CN116444349A - Preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol - Google Patents
Preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol Download PDFInfo
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- CN116444349A CN116444349A CN202310720461.5A CN202310720461A CN116444349A CN 116444349 A CN116444349 A CN 116444349A CN 202310720461 A CN202310720461 A CN 202310720461A CN 116444349 A CN116444349 A CN 116444349A
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- biphenol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 75
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 68
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 68
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 68
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims description 78
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 60
- 239000001301 oxygen Substances 0.000 claims description 60
- 229910052760 oxygen Inorganic materials 0.000 claims description 60
- 229910002651 NO3 Inorganic materials 0.000 claims description 56
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 56
- 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 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000012265 solid product Substances 0.000 claims description 30
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 19
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 aluminum ions Chemical class 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 41
- 239000002351 wastewater Substances 0.000 abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 66
- 239000012043 crude product Substances 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000001816 cooling Methods 0.000 description 27
- 239000012295 chemical reaction liquid Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000577 2,6-xylenyl group Chemical group [H]C1=C([H])C(=C(O*)C(=C1[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of preparation of biphenol, and provides a preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol. The invention oxidizes 2, 6-dialkyl phenol into 3,3', 5' -tetraalkyl-4, 4' -biphenol under the catalysis of aluminum-based hydrotalcite catalyst. The aluminum-based hydrotalcite catalyst has good catalytic activity, stability and specificity, can reduce the generation of byproducts, can achieve the yield of more than 91 percent of 3,3', 5' -tetraalkyl-4, 4' -biphenol, and has the purity of 99.9 percent after refining, and the aluminum-based hydrotalcite catalyst is solid, can realize the easy separation of the catalyst and products, and avoids the generation of phenolic wastewater or waste salt.
Description
Technical Field
The invention relates to the field of preparation of biphenol, in particular to a preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol.
Background
The 3,3', 5' -tetraalkyl-4, 4' -biphenol is an important chemical raw material with good heat resistance, and is used as a modified monomer in the processing field of various polymers such as polyurethane, polycarbonate, epoxy resin and the like to obtain engineering materials with excellent performance. Because of the good inhibiting effect on polymer aging, the modified polyethylene can be used as an anti-aging agent for rubber, latex and other materials, can be used as an important intermediate for synthesizing 4, 4-dihydroxybiphenyl, and can also be used for producing light synthetic resins such as formaldehyde resin and the like.
U.S. Pat. No. 5, 5099076 discloses a method for synthesizing 3,3', 5' -tetraalkyl-4, 4 '-biphenol, specifically, 2, 6-dialkylphenol is used as a raw material, aqueous solution of KOH or NaOH is used as a catalyst, oxygen is used as an oxidant, and 3,3',5 '-tetraalkyl-4, 4' -biphenol is prepared by oxidative coupling. In the method, the catalyst is difficult to separate from the product, the catalyst can only be removed by using a large amount of water washing or after being neutralized by using acid, and a large amount of phenol-containing wastewater or waste salt can be generated in the separation process.
Chinese patent CN 109999912A discloses a method for preparing 3,3', 5' -tetraalkyl-4, 4' -biphenol by catalytic synthesis with a bifunctional heterogeneous ruthenium-based catalyst, wherein 2, 6-dimethylphenol is used as a raw material, tert-butanol is used as a solvent, the bifunctional heterogeneous ruthenium-based catalyst is used to oxidize 2, 6-dimethylphenol as a raw material into 3,3', 5' -tetraalkyl-4, 4' -biphenol, and hydrogen is introduced for reduction, thereby preparing 3,3', 5' -tetraalkyl-4, 4' -biphenol. The method has complicated catalyst preparation steps, is difficult to produce in mass production, and is not suitable for industrial production. Meanwhile, the solubility of the intermediate product 3,3', 5' -tetraalkyl-4, 4' -biphenyl diquinone in a conventional solvent is very low, and continuous feeding is not easy to realize, so that continuous production is difficult to realize.
In view of the above, the current industrially applied preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol has the problems that liquid alkali is used as a catalyst, the separation of the catalyst from a product is difficult, and a large amount of water is required for washing in the catalyst removal process, so that a large amount of phenol-containing wastewater or waste salt can be generated.
Disclosure of Invention
In view of this, the present invention provides a process for preparing 3,3', 5' -tetraalkyl-4, 4' -biphenol. The invention utilizes the aluminum-based hydrotalcite catalyst, the catalyst is easy to separate from products, the generation of phenol-containing wastewater or waste salt is avoided, the flow is short, the byproducts are few, and continuous production can be realized.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol, which comprises the following steps:
under the action of an aluminum-based hydrotalcite catalyst, carrying out an oxidation reaction on 2, 6-dialkylphenol in an oxygen-containing atmosphere to obtain 3,3', 5' -tetraalkyl-4, 4' -biphenol; the metal ions in the aluminum-based hydrotalcite comprise aluminum ions and one or more of zinc ions, calcium ions, copper ions, barium ions and magnesium ions.
Preferably, the 2, 6-dialkylphenol is used in the form of a solution, and the solvent is one or more of methanol, ethanol, octanol and heavy aromatic hydrocarbon; the mass ratio of the solvent to the 2, 6-dialkylphenol is 2-20:1.
Preferably, the temperature of the oxidation reaction is 100-280 ℃; the pressure of the oxidation reaction is 0.1-2 MPa, and the liquid hourly space velocity of the oxidation reaction is 1-15 h -1 。
Preferably, the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen; the volume fraction of oxygen in the mixed gas is 5-30%; the gas airspeed of the oxygen-containing atmosphere is 260-400 h -1 。
Preferably, the 2, 6-dialkylphenol is 2, 6-di-tert-butylphenol or 2, 6-dimethylphenol.
Preferably, the oxidation reaction is carried out in a fixed bed reactor.
Preferably, the preparation method of the aluminum-based hydrotalcite comprises the following steps:
mixing inorganic alkali with water to obtain alkali liquor;
mixing the alkali liquor with a nitrate solution, and filtering to obtain a solid product;
dropwise adding an inorganic salt solution into the solid product until the pH value is stable, sequentially aging and washing the solid product after dropwise adding the inorganic salt solution, adding the solid product into a sodium carbonate solution for soaking, and sequentially washing, drying and calcining the soaked solid product to obtain aluminum-based hydrotalcite;
the nitrate in the nitrate solution comprises a first nitrate and a second nitrate; the first nitrate is aluminum nitrate, and the second nitrate is one or more of zinc nitrate, calcium nitrate, copper nitrate, barium nitrate and magnesium nitrate.
Preferably, the molar ratio of the first nitrate to the second nitrate is 2: 3-20.
Preferably, the aging temperature is 60-100 ℃, and the aging time is 15-32 hours.
Preferably, the calcination temperature is 350-850 ℃, and the calcination time is 3-8 hours.
The invention provides a preparation method of 3,3', 5' -tetraalkyl-4, 4 '-biphenol, which comprises the steps of carrying out oxidation reaction on 2, 6-dialkylphenol in an oxygen-containing atmosphere under the action of an aluminum-based hydrotalcite catalyst to obtain 3,3',5 '-tetraalkyl-4, 4' -biphenol. In the invention, the aluminum-based hydrotalcite catalyst has higher catalytic activity, stability and specificity, can reduce the generation of byproducts, ensures that the yield of the prepared 3,3', 5' -tetraalkyl-4, 4' -biphenol reaches more than 91 percent, and the purity after refining can reach 99.9 percent; in addition, the aluminum-based hydrotalcite catalyst is solid, so that the catalyst and a product can be easily separated, and the generation of phenol-containing wastewater or waste salt is avoided. In addition, the 3,3', 5' -tetraalkyl-4, 4' -biphenol is prepared by one-step reaction with the aluminum-based hydrotalcite catalyst, the preparation process is short, and the operation is simple.
Furthermore, the invention adopts the fixed bed reactor to carry out oxidation reaction, aluminum-based hydrotalcite is fixed in the fixed bed reactor, and the reactant flows through the catalyst bed layer, so that the separation of the catalyst and the product is not needed after the 3,3', 5' -tetraalkyl-4, 4' -biphenol is prepared, the discharge of waste water can be reduced, the continuous in-out of materials can be realized, and the operation efficiency is effectively improved.
Drawings
FIG. 1 is a chart showing the nuclear magnetic resonance hydrogen spectrum of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol according to example 1 of the present invention;
FIG. 2 is a liquid chart of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol according to example 1 of the present invention;
FIG. 3 is an infrared spectrum of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol according to example 1 of the present invention.
Detailed Description
The invention provides a preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol, which comprises the following steps:
under the action of an aluminum-based hydrotalcite catalyst, carrying out an oxidation reaction on 2, 6-dialkylphenol in an oxygen-containing atmosphere to obtain 3,3', 5' -tetraalkyl-4, 4' -biphenol; the metal ions in the aluminum-based hydrotalcite comprise aluminum ions and one or more of zinc ions, calcium ions, copper ions, barium ions and magnesium ions.
In the present invention, the desired materials are commercially available products well known to those skilled in the art unless specified otherwise.
In the invention, the metal ions in the aluminum-based hydrotalcite comprise aluminum ions and one or more of zinc ions, calcium ions, copper ions, barium ions and magnesium ions; further, the metal ions in the aluminum-based hydrotalcite preferably comprise aluminum ions, magnesium ions and one or two of copper ions and calcium ions; in a specific embodiment of the present invention, the metal ions in the aluminum-based hydrotalcite are preferably calcium ions, magnesium ions, and aluminum ions, or preferably copper ions, magnesium ions, and aluminum ions.
In the present invention, the preparation method of the aluminum-based hydrotalcite preferably comprises the following steps:
mixing inorganic alkali with water to obtain alkali liquor;
mixing the alkali liquor with a nitrate solution, and filtering to obtain a solid product;
dropwise adding an inorganic salt solution into the solid product until the pH value is stable, sequentially aging and washing the solid product after dropwise adding the inorganic salt solution, adding the solid product into a sodium carbonate solution for soaking, and sequentially washing, drying and calcining the soaked solid product to obtain aluminum-based hydrotalcite;
the nitrate in the nitrate solution comprises a first nitrate and a second nitrate; the first nitrate is aluminum nitrate, and the second nitrate is one or more of zinc nitrate, calcium nitrate, copper nitrate, barium nitrate and magnesium nitrate.
The invention mixes inorganic alkali and water to obtain alkali solution. In the present invention, the inorganic base is preferably NaOH; in the invention, the mass ratio of the water to the inorganic base is preferably 5.25-7.25: 1, further preferably 6.25:1.
after the alkali liquor is obtained, the invention mixes the alkali liquor with nitrate solution and filters the mixture to obtain a solid product. In the present invention, co-precipitation of nitrate occurs during the mixing process. In the present invention, the preparation method of the nitric acid solution preferably comprises: and dissolving nitrate and deionized water at 50-70 ℃, and regulating the pH value to 2-3 to obtain a nitrate solution.
In a specific embodiment of the present invention, the process of mixing the mixed solution with the nitrate solution is preferably: and slowly dripping the nitrate solution and the mixed solution into a container at the same time for mixing, keeping the pH value of the mixed solution to be 9-10, and filtering after the dripping is finished to obtain a precipitated solid product.
In the present invention, the nitrate of the nitrate solution includes a first nitrate and a second nitrate; the first nitrate is aluminum nitrate, and the second nitrate is one or more of zinc nitrate, calcium nitrate, copper nitrate, barium nitrate and magnesium nitrate; the molar ratio of the first nitrate to the second nitrate is preferably 2:3 to 20, more preferably 2: 4.25-14; when the second nitrate contains two nitrates, the two nitrates are preferably copper nitrate and magnesium nitrate or zinc nitrate and magnesium nitrate, and the molar ratio of the copper nitrate (or zinc nitrate) to the magnesium nitrate is preferably 0-10: 3 to 10, more preferably 0.25 to 5: 4-9, wherein the molar ratio of aluminum nitrate, copper nitrate (or zinc nitrate) to magnesium nitrate is preferably 2: 0-10: 3 to 10, more preferably 2: 0.25-5: 4-9.
And after obtaining a solid product, dropwise adding an inorganic salt solution into the solid product until the pH value is stable, sequentially aging and washing the solid product after dropwise adding the inorganic salt solution, adding the solid product into a sodium carbonate solution for soaking, and sequentially washing, drying and calcining the soaked solid product to obtain the aluminum-based hydrotalcite.
In the invention, the aging temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and the aging time is preferably 15-32 h, more preferably 20-25 h.
In the present invention, the washing preferably washes the solid product to ph=7 to 8.
In the invention, the inorganic salt solution is preferably sodium carbonate solution, and the concentration of the inorganic salt solution is preferably 0.2-1M; in the invention, after the solid product is obtained, an inorganic salt solution is dropwise added to the solid product, preferably until the pH is stabilized to 9.2-9.8.
In the invention, the concentration of the sodium carbonate solution is preferably 0.1-1M; the soaking time is preferably 12-20 hours, more preferably 15-18 hours.
In the invention, the washing is preferably to wash the soaked solid product to pH=7-8; the drying temperature is preferably 60-100 ℃; the calcination temperature is preferably 350-850 ℃, more preferably 450-750 ℃, and the calcination time is preferably 3-8 hours, more preferably 5-6 hours.
In the invention, the aluminum-based hydrotalcite catalyst has higher catalytic activity, stability and specificity, can reduce the generation of byproducts, ensures higher yield and purity of the prepared 3,3', 5' -tetraalkyl-4, 4' -biphenol, and can be reused at higher catalytic level; in addition, the aluminum-based hydrotalcite catalyst is solid, so that the catalyst and a product can be easily separated, and the generation of phenol-containing wastewater or waste salt is avoided. In addition, the 3,3', 5' -tetraalkyl-4, 4' -biphenol is prepared by one-step reaction by utilizing the aluminum-based hydrotalcite catalyst, so that the preparation process is short and the preparation method is simple to operate.
In the present invention, the 2, 6-dialkylphenol is preferably used in the form of a solution, and the solvent is preferably one or more of methanol, ethanol, octanol and heavy aromatic hydrocarbon; the mass ratio of the solvent to the 2, 6-dialkylphenol is preferably 2-20: 1, more preferably 5 to 15:1, more preferably 9:1. in the invention, the solvent can effectively dissolve the by-product 3,3', 5' -tetraalkyl-4, 4 '-biphenyl diquinone of excessive oxidation, and avoid the blockage of the reactor by solid 3,3',5 '-tetraalkyl-4, 4' -biphenyl diquinone.
In the invention, the temperature of the oxidation reaction is preferably 100-280 ℃, more preferably 140-240 ℃, and even more preferably 200 ℃; the pressure of the oxidation reaction is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa.
In the present invention, the oxygen-containing atmosphere is preferably a mixed gas of nitrogen and oxygen; the volume fraction of oxygen in the mixed gas is preferably 5-30%, and more preferably 20%; the gas space velocity of the oxygen-containing atmosphere is preferably 260-400 h -1 Further preferably 270 h -1 。
In the invention, the liquid hourly space velocity of the oxidation reaction is preferably 1-15 h -1 More preferably 3 to 4 hours -1 。
In the present invention, the 2, 6-dialkylphenol is preferably 2, 6-di-t-butylphenol or 2, 6-dimethylphenol, and more preferably 2, 6-dimethylphenol. In the present invention, when the 2, 6-dialkylphenol is 2, 6-di-t-butylphenol, the 3,3', 5' -tetraalkyl-4, 4 '-biphenol produced is 3,3',5 '-tetra-t-butyl-4, 4' -biphenol; when the 2, 6-dialkylphenol is 2, 6-dimethylphenol, the 3,3', 5' -tetraalkyl-4, 4 '-biphenol produced is 3,3',5 '-tetramethyl-4, 4' -biphenol.
In the present invention, the oxidation reaction is preferably carried out in a fixed bed reactor, specifically, aluminum-based hydrotalcite is packed in a fixed bed reactor, and then the oxidation reaction is carried out by introducing a solution of 2, 6-dialkylphenol and an oxygen-containing atmosphere. According to the invention, the 3,3', 5' -tetraalkyl-4, 4 '-biphenol is prepared by adopting the fixed bed reactor, the aluminum-based hydrotalcite can be fixed in the fixed bed reactor, and the reactant flows through the catalyst bed layer, so that the separation of the catalyst and the product is not needed after the 3,3',5 '-tetraalkyl-4, 4' -biphenol is prepared, the discharge of waste water can be reduced, the continuous in-out of materials can be realized, and the operation efficiency is effectively improved.
In the present invention, when the oxidation reaction is performed in the fixed bed reactor for oxidation reaction, it is also preferable to include a post-treatment step after the completion of the oxidation reaction, the post-treatment step including the steps of:
collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetraalkyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and carrying out suction filtration and drying to obtain a crude product of 3,3',5 '-tetraalkyl-4, 4' -biphenol; the temperature of the drying is preferably 150 ℃.
The following will clearly and fully describe the technical solutions in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
Preparation of an aluminum-based hydrotalcite catalyst:
will be 1.39gCa (NO 3 ) 2 ·4H 2 O、51.28gMg(NO 3 ) 2 ·6H 2 O and 30.01g Al (NO) 3 ) 3 ·9H 2 O is added into 250ml deionized water after being mixed, and dissolved in water bath at 60 ℃ until the solution is clear and transparent, thus obtaining the nitrateAn acid salt solution;
dissolving 40g of NaOH in 250ml of deionized water to obtain alkali liquor;
dropwise adding the obtained nitrate solution and alkali liquor into a three-neck flask, stirring, maintaining the pH value to be 9-10 until the dropwise adding of the nitrate solution is completed, and then dropwise adding 0.2M Na into the three-neck flask 2 CO 3 The solution was aged for 30 hours by transferring the three-necked flask to an oil bath at 60℃until the pH was stabilized to 9.3, and after centrifugal washing, 700ml of 0.1M Na was added 2 CO 3 The solution is soaked for 12 hours, washed, then dried for 12 hours at 60 ℃ in a drying oven, and then kept for 5 hours in a muffle furnace at a speed of 3 ℃/min to 550 ℃ to obtain the aluminum-based hydrotalcite.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
loading 50ml of aluminum-based hydrotalcite into a fixed bed reactor with an inner diameter of 25mm, introducing a heavy aromatic hydrocarbon solution of 2, 6-di-tert-butylphenol with a mass fraction of 10% into the reactor under an oxygen-containing atmosphere, wherein the reaction condition of the reactor is set to be that the liquid hourly space velocity is 4 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring for 12h at 50 ℃, then sequentially recrystallizing and filtering the 50 ℃ solution, cooling the filtrate at 4 ℃ to precipitate solid, and filtering to obtain a solid refined product.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product prepared in example 1 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 96.5% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.7%.
No phenol-containing wastewater was generated during the preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol in example 1, and the conversion of 2, 6-di-tert-butylphenol was 96.58%, and the mass yield based on 2, 6-di-tert-butylphenol was 93.2%. The purity of the refined crude product can reach 99.9 percent.
And (3) performing nuclear magnetic resonance hydrogen spectrum analysis, liquid analysis and infrared analysis on the 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol prepared in the example 1, wherein the obtained results are respectively shown in figures 1-3. As can be seen from FIGS. 1 to 3, the 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol prepared in example 1 of the present invention has higher purity.
Example 2
Preparation of an aluminum-based hydrotalcite catalyst:
30.77g of Mg (NO 3 ) 2 ·6H 2 O and 30.01g Al (NO) 3 ) 3 ·9H 2 After mixing O, adding the mixture into 250ml of deionized water, and dissolving the mixture under the water bath condition of 60 ℃ until the solution is clear and transparent to obtain nitrate solution;
dissolving 40g of NaOH in 250ml of deionized water to obtain alkali liquor;
dropwise adding the obtained nitrate solution and alkali liquor into a three-neck flask, stirring, maintaining the pH value to be 9-10 until the dropwise adding of the nitrate solution is completed, and then dropwise adding 0.2M Na into the three-neck flask 2 CO 3 The solution was aged for 30 hours by transferring the three-necked flask to an oil bath at 60℃until the pH was stabilized to 9.2, and after centrifugal washing, 700ml of 0.1M Na was added 2 CO 3 The solution is soaked for 12 hours, washed, then dried for 12 hours at 60 ℃ in a drying oven, and then kept for 5 hours in a muffle furnace at a speed of 3 ℃/min to 550 ℃ to obtain the aluminum-based hydrotalcite.
The process for preparing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol is the same as in example 1.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product prepared in example 2 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 95.2% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.7%.
In the reaction for producing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol in example 2, the conversion of 2, 6-di-tert-butylphenol was 95.59% and the mass yield based on 2, 6-di-tert-butylphenol was 91%. The purity of the refined crude product can reach 99.9 percent.
Example 3
Preparation of an aluminum-based hydrotalcite catalyst:
9.6g of Cu (NO) 3 ) 2 ·3H 2 O、51.28gMg(NO 3 ) 2 ·6H 2 O and 30.01gAl (NO) 3 ) 3 ·9H 2 Adding the mixed solution into 250ml of deionized water, and dissolving the mixed solution at the water bath condition of 60 ℃ until the solution is clear and transparent to obtain nitrate solution;
dissolving 40g of NaOH in 250ml of deionized water to obtain alkali liquor;
dropwise adding the obtained nitrate solution and alkali liquor into a three-neck flask, stirring, maintaining the pH value to be 9-10 until the dropwise adding of the nitrate solution is completed, and then dropwise adding 0.2M Na into the three-neck flask 2 CO 3 The solution was aged for 15 hours by transferring the three-necked flask into an oil bath at 40℃until the pH was stabilized to 9.5, and after centrifugal washing, 700ml of 0.1M Na was added 2 CO 3 The solution is soaked for 12 hours, washed, then dried for 12 hours at 60 ℃ in a drying oven, and then kept for 5 hours in a muffle furnace at a speed of 3 ℃/min to 550 ℃ to obtain the aluminum-based hydrotalcite.
The process for preparing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol is the same as in example 1.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 3 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 97.5% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.6%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 3 was 98.26%, and the mass yield based on 2, 6-di-t-butylphenol was 95.8%. The purity of the refined crude product can reach 99.9 percent.
Example 4
Preparation of an aluminum-based hydrotalcite catalyst:
9.6g of Cu (NO) 3 ) 2 ·3H 2 O、51.28gMg(NO 3 ) 2 ·6H 2 O and 30.01gAl (NO) 3 ) 3 ·9H 2 Adding the mixed solution into 250ml of deionized water, and dissolving the mixed solution at the water bath condition of 60 ℃ until the solution is clear and transparent to obtain nitrate solution;
dissolving 40g of NaOH in 250ml of deionized water to obtain alkali liquor;
Dropwise adding the obtained nitrate solution and alkali liquor into a three-neck flask, stirring, maintaining the pH value to be 9-10 until the dropwise adding of the nitrate solution is completed, and then dropwise adding 0.2M Na into the three-neck flask 2 CO 3 The solution was aged for 30 hours by transferring the three-necked flask to an oil bath at 60℃until the pH was stabilized to 9.4, and after centrifugal washing, 700ml of 0.1M Na was added 2 CO 3 The solution is soaked for 12 hours, washed, then dried for 12 hours at 60 ℃ in a drying oven, and then kept for 5 hours in a muffle furnace at a speed of 3 ℃/min to 550 ℃ to obtain the aluminum-based hydrotalcite.
The process for preparing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol is the same as in example 1.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product prepared in example 3 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 99.0% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.1%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 4 was 99.09%, and the mass yield based on 2, 6-di-t-butylphenol was 98.1%. The purity of the refined crude product can reach 99.9 percent.
Example 5
Preparation of an aluminum-based hydrotalcite catalyst:
9.6g of Cu (NO) 3 ) 2 ·3H 2 O 、51.28gMg(NO 3 ) 2 ·6H 2 O and 30.01gAl (NO) 3 ) 3 ·9H 2 Adding the mixed solution into 250ml of deionized water, and dissolving the mixed solution at the water bath condition of 60 ℃ until the solution is clear and transparent to obtain nitrate solution;
dissolving 40g of NaOH in 250ml of deionized water to obtain alkali liquor;
the obtained product is then processedDropwise adding the obtained nitrate solution and alkali liquor into a three-neck flask, stirring, maintaining the pH value to be 9-10 until the dropwise adding of the nitrate solution is completed, and then dropwise adding 0.2M Na into the three-neck flask 2 CO 3 The solution was aged for 30 hours by transferring the three-necked flask to an oil bath at 60℃until the pH was stabilized to 9.2, and after centrifugal washing, 700ml of 0.1M Na was added 2 CO 3 The solution is soaked for 12 hours, washed, then dried for 12 hours at 60 ℃ in a drying oven, and then kept for 8 hours in a muffle furnace at a speed of 3 ℃/min to 400 ℃ to obtain the aluminum-based hydrotalcite.
The process for preparing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol is the same as in example 1.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 3 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 98.0% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.6%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 5 was 98.16% and the mass yield based on 2, 6-di-t-butylphenol was 96.2%. The purity of the refined crude product can reach 99.9 percent.
Example 6
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, a heavy aromatic hydrocarbon solution of 5.56% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, and the reaction conditions of the reactor are set as follows: liquid hourly space velocity of 4 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring for 12h at 50 ℃, then sequentially recrystallizing and filtering the 50 ℃ solution, cooling the filtrate at 4 ℃ to precipitate solid, and filtering to obtain a solid refined product.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product prepared in example 6 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 96.6% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.8%.
In the reaction for producing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol in example 6, the conversion of 2, 6-di-tert-butylphenol was 97.72%, and the mass yield based on 2, 6-di-tert-butylphenol was 94.4%. The purity of the refined crude product can reach 99.9 percent.
Example 7
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, and a heavy aromatic hydrocarbon solution of 10% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, wherein the reaction conditions of the reactor are as follows: liquid hourly space velocity of 4 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 7 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 97.5% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.8%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 7 was 97.64%, and the mass yield based on 2, 6-di-t-butylphenol was 95.2%. The purity of the refined crude product can reach 99.9 percent.
Example 8
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, and a heavy aromatic hydrocarbon solution of 10% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, wherein the reaction conditions of the reactor are as follows: liquid hourly space velocity of 4 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 140 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of that of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 8 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 98.7% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.6%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 8 was 95.34%, and the mass yield based on 2, 6-di-t-butylphenol was 94.1%. The purity of the refined crude product can reach 99.9 percent.
Example 9
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, and a heavy aromatic hydrocarbon solution of 10% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, wherein the reaction conditions of the reactor are as follows: liquid hourly space velocity of 3 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
And collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 9 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 94.1% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.7%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 9 was 96.71%, and the mass yield based on 2, 6-di-t-butylphenol was 91.0%. The purity of the refined crude product can reach 99.9 percent.
Example 10
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
loading 50ml aluminum-based hydrotalcite into a fixed bed reactor with an inner diameter of 25mm, and placing the aluminum-based hydrotalcite with a mass fraction of 10 under an oxygen-containing atmosphere % of a heavy aromatic solution of 2, 6-di-tert-butylphenol is fed into a reactor, and the reaction conditions of the reactor are set as follows: liquid hourly space velocity of 4 h -1 Gas space velocity of 250 h -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 10 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 98.2% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.2%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 10 was 95.0%, and the mass yield based on 2, 6-di-t-butylphenol was 93.3%. The purity of the refined crude product can reach 99.9 percent.
Example 11
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, and a heavy aromatic hydrocarbon solution of 10% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, wherein the reaction conditions of the reactor are as follows: liquid hourly space velocity of 3 h -1 270 to h gas space velocity -1 The pressure is 0.2MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 5 percent of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 11 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 98.2% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.1%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 11 was 93.79% and the mass yield based on 2, 6-di-t-butylphenol was 92.1%. The purity of the refined crude product can reach 99.9 percent.
Example 12
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
Preparation of 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol:
50ml of aluminum-based hydrotalcite is taken and put into a fixed bed reactor with an inner diameter of 25mm, and a heavy aromatic hydrocarbon solution of 10% of 2, 6-di-tert-butylphenol is introduced into the reactor under the oxygen-containing atmosphere, wherein the reaction conditions of the reactor are as follows: liquid hourly space velocity of 4 h -1 270 to h gas space velocity -1 The pressure is 0.1MPa, the temperature is 200 ℃, and the oxygen-containing atmosphere is a mixed gas of nitrogen and oxygen with the volume of 20% of oxygen;
and collecting the reaction liquid flowing out of the fixed bed reactor at 75-100 ℃, then cooling to 15-25 ℃ to separate out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the reaction liquid in a crystal form, and then carrying out suction filtration and drying to constant weight at 150 ℃ to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The crude 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol product obtained in example 12 had a 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 98.2% and the overoxidation product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol content of 0.3%.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in example 12 was 95.72% and the mass yield based on 2, 6-di-t-butylphenol was 94.0%. The purity of the refined crude product can reach 99.9 percent.
Comparative example 1
10g of 2, 6-di-tert-butylphenol and 90g of octanol are added into a batch reaction vessel, after being fully dissolved, 2% NaOH catalyst relative to the mass of the 2, 6-di-tert-butylphenol is added, 1.5L (standard condition) of nitrogen and oxygen mixed gas with the oxygen concentration of 20% are introduced into the reaction vessel at the speed of 0.03L/min at the temperature of 200 ℃, and after the reaction is stopped for 50 min.
And (3) the temperature of the reaction kettle is reduced to 75-100 ℃, the reaction kettle is opened, the liquid after the reaction is taken out, poured into a separating funnel, mixed and washed with 200ml of deionized water at 80 ℃, uniformly shaken, split-phase separated, the water phase is removed, washing is carried out for 4 times, the PH value is tested to be neutral, and about 800ml of phenolic wastewater is produced.
And cooling the oil phase to 15-25 ℃, separating out 3, 5-tetra-tert-butyl-4, 4 '-biphenol in the oil phase in a crystal form, and then carrying out suction filtration and drying at 150 ℃ until the weight is constant to obtain 8.3g of crude product of 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol. The crude product had a 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol content of 95.1% and a 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol content of 4%.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in comparative example 1 was 83%, and the mass yield based on 2, 6-di-t-butylphenol was 78.93%. The purity of the refined crude product can reach 99.9 percent.
Comparative example 2
10g of 2, 6-di-tert-butylphenol and 90g of octanol are added into a batch reaction vessel, after being fully dissolved, 5% NaOH catalyst relative to the mass of the 2, 6-di-tert-butylphenol is added, 1.5L (standard condition) of nitrogen and oxygen mixed gas with the oxygen concentration of 20% are introduced into the reaction vessel at the temperature of 200 ℃ at the rate of 0.1L/min, and after the reaction is stopped for 15 min.
And (3) the temperature of the reaction kettle is reduced to 75-100 ℃, the reaction kettle is opened, the liquid after the reaction is taken out, poured into a separating funnel, mixed and washed with 200ml of deionized water at 80 ℃, shaken uniformly, split phases are carried out, the water phase is removed, washing is carried out for 4 times, the PH value is tested to be neutral, and about 800ml of phenolic wastewater is produced.
And cooling the oil phase to 15-25 ℃, separating out 3, 5-tetra-tert-butyl-4, 4 '-biphenol in the oil phase in a crystal form, and then carrying out suction filtration and drying at 150 ℃ until the weight is constant to obtain 8g of crude product of 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol. The content of 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the crude product was 94.2%, and the content of 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol was 5%.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
In the reaction for producing 3,3', 5' -tetra-tert-butyl-4, 4' -biphenol in comparative example 2, the conversion of 2, 6-di-tert-butylphenol was 81%, and the mass yield based on 2, 6-di-tert-butylphenol was 76.30%. The purity of the refined crude product can reach 99.9 percent.
Comparative example 3
10g of 2, 6-di-tert-butylphenol and 90g of octanol are added into a batch reaction vessel, after being fully dissolved, 5% NaOH catalyst relative to the mass of the 2, 6-di-tert-butylphenol is added, 3L (standard condition) of nitrogen and oxygen mixed gas with the oxygen concentration of 20% are introduced into the reaction vessel at the speed of 0.06L/min at the temperature of 200 ℃, and after the reaction is stopped for 50 min.
Collecting at 75-100 ℃, washing with 800ml of 80 ℃ water until the water is neutral to remove alkali, cooling to 15-25 ℃ to separate 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenyl diquinone in the water in a crystal form, and then carrying out suction filtration and drying at 150 ℃ until the weight is constant to obtain a crude product of the 3,3',5 '-tetra-tert-butyl-4, 4' -biphenyl diquinone.
The obtained crude product 3,3', 5' -tetra-tert-butyl-4, 4' -biphenyl diquinone and 90g of octanol are added into a batch reaction vessel, a palladium-carbon catalyst with the palladium content of 0.8 percent which is equivalent to 0.3g is added, 4MPa hydrogen is introduced, the pressure is kept at 4MPa, and the reaction is stopped after 3 hours of reaction.
Collecting at 75-100 ℃, then cooling to 15-25 ℃, separating out 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol in the mixture in a crystal form, carrying out suction filtration, and drying to constant weight at 100 ℃ to obtain 8.9g of crude product of 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol. The crude product had a 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol content of 98% and a 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol content of 1%.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The conversion of 2, 6-di-t-butylphenol in the reaction for producing 3,3', 5' -tetra-t-butyl-4, 4' -biphenol in comparative example 3 was 89%, and the mass yield based on 2, 6-di-t-butylphenol was 87.22%. The purity of the refined crude product can reach 99.9 percent.
Comparative example 4
Adding 0.06g of 2, 6-dimethylphenol into 15ml of Schlenk tube, adding 0.01g of self-made dual-function heterogeneous ruthenium-based catalyst, adding 3ml of tertiary butanol, uniformly dispersing by ultrasonic, vacuumizing, filling high-purity oxygen, reacting at 70 ℃ under an oxygen atmosphere for 24 hours, cooling to room temperature, vacuumizing, changing gas into high-purity hydrogen, continuing to react at 60 ℃ for 6 hours, adding chloroform solvent after the reaction is finished, uniformly dispersing by ultrasonic, centrifuging, and rotationally steaming pale yellow supernatant to obtain a 3,3', 5' -tetramethyl-4, 4' -biphenol crude product, wherein the product yield is 81.43%.
Example 13
The method for preparing aluminum-based hydrotalcite was the same as in example 1.
The process for preparing 3,3', 5' -tetramethyl-4, 4' -biphenol is the same as in example 1, except that 2, 6-di-tert-butylphenol is replaced with 2, 6-dimethylphenol.
The crude 3,3', 5' -tetramethyl-4, 4' -biphenol product prepared in example 13 had a 3,3', 5' -tetramethyl-4, 4' -biphenol content of 99.5% and the overoxidation product 3,3', 5' -tetramethyl-4, 4' -biphenol content of 0.1%.
The conversion of 2, 6-dimethylphenol in the reaction for preparing 3,3', 5' -tetramethyl-4, 4' -biphenol in example 13 was 98.59% and the mass yield based on 2, 6-dimethylphenol was 98.1%. The purity of the refined crude product can reach 99.9 percent.
Comparative example 5
10g of 2, 6-dimethylphenol and 90g of octanol are added into a batch reaction vessel, after being fully dissolved, 2% NaOH catalyst relative to the mass of the 2, 6-dimethylphenol is added, 1.5L (standard condition) of nitrogen with 20% oxygen concentration and oxygen mixed gas are introduced into the reaction vessel at the temperature of 200 ℃ at the rate of 0.03L/min, and after the reaction is stopped for 50 min.
Collecting at 75-100 ℃, washing with 500ml of water at 80 ℃ until the water is neutral to remove alkali, cooling to 15-25 ℃ to separate 3,3', 5' -tetramethyl-4, 4 '-biphenol out in the water in a crystal form, and then carrying out suction filtration and drying at 100 ℃ until the weight is constant to obtain 8.3g of crude product of 3,3',5 '-tetramethyl-4, 4' -biphenol.
The obtained crude product and methanol are mixed according to the mass ratio of 1:10, stirring at 50deg.C for 12 hr, filtering the solution at 50deg.C, and cooling at 4deg.C.
The 3,3', 5' -tetramethyl-4, 4' -biphenol crude product prepared in comparative example 5 has a 3,3', 5' -tetramethyl-4, 4' -biphenol content of 95.1% and a 3,3', 5' -tetramethyl-4, 4' -biphenol content of 4%.
The conversion of 2, 6-dimethylphenol in the reaction for preparing 3,3', 5' -tetramethyl-4, 4' -biphenol in comparative example 5 was 83%, and the mass yield based on 2, 6-dimethylphenol was 78.93%. The purity of the refined crude product can reach 99.9 percent.
Service life test
Preparation of an aluminum-based hydrotalcite catalyst:
40g of NaOH and Na 2 CO 3 Mixing with 250ml deionized water to obtain a mixed solution;
9.6g of Cu (NO) 3 ) 2 ·3H 2 O、51.28gMg(NO 3 ) 2 ·6H 2 O and 30.01gAl (NO) 3 ) 3 ·9H 2 Adding the mixed solution into 250ml of deionized water, and dissolving the mixed solution at the water bath condition of 60 ℃ until the solution is clear and transparent to obtain nitrate solution;
mixing the obtained mixed solution with a nitrate solution, and filtering to obtain a solid product;
the solid product was aged in an oil bath at 60℃for 30 hours and washed with water, and 700ml of 0.1M Na was added to the washed solid product 2 CO 3 Soaking in the solution for 12 hours, washing, drying the washed solid product in a drying oven at 60 ℃ for 12 hours, and then placing in a muffle furnace to rise to 550 ℃ at 3 ℃/min for 5 hours to obtain the aluminum-based hydrotalcite A1.
The above steps were repeated under the condition that only the calcination temperature and time were changed and the other conditions were kept unchanged, and the calcination temperature and time were adjusted to be raised to 400 ℃ at 3 ℃/min and kept for 8 hours, to obtain aluminum-based hydrotalcite A2.
The results of the continuous preparation of 3,3', 5' -tetra-t-butyl-4, 4' -biphenol using aluminum-based hydrotalcite A1 and A2 as catalysts, and the preparation of 3,3', 5' -tetra-t-butyl-4, 4' -biphenol as in example 1, the conversion of 2, 6-di-t-butylphenol and the yield of 3,3', 5' -tetra-t-butyl-4, 4' -biphenol as the reaction time increases, are shown in Table 1.
TABLE 1 service life of aluminium-based hydrotalcite catalysts
As shown in Table 1, both the aluminum-based hydrotalcite catalysts A1 and A2 have longer service lives, especially the yield of 3,3', 5' -tetra-tert-butyl-4, 4 '-biphenol can still be kept 91.95% after the reaction lasts for 2100 hours, and the yield of 3,3',5 '-tetra-tert-butyl-4, 4' -biphenol is reduced to below 90% after the reaction lasts for 1600 hours for the aluminum-based hydrotalcite catalyst A2, which is 86.54%, which indicates that the stability of the aluminum-based hydrotalcite catalyst A1 provided by the invention is better.
The embodiment shows that the aluminum-based hydrotalcite catalyst provided by the invention has good catalytic activity, stability and specificity, can reduce the generation of byproducts, ensures that the yield of the prepared 3,3', 5' -tetraalkyl-4, 4' -biphenol reaches more than 91%, and the purity after refining can reach 99.9%; in addition, the aluminum-based hydrotalcite catalyst is solid, so that the catalyst and a product can be easily separated, and the generation of phenol-containing wastewater or waste salt is avoided.
In addition, the preparation method of 3,3', 5' -tetraalkyl-4, 4' -biphenol provided by the invention can realize continuous production in a fixed bed reactor, simultaneously fix the aluminum-based hydrotalcite catalyst in the fixed bed reactor, and the separation of the catalyst and the product is not needed, so that the discharge of waste water can be reduced, the continuous in-out of materials can be realized, the operation efficiency is effectively improved, and the method is suitable for industrial scale-up production.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing 3,3', 5' -tetraalkyl-4, 4' -biphenol, comprising the steps of:
Under the action of an aluminum-based hydrotalcite catalyst, carrying out an oxidation reaction on 2, 6-dialkylphenol in an oxygen-containing atmosphere to obtain 3,3', 5' -tetraalkyl-4, 4' -biphenol; the metal ions in the aluminum-based hydrotalcite comprise aluminum ions and one or more of zinc ions, calcium ions, copper ions, barium ions and magnesium ions.
2. The preparation method according to claim 1, wherein the 2, 6-dialkylphenol is used in the form of a solution, and the solvent is one or more of methanol, ethanol, octanol and heavy aromatic hydrocarbon; the mass ratio of the solvent to the 2, 6-dialkylphenol is 2-20: 1.
3. the preparation method according to claim 1, wherein the temperature of the oxidation reaction is 100-280 ℃; the pressure of the oxidation reaction is 0.1-2 MPa; the liquid hourly space velocity of the oxidation reaction is 1-15 h -1 。
4. The method according to claim 1, wherein the oxygen-containing atmosphere is a mixture of nitrogen and oxygen; the volume fraction of oxygen in the mixed gas is 5-30%; the gas airspeed of the oxygen-containing atmosphere is 260-400 h -1 。
5. The method according to claim 1, wherein the 2, 6-dialkylphenol is 2, 6-di-t-butylphenol or 2, 6-dimethylphenol.
6. A production method according to claim 1 or 3, wherein the oxidation reaction is carried out in a fixed bed reactor.
7. The preparation method according to claim 1, wherein the preparation method of the aluminum-based hydrotalcite comprises the following steps:
mixing inorganic alkali with water to obtain alkali liquor;
mixing the alkali liquor with a nitrate solution, and filtering to obtain a solid product;
dropwise adding an inorganic salt solution into the solid product until the pH value is stable, sequentially aging and washing the solid product after dropwise adding the inorganic salt solution, adding the solid product into a sodium carbonate solution for soaking, and sequentially washing, drying and calcining the soaked solid product to obtain aluminum-based hydrotalcite;
the nitrate in the nitrate solution comprises a first nitrate and a second nitrate; the first nitrate is aluminum nitrate, and the second nitrate is one or more of zinc nitrate, calcium nitrate, copper nitrate, barium nitrate and magnesium nitrate.
8. The method of claim 7, wherein the first nitrate and the second nitrate are present in a molar ratio of 2: 3-20.
9. The method according to claim 7, wherein the aging temperature is 60-100 ℃, and the aging time is 15-32 hours.
10. The method according to claim 7, wherein the calcination temperature is 350-850 ℃, and the calcination time is 3-8 hours.
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