CN115806474A - Method for recovering 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol - Google Patents
Method for recovering 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol Download PDFInfo
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- CN115806474A CN115806474A CN202211593160.2A CN202211593160A CN115806474A CN 115806474 A CN115806474 A CN 115806474A CN 202211593160 A CN202211593160 A CN 202211593160A CN 115806474 A CN115806474 A CN 115806474A
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- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 42
- 238000011084 recovery Methods 0.000 claims abstract description 38
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 238000000746 purification Methods 0.000 claims abstract description 21
- 239000012043 crude product Substances 0.000 claims abstract description 15
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000001953 recrystallisation Methods 0.000 claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- -1 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol Chemical compound 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- LYQIPMLFCQTVQK-UHFFFAOYSA-N 3,5-ditert-butyl-4-(2,6-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1C1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C LYQIPMLFCQTVQK-UHFFFAOYSA-N 0.000 description 6
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003712 decolorant Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000550 effect on aging Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RNVAPPWJCZTWQL-UHFFFAOYSA-N octadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 RNVAPPWJCZTWQL-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of raw material recovery, in particular to a recovery method of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol, which adopts 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue as a recovery raw material, extracts 2,6-di-tert-butylphenol by reduced pressure distillation and temperature and pressure recovery, and then continuously recovers and extracts 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol by recrystallization; the method can recover and extract raw material 2,6-di-tert-butylphenol from 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue, and the recovery process is simple; and the residual byproduct 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol in the organic residue can be extracted and purified, so that 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is high in purity content and can meet the requirement of marketization, and the 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol crude product and reagents used for purification are rich, thereby being beneficial to controlling the extraction and purification cost, reducing the generation of solid waste and increasing the economic benefit of the product.
Description
Technical Field
The invention relates to the technical field of raw material recovery, in particular to a method for recovering 2,6-di-tert-butylphenol, 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol.
Background
3,5-di-tert-butyl-4-hydroxyphenyl-containing compounds have the effects of anti-inflammation, anti-virus, anti-tumor and the like, 3,5-di-tert-butyl-4-hydroxybenzoic acid and derivatives thereof are antioxidants and ultraviolet absorbers with wide application, are also intermediates for synthesizing mosquito-killing agents, and can also be used for synthesizing plastics, such as 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 ',4' -di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-n-hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-n-octadecyl ester and the like, rubber, photocuring coatings and the like which are widely used in the fields of antioxidants, light stabilizers and ultraviolet absorbers;
at present, the production method for producing 3,5-di-tert-butyl-4-hydroxybenzoic acid is as follows: 2,6-di-tert-butylphenol and alkali metal salt of alcohol or alkali metal hydroxide (such as potassium hydroxide and sodium hydroxide) are reacted to prepare 2,6-di-tert-butylphenol alkali metal salt, the alkali metal salt and carbon dioxide are subjected to Kolbe-Schmitt reaction in an autoclave, 3,5-di-tert-butyl-4-hydroxybenzoic acid is obtained after the reaction is finished and is acidified by dilute acid, and side reaction is generated in the reaction process to 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol, and the reaction equation is as follows:
2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is an important organic intermediate, and can be used for liquid polymers, electron transport materials, organic material stabilizers, metal decolorant ligands, flame retardants and the like; as an intermediate of the biphenyl liquid polymer, the synthesized polymer has the characteristics of high clearing point, good physical and chemical properties and the like due to the structural particularity; 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is excellent in heat resistance, can be used as a modified monomer of various products such as polyester, polyurethane, polycarbonate, polysulfone, epoxy resin and the like to manufacture excellent engineering plastics and composite materials, has a prevention effect on aging caused by oxygen and heat and no pollution, and can be used as rubber, an emulsion anti-aging agent and a plastic antioxidant; the flame retardant is particularly used for synthesizing a P-N flame retardant NTTBP, has good flame retardance and can enable the oxygen index of a base material to reach 27, so that 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol and a raw material 2,6-di-tert-butylphenol both have higher recovery value. In view of this, we propose a process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol.
Disclosure of Invention
In order to make up for the above deficiencies, the present invention provides a method for recovering 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol.
The technical scheme of the invention is as follows:
2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol recovery method, 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue is used as a recovery raw material, 2,6-di-tert-butylphenol is extracted by reduced pressure distillation and temperature and pressure recovery control, and 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol is continuously extracted by recrystallization recovery.
Preferably, the vacuum distillation method comprises the following specific steps: adding the recovered raw material organic residue into a reaction container, adding a decolorizing agent, controlling the distillation temperature to raise to 125-150 ℃, continuously stirring, controlling the distillation pressure to be between-0.095 and-0.080 MPa to distill 2,6-di-tert-butylphenol, and stopping distillation after 6-12 hours until no distillate exists.
Preferably, the stirring speed of the continuous stirring is 220-350rpm/min, and the temperature rising speed of the temperature rising from room temperature to the distillation temperature is as follows: heating to 1-100 deg.C at 2-3 deg.C/min, and heating to 125-150 deg.C at 1-2 deg.C/min.
Preferably, the decolorant is any one of aluminosilicate, bentonite or activated clay, and the mass fraction of the decolorant in the recovered raw material organic residue is as follows: 0.5 to 1.6 percent.
Preferably, the extraction method of the 2,2',6,6' -tetra-tert-butyl-4,4 ' -crude biphenyl diphenol comprises the following steps: cooling the reaction container which stops distilling to 50-60 ℃ by cold bath or natural cooling, preserving heat, then adding an extraction reagent into the reaction container, stirring for 0.5-1 hour, filtering, washing a first filter cake obtained by filtering by using the extraction reagent again, and drying the solution at 60 ℃ to obtain 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol crude product.
Preferably, the extraction reagent may be any one of methanol, ethanol, n-propanol and isopropanol.
Preferably, in the method for extracting crude 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol, the mass ratio of the extraction reagent to the residue inside the reaction vessel is: 1.5: 1-6: 1, and the mass ratio of the extracting reagent to the first filter cake is 1: 0.5-1: 3.
Preferably, the method for recrystallizing and purifying the crude 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol comprises the following steps: adding a purifying reagent into the 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenyl diphenol crude product, heating to 75-85 ℃ for dissolving, crystallizing at room temperature, filtering to obtain a second filter cake, washing with the purifying reagent, and recrystallizing at 70-80 ℃ to obtain purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenyl diphenol.
Preferably, the purification reagent may be any one of isopropyl alcohol, cyclohexane, n-octane, and tetrahydrofuran.
Preferably, in the method for purifying crude biphenyldiol by recrystallization of 2,2',6,6' -tetra-tert-butyl-4,4 '-crude biphenyldiol, the mass ratio of the purification reagent to the crude biphenyldiol 2,2',6,6 '-tetra-tert-butyl-4,4' -crude biphenyldiol is as follows: 2: 1-8: 1, and the mass ratio of the purification reagent to the second filter cake is: 2: 1-4: 1.
Compared with the prior art, the invention has the beneficial effects that:
the recovery method of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol can recover and extract raw material 2,6-di-tert-butylphenol from 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue, and the recovery process is simple; and residual by-products 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol in the organic residues can be extracted and purified, so that 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol has high purity and can meet the requirements of marketing, and the crude products of 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol and reagents used for purification are rich in types, so that the extraction and purification cost can be favorably controlled, and 2,6-di-tert-butyl phenol and 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol can be recycled, so that the generation of solid wastes is reduced, and the economic benefits of products are increased.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention details the above technical solution by the following embodiments:
2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol recovery method: weighing 700g of 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue, adding 700g of the organic residue into a 1L reaction kettle device, adding 7 g of a decolorizing agent bentonite, controlling the heating rate to be 3 ℃/min, heating to 100 ℃, then heating to 135 ℃ according to 1.5 ℃/min, preserving heat, distilling off 2,6-di-tert-butylphenol under reduced pressure under the condition of-0.090 MPa, and stopping distillation and heating when no distillate exists.
It should be noted that, according to the actual production process of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2,6-di-tert-butylphenol and alkali metal salt of alcohol or alkali metal hydroxide are reacted to prepare 2,6-di-tert-butylphenol alkali metal salt, kolbe-Schmitt reaction is carried out with carbon dioxide in an autoclave, 3,5-di-tert-butyl-4-hydroxybenzoic acid is obtained after the reaction is finished and is acidified by dilute acid, about 0.55 ton of organic residue is generated when one ton of 3,5-di-tert-butyl-4-hydroxybenzoic acid is produced, and the main components of the organic residue are 91-93% of 2,6-di-tert-butylphenol, 6-8% of 2,2', 4234 zxft-5334 ' -tetra-tert-butyl-5364 zxft-5364 ' -biphenol and about 1% of impurities; the content of each component of the organic residue in this example is specifically: 2,6-di-tert-butylphenol 92.4%, 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol 6.7%, and the balance of impurities 0.9%.
2,2',6,6' -tetra-tert-butyl-4,4 ' -crude product of biphenol: reducing the pressure to evaporate 2,6-di-tert-butylphenol, cooling the residue in the reaction kettle to 55 ℃, preserving the temperature, adding 190g of methanol as an extraction reagent, keeping the temperature at 55 ℃, stirring for 0.5h, filtering, screening out a first filter cake, continuously leaching for multiple times by using 80g of methanol, and drying the first filter cake in an oven at 60 ℃.
2,2',6,6' -tetra-tert-butyl-4,4 ' -crude product of biphenyldiol purification by recrystallization: adding 130g of isopropanol purification reagent into the 2,2',6,6' -tetra-tert-butyl-4,4 '-crude biphenyl diphenol, dissolving 2,2',6,6 '-tetra-tert-butyl-4,4' -crude biphenyl diphenol at 80 ℃, cooling at room temperature for crystallization, filtering, screening out a second filter cake, washing the second filter cake for multiple times by using 60g of isopropanol purification reagent, and finally drying at 70 ℃.
It is worth to be noted that any one of methanol, ethanol, n-propanol and isopropanol can be used as the extraction reagent, any one of isopropanol, cyclohexane, n-octane and tetrahydrofuran can be used as the purification reagent, which is mainly based on that phenolic compounds are easily soluble in alcohols and organic solvents, and both 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol are phenolic compounds, the recovery method respectively performs crude extraction and purification on 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol by the extraction reagent and the purification reagent, and can filter out partial impurities dissolved in the extraction reagent and the purification reagent by controlling the dissolution temperature and the crystallization temperature, thereby being beneficial to obtaining extracts with higher purity.
According to the measure of the embodiment, 624.8g of 2,6-di-tert-butylphenol is distilled out, wherein the effective content of 2,6-di-tert-butylphenol is 99.11 percent, and the recovery rate of 2,6-di-tert-butylphenol is 95.7 percent.
So as to obtain 43.3g of 2,2',6,6' -tetra-tert-butyl-4,4 '-crude diphenol, wherein the effective content of 2,2',6,6 '-tetra-tert-butyl-4,4' -crude diphenol is 98.71%.
The purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 40.1g and the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol effective content 99.81% are obtained.
Preliminary calculation, by taking the production of 200 tons of 3,5-di-tert-butyl-4-hydroxybenzoic acid per year as an example, about 110 tons of residues are generated, 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol which can be extracted by the recovery method are 100-103 tons, and about 1350 ten thousand yuan per ton can be brought from waste residue recovery according to the current market price of 2,6-di-tert-butyl 2.6 yuan, 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol of 150 ten thousand yuan per ton, so that about 1350 million yuan of diphenol is really realized, solid waste treatment and conversion is facilitated, and the recovery is beneficial to improving economic benefits and reducing production cost.
Comprehensively, the recovery rate of 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is 85.3 percent; and 2,6-di-tert-butylphenol with the purity content of not less than 99 percent and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol with the GC content of not less than 99.5 percent can be obtained by the recovery method, and the recovery method has higher recovery value.
Example 2
The difference between the embodiment 2 and the embodiment 1 is only that the embodiment 2 adopts ethanol as an extraction reagent, and compares the final 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenyldiol crude product with the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenyldiol yield and purity, and the specific results are as follows:
so as to obtain 41.6g of 2,2',6,6' -tetra-tert-butyl-4,4 '-crude diphenol, wherein the effective content of 2,2',6,6 '-tetra-tert-butyl-4,4' -crude diphenol is 97.95%.
The purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 37.6g and the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol effective content 99.68% are obtained.
Example 3
The difference between the embodiment 3 and the embodiment 1 is only that the embodiment 3 adopts n-propanol as an extraction reagent, and compares the final 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenyldiol crude product with the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenyldiol yield and purity, which are specifically as follows:
so as to obtain 2,2',6,6' -tetra-tert-butyl-4,4 '-crude biphenyl diphenol 42.8g, wherein the effective content of 2,2',6,6 '-tetra-tert-butyl-4,4' -crude biphenyl diphenol is 98.2%.
Purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 39.31g is obtained, and the effective content of purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol is 99.11%.
Example 4
The difference between the embodiment 4 and the embodiment 1 is only that the embodiment 4 adopts isopropanol as an extraction reagent, and compares the final 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol crude product with the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol yield and purity, which are concretely as follows:
40.5g of crude 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol is obtained, wherein the effective content of crude 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol is 98.35%.
The purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 37.76g and the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol effective content 99.36% are obtained.
Example 5
The difference between the embodiment 5 and the embodiment 1 is only that the embodiment 5 adopts cyclohexane as a purifying reagent, and the yield and the purity of the purified 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol are compared as follows:
the purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 39.54g and the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol effective content 99.63% are obtained.
Example 6
The difference between the embodiment 6 and the embodiment 1 is only that the embodiment 6 adopts tetrahydrofuran as a purifying reagent, and the yield and the purity of the purified 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol are compared as follows:
the purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 40.36g and the effective content of the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol 99.18% are obtained.
Example 7
The difference between the embodiment 7 and the embodiment 1 is only that the embodiment 7 adopts n-octane as a purifying reagent, and the yield and the purity of the purified 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol are compared as follows:
the purified 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenol 39.29g and the purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenol effective content 99.57% are obtained.
The effective contents of 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenyldiol recovered by the recovery method are not less than 99%, and the effective contents of 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenyldiol recovered by different extraction reagents and purification reagents are not greatly different and have higher extraction rates from the above examples 1-4, methanol can be preferably used as the extraction reagent, and the crude product content and the effective purity of the methanol are highest; in addition, the effective contents of 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol purified in the respective examples are similar to each other, but the highest purification content of recrystallization of the isopropanol purification reagent can be obtained from example 1 and examples 5 to 7, and isopropanol can be preferably used as the purification reagent.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
- The recovery method of 1.2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is characterized in that: 3,5-di-tert-butyl-4-hydroxybenzoic acid organic residue is used as a recovery raw material, 2,6-di-tert-butylphenol is extracted by reduced pressure distillation and temperature and pressure recovery, and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol is continuously extracted by recrystallization recovery.
- 2. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 1, wherein: the vacuum distillation method comprises the following specific steps: adding the recovered raw material organic residue into a reaction container, adding a decolorizing agent, controlling the distillation temperature to raise to 125-150 ℃, continuously stirring, controlling the distillation pressure to be between-0.095 and-0.080 MPa to distill 2,6-di-tert-butylphenol, and stopping distillation after 6-12 hours until no distillate exists.
- 3. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 2, wherein: the stirring speed of the continuous stirring is 220-350rpm/min, and the heating rate of the temperature rising from the room temperature to the distillation temperature is as follows: heating to 1-100 deg.C at 2-3 deg.C/min, and heating to 125-150 deg.C at 1-2 deg.C/min.
- 4. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 2, wherein: the decoloring agent adopts any one of aluminosilicate, bentonite or activated clay, and the decoloring agent accounts for the mass fraction of the recovered raw material organic residue as follows: 0.5 to 1.6 percent.
- 5. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 2, wherein: the extraction method of the 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol crude product comprises the following steps: cooling the reaction container which stops distilling to 50-60 ℃ by cold bath or natural cooling, preserving heat, then adding an extraction reagent into the reaction container, stirring for 0.5-1 hour, filtering, washing a first filter cake obtained by filtering by using the extraction reagent again, and drying the solution at 60 ℃ to obtain 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol crude product.
- 6. The process of claim 5 for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol, wherein: the extraction reagent can be any one of methanol, ethanol, n-propanol and isopropanol.
- 7. The process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 6, wherein: in the method for extracting the 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol crude product, the mass ratio of the extraction reagent to the residue in the reaction vessel is as follows: 1.5: 1-6: 1, and the mass ratio of the extraction reagent to the first filter cake is: 1: 0.5-1: 3.
- 8. The process of claim 5 for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol, wherein: the recrystallization purification method of the 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenyl diphenol crude product comprises the following steps: adding a purifying reagent into the 2,2',6,6' -tetra-tert-butyl-4,4 '-biphenyl diphenol crude product, heating to 75-85 ℃ for dissolving, crystallizing at room temperature, filtering to obtain a second filter cake, washing with the purifying reagent, and recrystallizing at 70-80 ℃ to obtain purified 2,2',6,6 '-tetra-tert-butyl-4,4' -biphenyl diphenol.
- 9. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 8, wherein: the purification reagent may be any one of isopropyl alcohol, cyclohexane, n-octane, and tetrahydrofuran.
- 10. A process for the recovery of 2,6-di-tert-butylphenol and 2,2',6,6' -tetra-tert-butyl-4,4 ' -biphenol according to claim 9, wherein: in the method for recrystallizing and purifying 2,2',6,6' -tetra-tert-butyl-4,4 '-crude diphenol, the mass ratio of the purifying reagent to 2,2',6,6 '-tetra-tert-butyl-4,4' -crude diphenol is as follows: 2: 1-8: 1, and the mass ratio of the purification reagent to the second filter cake is: 2: 1-4: 1.
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