CN114163311A - High-efficiency and clean production method of phenolic compound - Google Patents
High-efficiency and clean production method of phenolic compound Download PDFInfo
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- CN114163311A CN114163311A CN202010984758.9A CN202010984758A CN114163311A CN 114163311 A CN114163311 A CN 114163311A CN 202010984758 A CN202010984758 A CN 202010984758A CN 114163311 A CN114163311 A CN 114163311A
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- mother liquor
- hydrolyzed
- polar protic
- acidic
- acid
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- 150000002989 phenols Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000012452 mother liquor Substances 0.000 claims abstract description 45
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 36
- 230000002378 acidificating effect Effects 0.000 claims abstract description 32
- -1 arylamine compound Chemical class 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 claims abstract description 20
- 239000003586 protic polar solvent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 4
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 4
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 2
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- BOFZIDABVXHSBZ-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O.CC1=C(O)C=CC=C1O BOFZIDABVXHSBZ-UHFFFAOYSA-N 0.000 claims 1
- QUBXCQGQEOYAFM-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O.CC1=CC=C(O)C=C1O QUBXCQGQEOYAFM-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- FNYDIAAMUCQQDE-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000413 hydrolysate Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000005903 acid hydrolysis reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 5
- 229940018564 m-phenylenediamine Drugs 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 239000002351 wastewater 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An efficient and clean production method of a phenolic compound comprises the following steps: adding corresponding arylamine compound into a certain amount of acidic catalyst aqueous solution, heating for hydrolysis, cooling to room temperature, adding an extraction solvent to extract a generated phenolic compound, separating the extraction solvent from an extraction liquid to prepare a finished phenolic compound product, evaporating residual extraction solvent and partial water from the extracted acidic mother liquor, mixing a certain amount of polar protic solvent to precipitate inorganic ammonium salt in the mother liquor, dissolving salt formed by the arylamine compound which is not hydrolyzed and is incompletely hydrolyzed and the acidic catalyst and excessive acidic catalyst in the polar protic solvent, separating the inorganic ammonium salt precipitate, further distilling to remove the polar protic solvent, sleeving the salt of the arylamine compound which is not hydrolyzed and is incompletely hydrolyzed and the excessive acidic catalyst in the synthesis of the next batch, and continuing the hydrolysis reaction.
Description
The technical field is as follows: the invention belongs to the technical field of chemical raw material synthesis, and particularly designs an efficient and clean production method of a phenolic compound.
Secondly, background art: the phenolic compounds are important chemical raw materials, have wide application fields, are closely related to the production and the life of human beings, and can be applied to medicines, pesticides, veterinary drugs, materials, auxiliaries, dyes, pigments, coatings, adhesives, plastics, rubber, electronic chemicals and the like. There are a variety of methods for preparing such compounds, including: sulfonate alkali fusion method, amino compound acid hydrolysis method, amino diazotization hydrolysis method, hydrogen peroxide hydroxylation method, isopropyl compound oxidation hydrolysis method, halogenated hydrocarbon alkali hydrolysis method, hydroxylamine rephotography method and the like.
Due to localization or environmental protection, safety, technology, resources, and the like, with the development of science and technology and materials, the acidic hydrolysis of aromatic amines to convert the amino group of aromatic amines into hydroxyl group to prepare corresponding phenolic compounds gradually becomes some of the main industrial preparation methods of phenolic compounds, such as: p-methylphenol, m-methylphenol, 2-naphthol, 1-naphthol, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3, 5-dimethylphenol, p-phenylphenol, hydroquinone, resorcinol, 2, 4-dihydroxytoluene, 2-methylresorcinol, phloroglucinol, 1, 5-dihydroxynaphthalene, 3, 5-dihydroxybenzoic acid, 2, 5-dimethylphenol, 3, 4-dimethylphenol, 8-hydroxyquinoline, 4-hydroxydiphenylamine and the like.
The main reaction processes are exemplified as follows:
1. p-methylaniline is hydrolyzed in acid to prepare p-cresol:
2. m-phenylenediamine is hydrolyzed in acid to prepare resorcinol:
3. preparing m-hydroxybenzoic acid from m-aminobenzoic acid:
4.2, 4-diaminotoluene acidic hydrolysis to prepare 2, 4-dihydroxytoluene:
5. 2, 6-diaminotoluene acidic hydrolysis to prepare 2, 6-dihydroxytoluene:
the common acids for hydrolyzing the arylamine compounds comprise sulfuric acid, ammonium bisulfate, hydrochloric acid, hydrobromic acid, phosphoric acid and the like, when the arylamine compounds are hydrolyzed by a conventional method to prepare corresponding phenolic compounds, the excessive amount of the acids is more when the sulfuric acid is used as a catalyst, the utilization rate of acid radicals is less than 50 percent, mother liquor after the phenolic compounds are extracted is generally introduced into ammonia gas to neutralize residual acidity, a byproduct ammonium sulfate is prepared after concentration, and raw materials and intermediates which are not hydrolyzed are difficult to recover and utilize; the ammonium bisulfate is used as a catalyst, the excessive acid is also large, the generated ammonium sulfate needs high temperature when being converted into the ammonium bisulfate, and the raw materials and intermediates remained by hydrolysis are damaged and are difficult to be continuously utilized; phosphoric acid is used as a catalyst, the phosphoric acid is used in a large excess amount, in the existing documents, after the phosphoric acid aqueous solution after hydrolysis is supplemented with consumed phosphoric acid, the phosphoric acid aqueous solution is continuously used for 5-6 times, so that the utilization rate of the catalyst and raw materials is improved, but finally, a large amount of acidic mixed mother liquor by-product cannot be treated, the raw materials and intermediates which are not hydrolyzed completely are difficult to recover and utilize, and a large amount of phosphoric acid has to be neutralized by ammonia to prepare ammonium phosphate by-product.
However, no matter how the arylamine compound is hydrolyzed, a certain amount of waste acid is generated, not only part of raw materials and intermediates are mixed, but also alkaline substances are required to be added for neutralization so as to treat the waste mother liquor, so that more waste salt impurities are generated, the environmental hazard is large, and the product yield is low.
Thirdly, the invention content: (1) the purpose of the invention is as follows: the invention aims to overcome a series of problems of incomplete hydrolysis reaction, low raw material conversion rate, low utilization efficiency of a catalyst for neutralization treatment of a hydrolysis mother liquor, large environmental hazard and the like in the production of corresponding phenolic compounds by using corresponding arylamine compounds through acidic hydrolysis of the known phenolic compounds, and finds a method for recycling the stable hydrolysis catalyst and ammonium salt generated by simple precipitation of the mother liquor so as to improve the product yield and the utilization efficiency of the catalyst, reduce the environmental hazard and form a high-efficiency, clean and safe process method for preparing the phenolic compounds.
(2) The technical scheme is as follows: through a large number of experimental researches, the invention discovers that in sulfuric acid, ammonium bisulfate, phosphoric acid, hydrochloric acid and hydrobromic acid used for preparing corresponding phenolic compounds by hydrolyzing various conventional arylamine compounds, inorganic ammonium salts formed by the sulfuric acid, the ammonium bisulfate, the phosphoric acid, the hydrochloric acid and the hydrobromic acid have lower solubility in polar protic solvents, but amine salts formed by the arylamine compounds have certain solubility, inorganic ammonium salts generated by hydrolysis reaction can be precipitated and separated from a hydrolysis reaction system through proper design, and the amine salts formed by the arylamine compounds and an acid catalyst are circularly sleeved for the hydrolysis reaction after separating the polar protic solvents, so that the efficient and clean cyclic process for preparing the phenolic compounds by acidic hydrolysis of the arylamine compounds is formed.
(3) The technical effects are as follows: the invention relates to a high-efficiency and clean production method of phenolic compounds, which comprises the steps of adding corresponding arylamine compounds into a certain amount of acidic catalyst aqueous solution, heating for hydrolysis, cooling to room temperature, adding an extraction solvent to extract the generated phenolic compounds, separating the extraction solvent from an extraction liquid to prepare a finished phenolic compound product, evaporating residual extraction solvent and partial water from an extracted acidic mother solution, mixing a certain amount of polar protic solvent to precipitate inorganic ammonium salts in the mother solution, dissolving salts formed by the arylamine compounds and the acidic catalysts which are not hydrolyzed and are incompletely hydrolyzed and excessive acidic catalysts and the polar protic solvent into the polar protic solvent, separating the inorganic ammonium salts precipitate, further distilling to remove the polar protic solvent, and sleeving the salts of the arylamine compounds which are not hydrolyzed and incompletely hydrolyzed and the excessive acidic catalysts for the synthesis of the next batch, the hydrolysis reaction is continued. Thus, the product yield is improved, the use efficiency of the catalyst is improved, the environmental hazard is reduced, and the process method is efficient, clean and safe.
The concrete aspects are as follows:
1. the polar protic solvent is adopted as the precipitation solvent, so that the generated inorganic ammonium salt has low solubility in the polar protic solvent, and the polar protic solvent is added to be easily precipitated, so that the acidic catalyst in the hydrolysis mother liquor is conveniently recycled, the use efficiency of the catalyst is improved, the production cost is reduced, and the environmental hazard is reduced.
2. The invention adopts polar protic solvent as precipitation solvent, and the salt formed by the arylamine compound without hydrolysis and incomplete hydrolysis and the catalyst can be dissolved in the polar protic solvent, so that part of the compound can be continuously recycled to the hydrolysis reaction, thereby improving the conversion rate of raw materials, reducing the production cost and reducing the environmental hazard.
Fourthly, the specific implementation mode of the invention is as follows:
example 1: adding 176g of 85 percent phosphoric acid and 201.5g of water into a 500ml hydrolysis reaction tank, uniformly mixing, then adding 27g of 2, 4-diaminotoluene, replacing with nitrogen, pressurizing and heating to 230-240 ℃ for reaction for 6 hours, cooling to obtain 391.2g of hydrolysate (loss is 13.3g), transferring the hydrolysate into a separating funnel, adding 50ml of butyl acetate each time for extraction for 4 times, combining extract liquor, adding magnesium sulfate for drying, decoloring with active carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering and drying to obtain 22.5g of light brown 2, 4-dihydroxytoluene (molar yield is 82%)
Heating the extracted acidic mother liquor to evaporate an azeotrope of butyl acetate and water, adding 320g of residual acidic mother liquor into 1500g of methanol to separate out transparent crystals, washing and filtering the crystals by using the methanol, drying the crystals to obtain 39g of ammonium dihydrogen phosphate (TLC analysis, almost organic matters), continuously heating the mother liquor to evaporate the methanol, and continuously heating the mother liquor to evaporate the methanol to obtain 250g of residual mother liquor (TCL analysis, 2, 4-diaminotoluene and other components), titrating and analyzing to contain 103.5g of phosphoric acid, and storing for next batch of hydrolysis and reuse.
Example 2: adding 51g of 85 percent phosphoric acid and 82g of water into a 500ml hydrolysis reaction tank, uniformly mixing, then adding 27g of 2, 4-diaminotoluene, then using 245g of the mother liquor recovered in the example 1 again, replacing with nitrogen, then pressurizing and heating to 230-240 ℃ for reaction for 6 hours, cooling to obtain 393g of hydrolysate (loss of 12g), transferring the hydrolysate into a separating funnel, adding 50ml of butyl acetate each time for extraction for 4 times, combining the extract liquor, adding magnesium sulfate for drying, decoloring with active carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering and drying to obtain 25.5g of light brown 2, 4-dihydroxytoluene (molar yield 92.9%)
Heating the extracted acidic mother liquor to evaporate an azeotrope of butyl acetate and water, adding residual 322g of the acidic mother liquor into 1500g of methanol, separating out transparent crystals, washing and filtering the crystals by using methanol, drying the crystals to obtain 45.5g of ammonium dihydrogen phosphate (TLC analysis, almost organic substances), continuously heating the mother liquor to evaporate methanol, and continuously heating the residual 255g of the mother liquor (TCL analysis, 2, 4-diaminotoluene and other components), titrating and analyzing to obtain 106g of phosphoric acid, and storing for next batch of hydrolysis and reuse.
Example 3: adding 90g of 98% sulfuric acid and 280g of water into a 500ml hydrolysis reaction tank, uniformly mixing, then adding 46g of m-phenylenediamine, replacing with nitrogen, pressurizing and heating to 230-240 ℃ for reaction for 6 hours, cooling to obtain 401g of hydrolysate, (loss of 15g), transferring the hydrolysate into a separating funnel, adding 80ml of butyl acetate for extraction for 4 times, combining extract liquor, adding magnesium sulfate for drying, decoloring with activated carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering, and drying to obtain 39.8g of light brown resorcinol (molar yield of 85%)
Heating the extracted acidic mother liquor to evaporate azeotrope of butyl acetate and water, adding residual 290g of acidic mother liquor into 1500g of ethanol, separating out transparent crystals, washing with ethanol, filtering, drying the crystals to obtain 79g of ammonium bisulfate (TLC analysis, almost organic matter), continuously heating the mother liquor to evaporate ethanol, and continuously heating the residual 185g of mother liquor (TCL analysis, containing components such as m-phenylenediamine and the like), titrating to analyze that the sulfuric acid contains 4.2g, and storing the mother liquor for next hydrolysis.
Example 4: adding 90g of 98% sulfuric acid and 118g of water into a 500ml hydrolysis reaction tank, applying 182g of mother liquor recovered in example 3, uniformly mixing, adding 46g of m-phenylenediamine, replacing with nitrogen, pressurizing, heating to 230-240 ℃ for reaction for 6 hours, cooling to obtain 424g of hydrolysate (loss of 12g), transferring the hydrolysate into a separating funnel, adding 80ml of butyl acetate each time for extraction for 4 times, combining extract liquor, adding magnesium sulfate for drying, decoloring with active carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering, and drying to obtain 44.3g of light brown resorcinol (molar yield 94.5%)
Heating the extracted acidic mother liquor to evaporate an azeotrope of butyl acetate and water, adding 305g of residual acidic mother liquor into 1500g of ethanol, separating out transparent crystals, washing with ethanol, filtering, drying the crystals to obtain 90.5g of ammonium bisulfate (TLC analysis, almost organic matter), continuously heating the mother liquor to evaporate ethanol, collecting 194g of residual mother liquor (TCL analysis, containing components such as m-phenylenediamine and the like), titrating to analyze that the sulfuric acid contains 7.9g, and storing the mother liquor for next hydrolysis.
Example 5: adding 190g of 90% ammonium bisulfate and 210g of water into a 500ml hydrolysis reaction tank, uniformly mixing, then adding 27g of 2, 4-diaminotoluene, performing nitrogen replacement, pressurizing and heating to 230-240 ℃ for reaction for 6 hours, cooling, then discharging 414g of hydrolysate, (losing 13g), transferring the hydrolysate into a separating funnel, adding 50ml of butyl acetate for extraction for 4 times each time, combining extract liquor, adding magnesium sulfate for drying, decoloring by activated carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering, and drying to obtain 20.5g of light brown 2, 4-dihydroxytoluene (molar yield 74.7%)
Heating the extracted acidic mother liquor to evaporate an azeotrope of butyl acetate and water, adding 343g of residual acidic mother liquor into 700g of methanol, separating out transparent crystals, washing and filtering the crystals by using the methanol, drying the crystals to obtain 42g of diammonium sulfate (TLC analysis, almost organic matter), continuously heating the mother liquor to evaporate methanol, and continuously heating the mother liquor to evaporate 272g of residual mother liquor (TCL analysis, containing 2, 4-diaminotoluene and other components), titrating and analyzing to obtain 122g of ammonium bisulfate, and storing for next batch of hydrolysis and reuse.
Example 6: adding 50g of 90% ammonium bisulfate and 80g of water into a 500ml hydrolysis reaction tank, then using 267g of the mother liquor recovered in the example 5, uniformly mixing, then adding 27g of 2, 4-diaminotoluene, replacing with nitrogen, pressurizing and heating to 230-240 ℃ for reaction for 6 hours, cooling to obtain 413g of hydrolysate (loss of 11g), transferring the hydrolysate into a separating funnel, adding 50ml of butyl acetate for extraction for 4 times each time, combining extract liquor, adding magnesium sulfate for drying, decoloring with activated carbon, removing butyl acetate in vacuum, adding toluene for crystallization, filtering and drying to obtain 23.7g of light brown 2, 4-dihydroxytoluene (molar yield 86.4%)
Heating the extracted acidic mother liquor to evaporate an azeotrope of butyl acetate and water, adding residual 315g of the acidic mother liquor into 700g of methanol, separating out transparent crystals, washing and filtering the crystals by using methanol, drying the crystals to obtain 48.5g of diammonium sulfate (TLC analysis, almost organic matters), continuously heating the mother liquor to evaporate methanol, and continuously heating the residual 254g of the mother liquor (TCL analysis, 2, 4-diaminotoluene and other components), titrating and analyzing 116g of ammonium bisulfate, and storing for next batch of hydrolysis and reuse.
The invention relates to a clean production method of a phenolic compound, which solves a series of problems of low raw material conversion rate, neutralization treatment of hydrolysis mother liquor, large environmental hazard and the like existing when corresponding aromatic amine compounds are used for producing corresponding phenolic compounds through acidic hydrolysis of the known phenolic compounds Clean and safe. The method has the advantages of easily available raw materials, suitability for batch and continuous production, high automation degree, no need of using an alkaline neutralizing agent to treat wastewater, safety, environmental protection, high yield, good quality and low cost, and can be used for industrial production. The invention has the advantages of low investment cost, low production and driving risk and rich operating profit.
Finally, it is to be noted that: although the present invention has been described in detail with reference to the foregoing examples, those skilled in the art may still modify the technical solutions described in the foregoing examples, or equivalently replace some technical features of the embodiments, or simply change the technical solutions of the present invention into continuous engineering. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An efficient and clean production method of a phenolic compound comprises the following steps: adding corresponding arylamine compound into a certain amount of acidic catalyst aqueous solution, heating for hydrolysis, cooling to room temperature, adding an extraction solvent to extract a generated phenolic compound, separating the extraction solvent from an extraction liquid to prepare a finished phenolic compound product, evaporating residual extraction solvent and partial water from the extracted acidic mother liquor, mixing a certain amount of polar protic solvent to precipitate inorganic ammonium salt in the mother liquor, dissolving salt formed by the arylamine compound which is not hydrolyzed and is incompletely hydrolyzed and the acidic catalyst and excessive acidic catalyst in the polar protic solvent, separating the inorganic ammonium salt precipitate, further distilling to remove the polar protic solvent, sleeving the salt of the arylamine compound which is not hydrolyzed and is incompletely hydrolyzed and the excessive acidic catalyst in the synthesis of the next batch, and continuing the hydrolysis reaction.
2. The producible phenolic compounds as claimed in claim 1 include, but are not limited to: p-methylphenol, m-methylphenol, 2-naphthol, 1-naphthol, m-hydroxybenzoic acid, 3, 5-dimethylphenol, p-phenylphenol, hydroquinone, resorcinol, 2, 4-dihydroxytoluene (4-methylresorcinol), 2, 6-dihydroxytoluene (2-methylresorcinol), phloroglucinol, 1, 5-dihydroxynaphthalene, 3, 5-dihydroxybenzoic acid, 2, 5-dimethylphenol, 3, 4-dimethylphenol, 8-hydroxyquinoline, 4-hydroxydiphenylamine, and mixtures of two or more thereof.
3. The hydrolysis reaction as claimed in claim 1, wherein the acid catalyst comprises: sulfuric acid, ammonium bisulfate, phosphoric acid, hydrochloric acid, hydrobromic acid.
4. The hydrolysis reaction as claimed in claim 1 or 3, wherein the number of moles of the effective acidic groups in the aqueous acidic catalyst solution is 1 to 20 times, preferably 2 to 8 times, the number of moles of the amino groups in the aromatic amine compound.
5. The acidic mother liquor after extraction as claimed in claim 1, the mother liquor after distilling off the residual extraction solvent and part of the water content is controlled to a water content of from 1% to 90%, preferably from 30% to 60%.
6. The polar protic solvent as claimed in claim 1, comprising: methanol, ethanol, isopropanol, and ethylene glycol.
7. The amount of polar protic solvent as claimed in claims 1 and 6 added is from 1 to 20 times, preferably from 2 to 8 times, the total amount of mother liquor.
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| BE823455A (en) * | 1972-06-29 | 1975-06-17 | RESORCINOL MANUFACTURING PROCESS | |
| US3933925A (en) * | 1972-06-29 | 1976-01-20 | Koppers Company, Inc. | Hydrolysis of toluene diamines to produce methyl resorcinols |
| GB1437167A (en) * | 1974-12-09 | 1976-05-26 | ||
| JPH07242604A (en) * | 1994-01-13 | 1995-09-19 | Sumitomo Chem Co Ltd | Production of 4,6-diaminoresorcinol and its precursor |
| CN102826961A (en) * | 2012-08-14 | 2012-12-19 | 江苏扬农化工集团有限公司 | Cycling treatment method for waste acid produced in production of hydroquinone |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN103848724A (en) * | 2014-03-18 | 2014-06-11 | 南京工业大学 | Process for producing resorcinol by hydrolyzing m-phenylenediamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE823455A (en) * | 1972-06-29 | 1975-06-17 | RESORCINOL MANUFACTURING PROCESS | |
| US3933925A (en) * | 1972-06-29 | 1976-01-20 | Koppers Company, Inc. | Hydrolysis of toluene diamines to produce methyl resorcinols |
| GB1437167A (en) * | 1974-12-09 | 1976-05-26 | ||
| JPH07242604A (en) * | 1994-01-13 | 1995-09-19 | Sumitomo Chem Co Ltd | Production of 4,6-diaminoresorcinol and its precursor |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN102826961A (en) * | 2012-08-14 | 2012-12-19 | 江苏扬农化工集团有限公司 | Cycling treatment method for waste acid produced in production of hydroquinone |
| CN103848724A (en) * | 2014-03-18 | 2014-06-11 | 南京工业大学 | Process for producing resorcinol by hydrolyzing m-phenylenediamine |
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