mass of the hydroperoxide, 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 general formula B:
wherein R is C 1 ～C 8 One of alkyl groups; m is an integer of 0 to 6; preferably one or more of benzene, toluene and p-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,
preparation of hydrogen type cation exchange resin:
adding 100g of 001X 7 sodium type cation exchange resin into 150g of 10 weight percent hydrochloric acid, stirring for 12 hours at room temperature, filtering, and washing the resin with deionized water until the filtrate is neutral to obtain the 001X 7 hydrogen type cation exchange resin with completely exchanged ions.
Preparation of example 1
Dissolving 9.5g of magnesium chloride in 200 ml of water to prepare an ion exchange solution, adding 100g of 001 x 7 hydrogen type cation exchange resin into the solution, stirring for 8 hours at room temperature of 20 ℃, filtering and drying to obtain the magnesium ion crosslinking modified resin A, wherein the ion exchange rate is 10%.
Preparation of example 2
Dissolving 20.8g of barium chloride in 300 ml of water to prepare an ion exchange solution, adding 100g of DL-1H hydrogen type cation exchange resin into the solution, stirring for 15 hours at room temperature of 30 ℃, filtering and drying to obtain barium ion crosslinking modified resin B, wherein the ion exchange rate is 60%.
Preparation of example 3
Dissolving 15g of aluminum chloride in 300 ml of water to prepare an ion exchange solution, adding 100g of D001 hydrogen type cation exchange resin into the solution, stirring at the room temperature of 35 ℃ for 12 hours, filtering and drying to obtain the aluminum ion crosslinking modified resin C, wherein the ion exchange rate is 55%.
Preparation of 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, stirred for 12 hours at 40 ℃, filtered and dried to obtain the calcium ion crosslinking modified resin D, and the ion exchange rate is 40 percent.
Preparation of example 5
17.6g ferric nitrate dissolved in 200 ml water to prepare ion exchange solution, 100g 122 hydrogen type cation exchange resin is added into the solution, 40 degrees C under stirring for 12 hours, filtering, drying to obtain calcium ion cross-linking modified resin E, ion exchange rate is 42%.
Preparation of example 6
Resin F was obtained by following the procedure of preparation example 3 except that vanadium chloride was used in an ion exchange rate of 55%.
Resin swelling experiments: a20 g sample of the test resin was added to 100mL of cyclohexanone and soaked for 48 hours, and the sample was taken out for swelling and the test results are shown in Table 1:
TABLE 1 resin samples swell in Cyclohexanone in comparison
As can be seen from the data in Table 1, the swelling resistance of the resin catalyst treated by the method of the invention is obviously better than that of the sodium/hydrogen cation exchange resin sold on the market, and the resin catalyst can be better applied to the acid decomposition reaction of cyclohexylbenzene hydroperoxide.
Example 1
10g of the resin A catalyst was packed in a fixed bed reactor, and a cyclohexylbenzene oxidation solution (main composition: cyclohexylbenzene hydroperoxide, cyclohexylbenzene, phenylhexanone and phenylcyclohexanol, the same as in the other examples) containing 30% by weight of cyclohexylbenzene hydroperoxide was charged at 60 ℃ at 1.0ml/min and continuously reacted for 24 hours with a cyclohexylbenzene hydroperoxide conversion of 98%, phenol selectivity of 91% and cyclohexanone selectivity of 87%.
Example 2
Charging 10g of the resin B catalyst into a fixed bed reactor, adding 2.0ml/min of a cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide at 50 ℃ to continue the 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
Charging 10g of the resin A catalyst into a fixed bed reactor, adding cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide at 80 ℃ at 1.0ml/min, and continuing the reaction for 24 hours with a cyclohexylbenzene hydroperoxide conversion of 99%, phenol selectivity of 89%, and 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 001X 7 sodium type cation exchange resin was charged in a fixed bed reactor, and a cyclohexylbenzene oxidation solution containing 30% by weight of cyclohexylbenzene hydroperoxide was charged at 60 ℃ at 1.0ml/min, with the cyclohexylbenzene hydroperoxide conversion being 55%, phenol selectivity being 75%, and cyclohexanone selectivity being 70%.
Comparative example 2
10g of a 001X 7 hydrogen type cation exchange resin was charged in a fixed bed reactor, and a cyclohexylbenzene oxidation solution containing 25% by weight of cyclohexylbenzene hydroperoxide was charged at 80 ℃ and 1.0ml/min, the cyclohexylbenzene hydroperoxide conversion was 79%, the phenol selectivity was 60%, and the cyclohexanone selectivity was 53%.
Comparative example 3
The procedure of example 2 was followed, except that DL-1H hydrogen type cation exchange resin was used as the 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 were as shown in Table 2.
Comparative example 5
The procedure of example 6 was followed, except that a 122 hydrogen type cation exchange resin was used as a catalyst, and the reaction results were as shown in Table 2.
TABLE 2
As seen from the data in Table 2 above, the conversion and selectivity of the catalyst of the present invention have significant advantages, which indicates that the catalyst of the present invention has high acid decomposition efficiency, and in the present invention, the acid decomposition efficiency refers to the reaction efficiency of resin catalyzed peroxide.
Table 3 below shows the long-term reaction data for each catalyst, and in particular table 3.
TABLE 3 (reaction 100h, all other conditions being equal)
As can be seen from the data in Table 3 above, the catalyst of the present invention has very good stability, and can maintain high conversion and selectivity for 100h of reaction time.
The experimental results of the examples and the comparative examples show that the resin catalyst prepared by 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 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 above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of acid decomposition of a hydroperoxide, comprising:
(1) Performing ion exchange on hydrogen type cation exchange resin and a salt solution containing divalent cations and/or trivalent cations to obtain a resin catalyst, and controlling the exchange conditions to ensure that the hydrogen ion exchange rate is 10-60%;
(2) Contacting a hydroperoxide with the resin catalyst in the presence of an optional solvent.
2. The method according to claim 1, wherein, in step (1),
the divalent cations are alkaline earth metal cations and/or divalent transition metal cations; preferably 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 cation is one or more of cobalt ion, aluminum ion, iron ion, chromium ion and vanadium ion, and is preferably aluminum ion and/or iron ion.
4. The method according to any one of claims 1 to 3, wherein, in step (1),
the salt of the divalent cation and/or the trivalent cation is a chloride salt and/or a nitrate salt.
5. The method according to any one of claims 1 to 4, wherein, in step (1),
the hydrogen type cation exchange resin is hydrogen type monovalent cation exchange resin; preferably 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 to hydrogen form after hydrochloric acid treatment, 001 x 14 sodium type cation exchange resin which is completely exchanged to hydrogen form after hydrochloric acid treatment, DL12 sodium type cation exchange resin which is completely exchanged to hydrogen form after hydrochloric acid treatment and D001 sodium type cation exchange resin which is completely exchanged to hydrogen form after hydrochloric acid treatment, and preferably the concentration of hydrochloric acid is 5% to 37%.
6. The method according to any one of claims 1 to 5, wherein, in step (1),
the conditions for ion exchange include: the exchange temperature is 5-90 ℃, preferably 20-60 ℃; and/or the exchange time is 0.5 to 24 hours.
7. The method of any one of claims 1-6, wherein step (1) comprises: the resin catalyst is obtained by immersing a hydrogen type cation exchange resin in a salt solution containing divalent cations and/or trivalent cations for ion exchange, performing partial ion exchange under stirring, and displacing part of hydrogen ions.
8. The process according to any one of claims 1 to 7, wherein in step (2), the hydroperoxide is a tertiary alkyl substituted benzene hydroperoxide, more preferably cyclohexylbenzene hydroperoxide.
9. The method according to any one of claims 1 to 8, wherein step (2),
the conditions of the contact include:
the temperature is 40-150 ℃, preferably 50-80 ℃; and/or
The time is 0.5 to 24 hours.
10. The method according to any one of claims 1 to 9, wherein step (2),
the solvent is an aromatic compound and/or a ketone compound; preferably
The aromatic compound is represented by the general formula B:
wherein R is C 1 ～C 8 One of alkyl groups; m is an integer of 0 to 6; preferably one or more of benzene, toluene and p-xylene;
the ketone compound is a ketone compound having 3 to 6 carbon atoms, and preferably acetone and/or cyclohexanone.
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870217A (en) * | 1988-10-24 | 1989-09-26 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| JP2007099746A (en) * | 2005-09-06 | 2007-04-19 | Ube Ind Ltd | Method for producing phenol and cycloalkanone |
| CN102333750A (en) * | 2009-02-26 | 2012-01-25 | 埃克森美孚化学专利公司 | Process for producing phenol |
| US20120157718A1 (en) * | 2009-06-29 | 2012-06-21 | Polimeri Europa S.P.A. | Process for the preparation of phenol and cyclohexanone |
| CN103801397A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Bimetal resin catalyst and preparation method thereof |
| US20150045587A1 (en) * | 2010-01-25 | 2015-02-12 | Exxonmobil Chemical Patents, Inc. | Process for Producing Phenol |
| CN104640827A (en) * | 2012-09-17 | 2015-05-20 | 埃克森美孚化学专利公司 | Process for producing phenol and/or cyclohexanone from cyclohexylbenzene |
| CN105164093A (en) * | 2013-04-02 | 2015-12-16 | 埃克森美孚化学专利公司 | Process and apparatus for making phenol and/or cyclohexanone |
| EP2985280A1 (en) * | 2014-08-11 | 2016-02-17 | Reliance Industries Limited | A process for synthesis of furfural or derivatives thereof |
| CN105980369A (en) * | 2013-12-13 | 2016-09-28 | 巴斯夫欧洲公司 | Production of furfural from xylose |
| CN106029642A (en) * | 2014-01-27 | 2016-10-12 | 莱诺维亚公司 | Conversion of fructose-containing feedstocks to hmf-containing product |
| CN106397167A (en) * | 2015-07-31 | 2017-02-15 | 埃克森美孚化学专利公司 | Process for making cyclohexanone |
| CN109897020A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院宁波材料技术与工程研究所 | A kind of refining methd of crude product 5-hydroxymethyl-furfural |
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN111315729A (en) * | 2017-09-28 | 2020-06-19 | Ifp 新能源公司 | Method for producing 5-hydroxymethylfurfural in the presence of an organic dehydration catalyst and a chloride source |
| CN111995602A (en) * | 2020-08-13 | 2020-11-27 | 浙江恒澜科技有限公司 | Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose |
| CN112094187A (en) * | 2020-10-28 | 2020-12-18 | 中国科学院山西煤炭化学研究所 | Method for preparing and separating levulinic acid from fructose |
| CN113234043A (en) * | 2021-04-26 | 2021-08-10 | 浙江大学衢州研究院 | Preparation and separation method for preparing 5-hydroxymethylfurfural by fructose dehydration |
| CN113906014A (en) * | 2019-06-06 | 2022-01-07 | 荷兰普拉克公司 | Method for producing hydroxymethylfurfural |
| CN114075156A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Method for continuously producing 5-hydroxymethylfurfural |
| CN114805253A (en) * | 2021-01-28 | 2022-07-29 | 中国石油化工股份有限公司 | Method for preparing 5-hydroxymethylfurfural |
-
2021
- 2021-09-30 CN CN202111156683.6A patent/CN115894193A/en active Pending
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870217A (en) * | 1988-10-24 | 1989-09-26 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| JP2007099746A (en) * | 2005-09-06 | 2007-04-19 | Ube Ind Ltd | Method for producing phenol and cycloalkanone |
| CN102333750A (en) * | 2009-02-26 | 2012-01-25 | 埃克森美孚化学专利公司 | Process for producing phenol |
| US20120157718A1 (en) * | 2009-06-29 | 2012-06-21 | Polimeri Europa S.P.A. | Process for the preparation of phenol and cyclohexanone |
| US20150045587A1 (en) * | 2010-01-25 | 2015-02-12 | Exxonmobil Chemical Patents, Inc. | Process for Producing Phenol |
| CN104640827A (en) * | 2012-09-17 | 2015-05-20 | 埃克森美孚化学专利公司 | Process for producing phenol and/or cyclohexanone from cyclohexylbenzene |
| CN103801397A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Bimetal resin catalyst and preparation method thereof |
| CN105164093A (en) * | 2013-04-02 | 2015-12-16 | 埃克森美孚化学专利公司 | Process and apparatus for making phenol and/or cyclohexanone |
| US20160304481A1 (en) * | 2013-12-13 | 2016-10-20 | Basf Se | Production of furfural from xylose |
| CN105980369A (en) * | 2013-12-13 | 2016-09-28 | 巴斯夫欧洲公司 | Production of furfural from xylose |
| CN106029642A (en) * | 2014-01-27 | 2016-10-12 | 莱诺维亚公司 | Conversion of fructose-containing feedstocks to hmf-containing product |
| EP2985280A1 (en) * | 2014-08-11 | 2016-02-17 | Reliance Industries Limited | A process for synthesis of furfural or derivatives thereof |
| CN106397167A (en) * | 2015-07-31 | 2017-02-15 | 埃克森美孚化学专利公司 | Process for making cyclohexanone |
| CN111315729A (en) * | 2017-09-28 | 2020-06-19 | Ifp 新能源公司 | Method for producing 5-hydroxymethylfurfural in the presence of an organic dehydration catalyst and a chloride source |
| US20200290984A1 (en) * | 2017-09-28 | 2020-09-17 | IFP Energies Nouvelles | Process for producing 5-hydroxymethylfurfural in the presence of an organic dehydration catalyst and a chloride source |
| CN109897020A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院宁波材料技术与工程研究所 | A kind of refining methd of crude product 5-hydroxymethyl-furfural |
| CN113906014A (en) * | 2019-06-06 | 2022-01-07 | 荷兰普拉克公司 | Method for producing hydroxymethylfurfural |
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN111995602A (en) * | 2020-08-13 | 2020-11-27 | 浙江恒澜科技有限公司 | Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose |
| CN114075156A (en) * | 2020-08-14 | 2022-02-22 | 中国石油化工股份有限公司 | Method for continuously producing 5-hydroxymethylfurfural |
| CN112094187A (en) * | 2020-10-28 | 2020-12-18 | 中国科学院山西煤炭化学研究所 | Method for preparing and separating levulinic acid from fructose |
| CN114805253A (en) * | 2021-01-28 | 2022-07-29 | 中国石油化工股份有限公司 | Method for preparing 5-hydroxymethylfurfural |
| CN113234043A (en) * | 2021-04-26 | 2021-08-10 | 浙江大学衢州研究院 | Preparation and separation method for preparing 5-hydroxymethylfurfural by fructose dehydration |
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