CN107879900B - Process method for separating and purifying cresol mixed isomer - Google Patents
Process method for separating and purifying cresol mixed isomer Download PDFInfo
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- CN107879900B CN107879900B CN201711405686.2A CN201711405686A CN107879900B CN 107879900 B CN107879900 B CN 107879900B CN 201711405686 A CN201711405686 A CN 201711405686A CN 107879900 B CN107879900 B CN 107879900B
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- 238000000034 method Methods 0.000 title claims abstract description 65
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229930003836 cresol Natural products 0.000 title claims abstract description 23
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 128
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 238000013375 chromatographic separation Methods 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000001768 cations Chemical group 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000011552 falling film Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 150000002931 p-cresols Chemical class 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 10
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000035900 sweating Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic nitrile Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 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 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a process method for separating and purifying cresol mixed isomer, which is characterized in that a mixture mainly containing m-cresol and p-cresol isomer is taken as a feed and is input into a sequential simulated moving bed for adsorption separation, a high-purity p-cresol solution is obtained from a liquid extraction port, and a desorption solvent is removed through rectification separation to obtain a p-cresol product; and (3) obtaining a mixed solution mainly containing m-cresol from a raffinate port, rectifying and separating the mixed solution to remove a desorption solvent to obtain a m-cresol-rich mixture, and carrying out recrystallization and separation to obtain a m-cresol product. The sequential simulated moving bed at least comprises 4 chromatographic separation columns, and at least comprises a raw material feed port, a desorbent feed port, a drawing liquid discharge port and a raffinate discharge port. The process method can continuously and efficiently obtain high-purity p-cresol and m-cresol products simultaneously, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical separation, relates to a process method for separating and purifying cresol mixed isomer compounds, and in particular relates to a method for separating and purifying cresol and m-cresol products with high purity by an adsorption-crystallization combined process.
Background
The cresol has three isomers, i.e. o-cresol, m-cresol and p-cresol respectively. Each monomer is an important fine chemical intermediate. The o-cresol is mainly used for synthetic resin, herbicide, disinfectant, preservative, plasticizer, perfume and the like. The m-cresol can be used as an analysis reagent and is also an important raw material of antioxidants, vitamin E, synthetic resin, color film developer and the like. The p-cresol is the main raw material for producing antioxidant, plasticizer, medical disinfectant, dye, perfume, curing agent, fluorescent whitening agent and other products. Along with the continuous development of downstream products of cresol monomers, the demand for high-purity cresol monomers is increasing at home and abroad.
The cresol isomers, i.e. intermediate cresol and p-cresol, are very close in boiling point and are difficult to separate and purify by conventional rectification methods, and the basic physicochemical properties are shown in the following table:
| Parameter item | M-cresol | Para-cresol | O-cresol |
| Melting Point/. Degree.C | 10.90 | 34.69 | 30.90 |
| Boiling point/. Degree.C | 202.80 | 201.90 | 190.80 |
| Critical temperature/°c | 432 | 426 | 422 |
| Critical pressure/MPa | 4.56 | 4.07 | 4.17 |
The boiling point difference between the o-cresol and the m-cresol is more than 10 ℃, the o-cresol and the m-cresol can be separated by a rectification separation and purification method, and the boiling point difference between the p-cresol and the m-cresol is only 0.9 ℃, and the o-cresol and the m-cresol are difficult to separate and purify by a conventional rectification method, so the invention has great significance in producing high-purity p-cresol and m-cresol monomers by the separation and purification method. The separation methods of m-cresol and p-cresol can be divided into two major categories, namely physical methods and chemical methods. Physical methods include azeotropic distillation, dissociation extraction, high-pressure crystallization separation and molecular sieve adsorption separation; the chemical method includes chelate separation and alkylation separation. Wherein, in the presence of sodium paracresol, the paracresol can be distilled off azeotropically with water by an azeotropic distillation method, but the energy consumption is too large; the dissociation and extraction method uses a large amount of organic solvents, so as to pollute the environment; the high-pressure crystallization separation method requires 100-300 MPa of pressure, has too high equipment requirement and has too large investment; the alkylation separation method requires a large amount of alkylation catalyst and dealkylation catalyst, and has the disadvantages of complex equipment and high investment; the chelate separation method has the problems of complex process, difficult operation, high pollution, high energy consumption and the like, and the purity and recovery rate of the cresol monomer are lower. The article "separation of para-cresol from meta-cresol" (Tianjin chemical, no. 4), the same amount of para-cresol is produced, the feed amount of mixed cresol is reduced by about 30% compared with that of crystallization method, and the utilization rate of liquid phase operation equipment is very high, so that the investment of adsorption method is reduced by 15% -20% and the operation cost is reduced by 5% -10% compared with that of crystallization method.
Literature (Ind. Eng. Chem. Res.,2000,39 (4), 1035-1038) indicates that the purity of m-cresol and p-cresol can reach more than 98% under the conditions that SiCl 4 modified HZSM-5 molecular sieve is used as an adsorbent, compressed propane is used as a carrier and desorbent, and the optimal separation condition of m-cresol and p-cresol is 373K, 3.45MPa and propane flow rate is 2.0 mL/min. The method has the problems of complex preparation process of the adsorbent, high operation pressure, high cost and the like.
The literature (university of Zhejiang, journal of the university of science (Nature science edition) vol.38, no. 4) states that the modified adsorbent is found to contribute to the improvement of adsorption efficiency by preparing ZSM-5 zeolite of a hierarchical pore structure by modifying ZSM-5. The method has the advantages of complex adsorbent preparation, high cost and undefined optimal process conditions.
The adsorption separation method reported in the above patent documents requires a plurality of layers of adsorption towers to operate, not only has limited feed concentration and amount, but also has large consumption of desorbant and high production cost, and can only obtain one product of p-cresol. The process disclosed by the invention is capable of separating and purifying p-cresol and m-cresol products simultaneously by using sequential simulated moving bed adsorption with fewer adsorption bed layers and combining a crystallization separation process, has the characteristics of simplicity and high efficiency, and is suitable for industrial application.
Disclosure of Invention
The invention aims to effectively separate and purify the mixture mainly containing m-cresol and p-cresol isomers, simultaneously continuously obtain pure products of the m-cresol and the p-cresol isomers, and reduce the production cost.
The invention combines the sequential simulated moving bed adsorption separation process and the crystallization separation process, and then cooperates with the method of rectifying and removing the desorbent, thereby being capable of producing high-purity p-cresol and m-cresol products simultaneously.
The invention provides a process method for separating and purifying cresol mixed isomer, which comprises the following steps:
A. the mixed isomer mainly containing m-cresol and p-cresol is taken as a raw material to be input into a sequential simulated moving bed, and after the adsorption effect of an adsorbent and the desorption effect of a desorbing agent, the extract is obtained into a high-purity p-cresol solution, and the raffinate is obtained into an enriched m-cresol solution;
B. rectifying the extract and raffinate of the step A to obtain high-purity p-cresol product and enriched m-cresol, and recovering and utilizing the desorbent separated by rectification;
C. Conveying the concentrated m-cresol mixture obtained in the step B into a falling film crystallizer for gradual cooling, and crystallizing and separating out the p-cresol at the final temperature ranging from 11.0 ℃ to 24.0 ℃ to obtain refined m-cresol feed liquid;
D. Gradually cooling the refined m-cresol feed liquid obtained in the step C until solidification, then gradually heating to a final temperature ranging from 11.0 ℃ to 24.0 ℃ to obtain a high-purity m-cresol product, and carrying out adsorption separation again by taking malcrystalline as an isomer raw material.
The invention provides a process method for separating and purifying cresol mixed isomers, which is characterized in that a sequential simulated moving bed comprises at least 4 chromatographic columns, preferably 4-12 chromatographic columns, and more preferably 6-12 chromatographic columns, wherein each chromatographic separation column comprises two feed inlets which are respectively a raw material feed inlet and a desorbent feed inlet, and each chromatographic separation column comprises three discharge outlets which are respectively a raffinate discharge outlet a1, a raffinate discharge outlet b1 and a raffinate discharge outlet c1.
The invention provides a process method for separating and purifying cresol mixed isomers, which is characterized in that each chromatographic column is subjected to three steps S1, S2 and S3, and when one chromatographic column finishes the steps S1-S3, the steps S1-S3 are automatically switched to the next chromatographic column according to the sequence, and the steps S1-S3 are repeated. S1, material is closed and self-circulated in the sequential simulated moving bed chromatographic separation, no material enters and exits the system, and the circulation amount is 31-76%, preferably 45-55% of the volume of a single chromatographic column; s2, desorbing agent is fed into a desorbing agent feed port, a part of raffinate is discharged from a raffinate discharge port c1, and the feeding and desorbing dosage is 2-34% of the volume of a single chromatographic column, preferably 15-20%; s3, desorbing agent is fed into the desorbing agent feed port, the extract is discharged from the extract discharge port a1, the raw material is fed into the raw material feed port, the raffinate is discharged from the raffinate discharge port b1, the feeding and desorbing dose is 2-34% of the volume of a single chromatographic column, preferably 18-22%, and the feeding volume of the raw material is 2-34% of the volume of the single chromatographic column, preferably 10-14%; the extraction liquid outlet a1 and the extraction liquid outlet b1c1 are separated by at least 1 chromatographic column.
The invention provides a process method for separating and purifying cresol mixed isomer, which is characterized in that the active component is one or more of ion-exchanged X molecular sieve, ion-exchanged Y molecular sieve and ZSM-5 molecular sieve, preferably ion-exchanged X molecular sieve with a silicon-aluminum molecular ratio of 2.2-2.5. Preferably. The adsorbent comprises 90.0-100% cation exchange degree, preferably 95.0-100%. The adsorbent comprises 0.1 to 20wt% of binder, preferably 0.1 to 6.0wt% of binder. The water content is 0.1 to 10wt%, preferably 0.9 to 5.0wt%.
The invention provides a process method for separating and purifying cresol mixed isomer, which is characterized in that a desorbent is one or more of C1-C12 saturated alcohol, toluene, dimethylbenzene, phenol, aliphatic nitrile, propionitrile and butyronitrile. The X-type molecular sieve desorbent is preferably n-amyl alcohol, n-hexyl alcohol, toluene and phenol. The ZSM-5 molecular sieve desorbent is preferably toluene and phenol.
The cations exchanged by the X-type and Y-type molecular sieves of the invention are mainly one or more of Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Cu2+、Ag+、NH4 +, preferably one or more of K +、Ca2+、Ba2+, and most preferably K + and Ba 2+.
The binder used by the adsorbent provided by the invention is one or more of kaolin, bentonite, rectorite, montmorillonite, diatomite, halloysite or palygorskite, and is preferably kaolin and rectorite.
The combined method for separating and purifying the mixed isomer of m-cresol and p-cresol is characterized in that the adsorption separation temperature is 49.9-249.9 ℃, preferably 150-200 ℃, and the pressure is 0.1-4.0 MPa, preferably 1.0-2.0 MPa.
The process method for separating and purifying the cresol mixed isomer is characterized in that the final temperature of cooling is 11.0-24.0 ℃, preferably 22.0-24.0 ℃; the cooling rate is 1.0-20 ℃/h, preferably 14-17 ℃/h. The final temperature of the m-cresol sweating is 11.0-24.0 ℃, preferably 12.5-15.5 ℃; the heating rate is 0.5-20 ℃/h, preferably 1.5-3.5 ℃/h.
The process disclosed by the invention has the advantages of low running cost, high purity of the separated product, simple operation steps and improved production efficiency.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
fig. 1: the process flow chart for separating and purifying cresol mixed isomer comprises the following steps:
1. a sequential simulated moving bed; 1.1, a chromatographic separation column; d, F, A, B, C outside the chromatographic separation column are respectively a desorbent tank, a raw material tank, a raffinate collecting tank, a raffinate b component collecting tank and a raffinate c component collecting tank; D. f, A, B, C are respectively connected with a desorbent feed port, a raw material feed port, a drawing liquid discharge port a1, a drawing liquid discharge port b1 and a drawing liquid discharge port c1 on each chromatographic separation column; 1.2, desorbent pump; 1.3, a raw material pump; 1.4, a circulating pump;
2. a draw-out liquid rectifying tower; a. extracting liquid; (a) an extraction fluid inlet; e. a light component; (e), a light component outlet; f. a heavy component; (f), heavy component outlet;
3. A raffinate rectification column; bc. A raffinate; (bc), a raffinate inlet; g. a light component; (g), a light component outlet; h. a heavy component; (h), heavy component outlet;
4. A falling film crystallizer; i. an enriched m-cresol feed solution; (i) an enriched m-cresol feed solution inlet; j. a cooling medium; 4.1, a cooling medium circulating pump; k. melting the material; 4.2, a molten material circulating pump; m, refined m-cresol feed liquid; (m) a refined m-cresol feed solution outlet; n, malcrystalline; (n), malcrystalline outlets;
5. A melt crystallizer; (o) inlet of refined m-cresol feed liquid; p, a cooling medium; 5.1, a cooling medium circulating pump; q, heating medium; 5.2, a heating medium circulating pump; r, m-cresol product; (r), m-cresol product outlet; s, malcrystalline; (s), malcrystalline outlets.
When the boiling point of the desorbent is lower than that of cresol, the heavy component of the raffinate rectifying tower is enriched m-cresol feed liquid, and at the moment, the heavy component outlet of the raffinate rectifying tower is connected with the feed inlet of the falling film crystallizer; when the boiling point of the desorbent is higher than that of cresol, the light component of the raffinate rectifying tower is the enriched m-cresol feed liquid, and at the moment, the light component outlet of the raffinate rectifying tower is connected with the feed inlet of the falling film crystallizer.
Fig. 2: a step schematic diagram of the sequential simulated moving bed S1, wherein the shadows of the chromatographic separation column indicate that the feed liquid flows in the chromatographic separation column, and the blank in the chromatographic separation column indicates that the feed liquid does not flow; D. the F, A, B, C port has no material entering and exiting the separation column.
Fig. 3: step S2, a schematic diagram of a sequential simulated moving bed, wherein the shadow of a chromatographic separation column indicates that feed liquid flows in the chromatographic separation column, and the blank in the chromatographic separation column indicates that the feed liquid does not flow; the D and C ports are provided with material inlet and outlet separation columns, and the F, A, B ports are provided with no material inlet and outlet separation columns.
Fig. 4: step 3, a sequential simulated moving bed S3 is schematically shown, wherein the shadow of the chromatographic separation column indicates that the feed liquid flows in the chromatographic separation column, and the blank in the chromatographic separation column indicates that the feed liquid does not flow; D. f, A, B ports have no material in and out of the separation column, and C ports have no material in and out of the separation column.
Detailed Description
Embodiments of the present invention and the effects produced are further illustrated by examples and comparative examples, but the scope of the present invention is not limited to what is shown in the examples.
Comparative example 1
NaY molecular sieve is prepared according to the method of the example 1 of the patent CN 102107882, rectorite is used as a binder, ball forming crystallization is carried out, 0.3-0.8 mm balls are prepared, ion exchange is carried out according to the method of the example 3, K + accounts for 3.9% of total cation position after the ion exchange, ba 2+ accounts for 95.3% of total cation position, the adsorbent VS is used, and the component content and physical properties of the adsorbent VS are shown in the table 1.
Example 1
102Kg of X molecular sieve with 15wt% of water and 0.45 mu m average grain diameter and silicon-aluminum molecular ratio of 2.37, 10.5kg of kaolin (90.2 wt% of kaolinite content) as a binder, deionized water as an auxiliary agent (10.9 wt% of deionized water as solid powder), rolling balls to form balls with 0.3-0.8 mm, drying at 120 ℃ for 24h, and roasting at 550 ℃ for 6h. The pellets were treated with 1.4mol/L NaOH aqueous solution at 95℃for 6 hours at a solid-to-liquid ratio of 1.6:1. Washing the pellets to pH value of 10 by using deionized water, drying at 85 ℃ for 24 hours, roasting at 550 ℃ for 6 hours, screening out pellets with the diameter of 0.3-0.8 mm, then fluidizing and dehydrating at 240 ℃, controlling the water content of the adsorbent to be 1.8wt%, and recording the obtained adsorbent as I. A3 mL cylindrical barrel was prepared, 2.5mL of the adsorbent sample was added to the barrel, the pressure was applied at a strength of 200N, and the adsorbent crushing ratio was counted and recorded as the crushing ratio. The content of the component I and the physical properties of the adsorbent are shown in Table 1.
Example 2
The preparation process is the same as in example 1, except that rectorite is used as binder to form a rolling ball, and the adsorbent II is prepared through post-treatment, wherein the component content and physical properties are shown in Table 1.
Example 3
The preparation process is the same as that of example 1, the adsorbent obtained in example 1 is subjected to K + exchange for 20h by 0.5mol/L KNO 3 aqueous solution under the conditions of 95 ℃,0.2 MPa and 3.0h -1 of exchange liquid volume space velocity, then 0.18mol/L Ba (NO 3)2 aqueous solution is used for 24h in the same condition), K + accounts for 4.1% of total cation positions after exchange, ba 2+ accounts for 95.5% of total cation positions, and the adsorbent is adsorbent III, and the component content and physical properties are shown in Table 1.
Example 4
The adsorbents prepared according to the procedure of example 2 were subjected to ion exchange of K + and Ba 2+ in accordance with the procedure of example 3, K + representing 3.8% of the total cation sites and Ba 2+ representing 95.9% of the total cation sites after the exchange, and were adsorbent IV, the component contents and physical properties of which are shown in Table 1.
Example 5
The adopted sequential simulated mobile chromatography equipment consists of 6 chromatographic columns (with the inner diameter of 30mm and the length of 800 mm), wherein each chromatographic column is 565mL, and the total amount of the chromatographic columns is 3.4L, and the two feeding hole positions and the two discharging hole positions are controlled by an electromagnetic valve to sequentially simulate a moving bed process flow chart as shown in figure 1. 3000g of adsorbent III with the thickness of 0.3-0.8 mm is filled into 6 adsorption columns, and the operation temperature of the sequential simulated moving bed is 150 ℃ and the pressure is 1.1MPa. The desorbent is n-amyl alcohol and the adsorbent is adsorbent III.
The mixed cresol raw material F-1 (the raw material composition is shown in table 2) is conveyed into a sequential simulated moving bed separation adsorption column through a metering pump at a flow rate of 25.2g/h, and the circulation amount is 48% of the volume of the chromatographic column; first, step S1 is performed. And S2, namely, the n-amyl alcohol serving as an inlet desorbent is 16% of the volume of the chromatographic column, and is conveyed to an adsorption bed through a metering pump at a flow rate of 34.6g/h at a weight space velocity, and a component c of the raffinate is discharged at a raffinate discharge port c1 at a weight space velocity of 34.6 g/h. And finally, S3, namely, S3 simultaneously feeds the desorbent and the raw material, wherein the n-amyl alcohol amount is 20% of the volume of the chromatographic column, the weight space velocity is 34.6g/h, the extract a component is discharged at the extract discharge port a1, the feed F-1 amount is 13% of the volume of the chromatographic column, and the raffinate b component is discharged at the raffinate discharge port b1 at the weight space velocity of 12.6 g/h. Wherein the purity of the extracted liquid p-cresol is 99.2 percent, and the yield is 91 percent. The purity of the raffinate m-cresol is 95.5%.
And (3) mixing and rectifying the raffinate obtained in the steps S2 and S3, and then refining, wherein the final temperature is reduced to 22 ℃, the cooling rate is 15 ℃/h, and the purity of the filtrate m-cresol is 98.8%. And heating the filtrate after solidification, wherein the final sweating temperature is 12 ℃, and the heating rate is 2.4 ℃/h, so that the purity of the m-cresol product is 99.4%, and the yield is 71.3%. And mixing the crystals obtained respectively and then taking the mixed crystals as raw materials to continuously participate in adsorption separation.
Example 6
The procedure and operating conditions of example 5 were followed, except that adsorbent IV was used as the adsorbent. The purity of the extracted liquid p-cresol is 99.7 percent, and the yield is 92.2 percent. The purity of the raffinate m-cresol is 95.9%. After crystallization, m-cresol with purity of 99.5% is obtained, and the yield is 75.5%.
Comparative example 2
The procedure and operating conditions in example 5 were followed, except that adsorbent VS was used as the adsorbent. The purity of the extracted liquid p-cresol is 98.5 percent, and the yield is 88.2 percent. The purity of the raffinate m-cresol is 93.1 percent. After crystallization, m-cresol with the purity of 98.1 percent is obtained, and the yield is 68.1 percent.
Example 7
The procedure and operating conditions in example 6 were followed, except that feed F-2 was used. The purity of the extracted liquid p-cresol is 99.2 percent, and the yield is 92.6 percent. The purity of the raffinate m-cresol is 95.3 percent. After crystallization, m-cresol with purity of 99.2% is obtained, and the yield is 70.3%.
Example 8
The procedure and operating conditions in example 6 were used, except that F-3 was used as the starting material (the composition of the starting material is shown in Table 2). The purity of the extracted liquid p-cresol is 98.9 percent, and the yield is 92.1 percent. The purity of the raffinate m-cresol is 93.4%. After crystallization, m-cresol with purity of 98.8% is obtained, and the yield is 70.1%.
Example 9
The process flow and operating conditions of example 6 were employed except that the cooling rate was 20 ℃/h. The purity of the extracted liquid p-cresol is 99.7 percent, and the yield is 92.2 percent. The purity of the raffinate m-cresol is 95.9%. After crystallization, m-cresol with purity of 99.6% is obtained with yield of 69.4%.
Example 10
The procedure and operating conditions of example 6 were used, except that the sweating ramp rate was 3.0 ℃/h. The purity of the extracted liquid p-cresol is 99.7 percent, and the yield is 92.2 percent. The purity of the raffinate m-cresol is 95.9%. After crystallization, m-cresol with purity of 99.1% is obtained, and the yield is 73.6%.
Example 11
The procedure and operating conditions in example 6 were used, except that the adsorption separation temperature was 180 ℃. The purity of the extracted liquid p-cresol is 99.5 percent, and the yield is 91.2 percent. The purity of the raffinate m-cresol is 95.2%. After crystallization, m-cresol with purity of 99.2% is obtained, and the yield is 74.7%.
Comparative example 3
The adopted traditional process simulation mobile chromatographic equipment consists of 24 chromatographic columns (with the inner diameter of 30mm and the length of 200 mm), and each chromatographic column is 141mL and 3.4L in total. There are 5 chromatographic separation columns (desorption zone) before the desorbent and the draw-off outlet, 10 chromatographic separation columns (purification zone) between the draw-off outlet and the feed inlet, 6 chromatographic separation columns (adsorption zone) between the feed inlet and the raffinate outlet, and 3 chromatographic separation columns (buffer zone) between the raffinate outlet and the desorbent inlet.
3000G of adsorbent IV with the thickness of 0.3-0.8 mm is filled into 24 chromatographic separation columns, the operation temperature is 150 ℃, the pressure is 1.1MPa, and the desorbent is n-amyl alcohol.
The flow rates of the materials in and out of the adsorption separation operation are as follows: 1200ml/h desorbent, 270ml/h extract, 180ml/h raw material, 1110ml/h raffinate.
Reflux ratios of the 4 areas of the adsorption separation system are respectively as follows: adsorption zone 2.632, purification zone 0.904, desorption zone 1.534, buffer zone-0.836 (negative values represent buffer zone reflux relative flow direction opposite to other zone reflux). The purity of the p-cresol is 98.9 percent, and the yield is 90.3 percent. The purity of the raffinate m-cresol is 93.6%.
TABLE 1 composition, bulk Density and particle size distribution of adsorbents
TABLE 2 composition of raw materials
The foregoing is a specific embodiment of the present invention, and the present invention is not limited to the above embodiment. Any person skilled in the art will recognize that while some changes or modifications can be made to the equivalent embodiments of the invention by using the above disclosed technical disclosure without departing from the scope of the invention, any simple modifications, equivalent substitutions and improvements made to the above embodiments within the spirit and principles of the invention are still within the scope of the invention.
Claims (6)
1. A process method for separating and purifying cresol mixed isomer is characterized by comprising the following process steps:
A. the mixed isomer mainly containing m-cresol and p-cresol is taken as a raw material to be input into a sequential simulated moving bed, and after the adsorption effect of an adsorbent and the desorption effect of a desorbing agent, the extract is obtained into a high-purity p-cresol solution, and the raffinate is obtained into an enriched m-cresol solution;
B. Rectifying the extract and raffinate of the step A to remove desorbent to obtain high-purity p-cresol product and enriched m-cresol respectively, and recycling the desorbent separated by rectification;
C. Conveying the concentrated m-cresol mixture obtained in the step B into a falling film crystallizer for gradual cooling, and crystallizing and separating out the p-cresol at the final temperature ranging from 11.0 ℃ to 24.0 ℃ to obtain refined m-cresol feed liquid;
D. gradually cooling the refined m-cresol feed liquid obtained in the step C until solidification, then gradually heating up to a final temperature range of 11.0-24.0 ℃ to obtain a high-purity m-cresol product, and carrying out adsorption separation again by taking malcrystalline as an isomer raw material;
The sequential simulated moving bed comprises at least 4 chromatographic separation columns, wherein each chromatographic separation column comprises two feed inlets which are respectively a raw material feed inlet and a desorbent feed inlet, and each chromatographic separation column comprises three discharge outlets which are respectively a raffinate discharge outlet a1, a raffinate discharge outlet b1 and a raffinate discharge outlet c1;
The preparation steps of the adsorbent are as follows: 102 The method comprises the steps of (1) kg of an X molecular sieve with 15 wt% water content and an average grain diameter of 0.45 mu m and a silicon-aluminum molecular ratio of 2.37, 10.5 kg rectorite as a binder, deionized water as an auxiliary agent, 10.9-wt% of solid powder, rolling and forming to obtain balls with the diameter of 0.3-0.8 mm, drying at 120 ℃ for 24h, roasting at 550 ℃ for 6 h, treating the balls with 1.4 mol/L NaOH aqueous solution at 95 ℃ according to a solid-to-liquid ratio of 1.6:1 for 6 h, washing the balls with deionized water to a pH value of 10, drying at 85 ℃ for 24h, roasting at 550 ℃ for 6 h, screening out balls with the diameter of 0.3-0.8 mm, and then fluidizing and dehydrating at 240 ℃, wherein the water content of the adsorbent is controlled to be 1.8 wt%;
carrying out K + exchange on the obtained adsorbent by 0.5mol/L KNO 3 aqueous solution under the conditions of 95 ℃,0.2 MPa and 3.0 h -1 of exchange liquid volume space velocity, and then carrying out 0.18 mol/L Ba (24 h is replaced by NO 3)2 aqueous solution under the same conditions, after exchange, K + accounts for 3.8% of total cation positions, and Ba 2+ accounts for 95.9% of total cation positions);
In the adsorption separation process, each chromatographic column sequentially completes 3 process steps from S1 to S3:
a) Firstly, S1, namely, closing self-circulation of materials in sequential simulated moving bed chromatographic separation, wherein no materials enter and exit a system;
b) S2, namely, desorbing agent is fed into a desorbent feeding port, and a part of raffinate is discharged from a raffinate discharging port c 1; other chromatographic columns are kept in a material inlet and outlet state;
c) Finally, S3, namely, desorbing agent is fed into a desorbing agent feeding port, a pumped liquid is discharged from a pumped liquid discharging port a1, raw materials are fed into a raw material feeding port, and a raffinate is discharged from a raffinate discharging port b 1; other chromatographic columns are kept in a material inlet and outlet state;
The extraction liquid outlet a1 and the extraction liquid outlet b1c1 are separated by at least 1 chromatographic column.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
In the step S1, the circulation amount is 31-76% of the volume of a single chromatographic column; in the S2 process, the desorption dosage is 2-24% of the volume of a single chromatographic column; in the S3 process, the desorption dosage is 2-24% of the volume of a single chromatographic column; the feed amount is 2-16% of the volume of a single chromatographic column.
3. The method of claim 1, wherein the desorbent is one or more of a C1-C12 saturated alcohol, toluene, xylene, phenol, propionitrile, butyronitrile.
4. The method according to claim 1, wherein the adsorption separation temperature is 49.9-249.9 ℃ and the pressure is 0.1-4.0 MPa.
5. The method according to claim 1, wherein the final temperature in step C is 22.0-24.0 ℃ and the cooling rate is 1.0-20 ℃/h.
6. The method of claim 1, wherein the intermediate cresol perspiration temperature in step D ranges from 12.5 to 15.5 ℃; the temperature rising rate is 0.5-20 ℃/h.
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| CN110511121B (en) * | 2018-05-22 | 2022-02-08 | 中国石油化工股份有限公司 | Method for separating p-cresol by liquid phase adsorption |
| CN110511118B (en) * | 2018-05-22 | 2022-02-08 | 中国石油化工股份有限公司 | Method for separating paracresol by liquid phase adsorption |
| CN110511122B (en) * | 2018-05-22 | 2022-03-11 | 中国石油化工股份有限公司 | Method for separating cresol isomer by liquid phase adsorption |
| CN109232192B (en) * | 2018-10-29 | 2021-09-17 | 国家能源投资集团有限责任公司 | Separation method of paracresol |
| CN109432822B (en) * | 2018-11-14 | 2023-09-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Efficient simulated moving bed equipment and efficient simulated moving bed process |
| CN111689838B (en) * | 2019-03-12 | 2023-01-13 | 中国石油化工股份有限公司 | Method for adsorbing and separating p-cresol and m-cresol |
| CN112110797B (en) * | 2019-06-21 | 2022-06-21 | 辽宁科技大学 | Preparative liquid chromatography for separating cresol isomer mixture |
| CN112110798B (en) * | 2019-06-21 | 2022-06-21 | 辽宁科技大学 | Simulated moving bed chromatography for separating cresol isomer mixture |
| CN113731352A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Adsorbent and method for adsorbing and separating m-cresol and p-cresol by using same |
| CN115974656A (en) * | 2022-12-12 | 2023-04-18 | 南京工业大学 | Method for separating cresol isomer by membrane |
| CN116239451A (en) * | 2022-12-16 | 2023-06-09 | 中触媒新材料股份有限公司 | Separation and purification method of m-cresol |
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