CN109970513B - Method for catalytically recovering phenol in anisole synthesis process by methanol method - Google Patents
Method for catalytically recovering phenol in anisole synthesis process by methanol method Download PDFInfo
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- CN109970513B CN109970513B CN201910158860.0A CN201910158860A CN109970513B CN 109970513 B CN109970513 B CN 109970513B CN 201910158860 A CN201910158860 A CN 201910158860A CN 109970513 B CN109970513 B CN 109970513B
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- phenol
- anisole
- methanol
- dimethyl
- deionized water
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 68
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 3
- GFNZJAUVJCGWLW-UHFFFAOYSA-N 2-methoxy-1,3-dimethylbenzene Chemical compound COC1=C(C)C=CC=C1C GFNZJAUVJCGWLW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010574 gas phase reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 150000001844 chromium Chemical class 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004817 gas chromatography Methods 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000001035 methylating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UJCFZCTTZWHRNL-UHFFFAOYSA-N 2,4-Dimethylanisole Chemical compound COC1=CC=C(C)C=C1C UJCFZCTTZWHRNL-UHFFFAOYSA-N 0.000 description 1
- NNVKEOMPDSKFGZ-UHFFFAOYSA-N 2-methoxy-1,3,5-trimethylbenzene Chemical compound COC1=C(C)C=C(C)C=C1C NNVKEOMPDSKFGZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
- C07C37/055—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 the substituted group being bound to oxygen, e.g. ether group
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- 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
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
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Abstract
The invention discloses a method for synthesizing phenol in an anisole process by a methanol catalytic recovery method, which comprises the steps of reacting phenol and methanol in a gas phase to synthesize the phenol recovered in the anisole process and 2, 6-dimethyl anisole in a mixture of the phenol and the 2, 6-dimethyl anisole by a catalytic conversion method to generate 2, 6-dimethyl phenol and methanol under the action of a catalyst, and then realizing effective separation of the phenol and the 2, 6-dimethyl anisole by a conventional rectification process, thereby overcoming the problem that the 2, 6-dimethyl anisole and the phenol cannot be separated by adopting a rectification tower due to the fact that the boiling points are close to each other. The catalyst used in the method has the advantages of simple preparation process, low cost, high conversion rate for catalyzing the reaction of 2, 6-dimethyl anisole, good selectivity and long service life, and can realize the purpose of simply and rapidly separating phenol and 2, 6-dimethyl anisole, simultaneously the generated 2, 6-dimethyl phenol can be sold as a product, and the separated phenol and methanol can be continuously recycled as raw materials for synthesizing anisole.
Description
Technical Field
The invention belongs to the technical field of separation and purification of phenol, and particularly relates to a method for recovering phenol in a process of producing anisole by reacting methanol and phenol through catalytic conversion.
Background
Anisole, also called as anisyl ether, anisole, methoxybenzene, is an important chemical raw material, and can be used as an additive of soap and detergent due to its special fragrance; as intermediates in the synthesis of fragrances, dyes, enteral insecticides; it can be used as excellent general-purpose reagent, initiator, solvent and thermostat filler because of its large dielectric constant and high boiling point, and can be used as gasoline additive instead of methyl tert-butyl ether, also can be used as solvent and additive of synthetic resin and fuel in printing industry and paint and pigment industry. In recent years, the demand for anisole in the market has increased dramatically.
The synthetic method of anisole mainly includes a dimethyl sulfate method, a dimethyl carbonate method and a methanol method according to the difference of methylating agents. The dimethyl sulfate method has the advantages of low reaction temperature, good selectivity of target products and low cost, but the used dimethyl sulfate is a highly toxic product, phenol needs to be converted into sodium phenolate in the production process, a large amount of sodium hydroxide needs to be used, a large amount of salt-containing wastewater is generated, the post-treatment is difficult, the environmental pollution of the method is serious, and the process is eliminated; the dimethyl carbonate method and the methanol method adopt green methylating reagents dimethyl carbonate and methanol, do not generate solid waste in the production process, and are two green synthetic routes. However, carbon dioxide and methanol are generated in the reaction process of the dimethyl carbonate method, and the carbon dioxide and the methanol need to be recovered, so that the production process is relatively complex, the equipment investment cost is relatively high, and the anisole cost and the market competitiveness are relatively weak directly; the methanol method has the advantages of low raw material cost, no secondary pollution and simple post-treatment, and is the main research direction of various researchers in recent years.
The reaction of phenol and methanol has many side reactions, such as the formation of cresol by methylation on the benzene ring, the continued reaction of cresol with alcohol to form cresol or methyl anisole, etc., and the formation of cresol also continues to react with methanol to form methyl anisole, such as 2, 6-dimethyl anisole, 2,4, 6-trimethyl anisole, 2, 4-dimethyl anisole, etc., which makes the subsequent separation difficult. Especially, the boiling point of the generated small amount of 2, 6-dimethylanisole is 181 ℃, the boiling point of the generated small amount of 2, 6-dimethylanisole is close to that of phenol and has a difference of 0.9 ℃, the generated small amount of 2, 6-dimethylanisole cannot be separated by adopting a rectifying tower, so that the small amount of 2, 6-dimethylanisole is directly recovered together and enters a reaction system for circulation again in a subsequent phenol recovery process, the whole system can be cleaned only by stopping a vehicle after long-time accumulation, the energy consumption and the catalyst load are greatly increased, the catalyst efficiency is reduced, and the product cost is increased, so that the development of a method for separating 2, 6-dimethylanisole and phenol is urgent.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention aims to provide a method for recovering phenol by adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole and reacting the 2, 6-dimethyl anisole on a catalyst to generate 2, 6-dimethyl phenol and methanol, so that the phenol and the 2, 6-dimethyl anisole are separated at low cost.
Aiming at the above purpose, the technical scheme adopted by the invention comprises the following steps:
1. adding a chromium salt and a modifier into deionized water, adjusting the pH value to 7-9 by using ammonia water, adding alumina, stirring at normal temperature for 2-6 h, filtering, washing, drying at 80-100 ℃ for 10-12 h, and roasting at 200-250 ℃ for 3-6 h in a nitrogen atmosphere to prepare a catalyst carrier; the mass ratio of the chromium salt to the modifier, the deionized water and the alumina is 1 (0.005-0.01): 4-8): 0.01-0.04), wherein the chromium salt is any one or more of chromium chloride, chromium nitrate and chromium sulfate, and the modifier is any one or more of cerium nitrate, zirconium nitrate and lanthanum nitrate.
2. Adding a catalyst carrier into deionized water, adding an active component, soaking at normal temperature for 1-3 h, filtering, washing, drying, and roasting at 250-400 ℃ for 4-8 h to prepare a catalyst; the mass ratio of the catalyst carrier to the active component is 1 (0.01-0.05), wherein the active component is any one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
3. Granulating and molding the catalyst into cylindrical particles with the diameter of 3-6 mm and the height of 3-6 mm, and filling the cylindrical particles into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 60-120 ℃, and continuously passing through a fixed bed reactor, wherein the mass ratio of the 2, 6-dimethyl anisole to the deionized water is 1 (1.2-1.8), and the reaction is carried out under the conditions that the temperature is 60-120 ℃, the material residence time is 1-5 min, and the pressure is 0.1-3 MPa; after the reaction is finished, rectifying and separating the methanol, the water, the phenol and the 2, 6-dimethylphenol.
In the step 1, the mass ratio of the chromium salt to the modifier, the deionized water and the aluminum oxide is preferably 1 (0.007-0.008): 5-6): 0.02-0.03, wherein the modifier is preferably one or two of cerium nitrate and zirconium nitrate.
In the step (1), the mass fraction of the ammonia water is 15-21%.
In the step 2, the mass ratio of the catalyst carrier to the active component is preferably 1 (0.03-0.04), wherein the active component is preferably one or two of phosphotungstic acid and phosphomolybdic acid.
In the step 2, the roasting is preferably carried out at 300-350 ℃ for 5-6 h.
In the step 3, deionized water is added into a mixture of phenol and 2, 6-dimethyl anisole recovered in the process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, and the mixture is preferably heated to 80-100 ℃ and then continuously passes through a fixed bed reactor, wherein the mass ratio of the 2, 6-dimethyl anisole to the deionized water is preferably 1 (1.4-1.6).
In the step 3, the reaction is further preferably carried out at a temperature of 80-100 ℃, a material residence time of 2-3 min and a pressure of 1-2 MPa.
The invention has the following beneficial effects:
according to the invention, by a catalytic conversion method, phenol recovered by a process of synthesizing anisole by reacting phenol with methanol in a gas phase is reacted with 2, 6-dimethyl anisole in a mixture of 2, 6-dimethyl anisole under the action of a catalyst to generate 2, 6-dimethyl phenol and methanol, and then effective separation of phenol and 2, 6-dimethyl anisole can be realized by a conventional rectification process, so that the problem that the 2, 6-dimethyl anisole and phenol cannot be separated by adopting a rectification tower due to the close boiling points of the 2, 6-dimethyl anisole and the phenol is solved. The catalyst used in the method has the advantages of simple preparation process, low cost, high conversion rate for catalyzing the reaction of 2, 6-dimethyl anisole, good selectivity and long service life, and can realize the purpose of simply and rapidly separating phenol and 2, 6-dimethyl anisole, simultaneously the generated 2, 6-dimethyl phenol can be sold as a product, and the separated phenol and methanol can be continuously recycled as raw materials for synthesizing anisole.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
In the following examples, the mass content of 2, 6-dimethylanisole in the mixture of phenol and 2, 6-dimethylanisole is 5%, the 2, 6-dimethylanisole content in the reaction product (mixture of methanol, phenol, 2, 6-dimethylanisole, 2, 6-dimethylphenol) is detected by gas chromatography, and the conditions of gas chromatography are as follows: FID detector, vaporizing chamber 240 deg.C, detector 240 deg.C, column temperature 60 deg.C, constant temperature for 2min, 10 deg.C to 230 deg.C, constant temperature for 1min, and chromatographic column HP-5.
Example 1
1. Adding 200g of chromium chloride into 800g of deionized water, adding 1g of cerium nitrate, uniformly stirring, adjusting the pH value to 7 by using ammonia water with the mass fraction of 15%, adding 2g of alumina, stirring at normal temperature for 2h, filtering, washing, drying at 90 ℃ for 12h, and roasting at 200 ℃ for 3h in a nitrogen atmosphere to prepare the catalyst carrier.
2. Adding 100g of catalyst carrier into deionized water, adding 1g of phosphotungstic acid, soaking at normal temperature for 2h, filtering, washing, drying at 80 ℃ for 12h, and then roasting at 300 ℃ for 4h to prepare the catalyst.
3. Granulating and molding the catalyst into cylindrical particles with the diameter of 4mm and the height of 4mm, and filling the cylindrical particles into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 60 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.2, and reacting at the temperature of 60 ℃, the material retention time of 1min and the pressure of 0.1 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.1 percent by adopting gas chromatography.
Example 2
Steps 1 and 2 of this example are the same as example 1. In the step 3, the catalyst is granulated and formed into cylindrical particles with the diameter of 4mm and the height of 4mm, and the cylindrical particles are filled into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 80 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.4, and reacting at 80 ℃, the material retention time is 1min and the pressure is 0.5 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.09 percent by adopting gas chromatography.
Example 3
Steps 1 and 2 of this example are the same as example 1. In the step 3, the catalyst is granulated and formed into cylindrical particles with the diameter of 4mm and the height of 4mm, and the cylindrical particles are filled into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 100 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.4, and reacting at 100 ℃, the retention time of materials is 2min and the pressure is 1 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.08 percent by adopting gas chromatography.
Example 4
Steps 1 and 2 of this example are the same as example 1. In the step 3, the catalyst is granulated and formed into cylindrical particles with the diameter of 4mm and the height of 4mm, and the cylindrical particles are filled into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 100 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.4, and reacting at 100 ℃, 5min for material retention time and 2 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.058 percent by adopting gas chromatography.
Example 5
Steps 1 and 2 of this example are the same as example 1. In the step 3, the catalyst is granulated and formed into cylindrical particles with the diameter of 4mm and the height of 4mm, and the cylindrical particles are filled into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 100 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.6, and reacting at 100 ℃, 3min for material retention time and 3 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.065 percent by adopting gas chromatography.
Example 6
Steps 1 and 2 of this example are the same as example 1. In the step 3, the catalyst is granulated and formed into cylindrical particles with the diameter of 4mm and the height of 4mm, and the cylindrical particles are filled into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 120 ℃, continuously passing through a fixed bed reactor, adding deionized water into the mixture, wherein the mass ratio of the 2, 6-dimethyl anisole to water is 1:1.8, and reacting at the temperature of 120 ℃, the material retention time of 3min and the pressure of 2 MPa. After the reaction, the traditional rectifying tower is adopted to separate methanol, water, phenol and 2, 6-dimethylphenol. After the fixed bed reactor is operated and reacts for 200 hours, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.07 percent by adopting gas chromatography.
Example 7
1. Adding 200g of chromium nitrate into 1000g of deionized water, adding 1.4g of cerium nitrate, uniformly stirring, adjusting the pH value to 8 by using ammonia water with the mass fraction of 15%, adding 4g of alumina, stirring at normal temperature for 4h, filtering, washing, drying at 90 ℃ for 12h, and roasting at 200 ℃ for 5h in a nitrogen atmosphere to prepare the catalyst carrier.
2. Adding 100g of catalyst carrier into deionized water, adding 3g of phosphotungstic acid, soaking at normal temperature for 2h, filtering, washing, drying at 80 ℃ for 12h, and then roasting at 350 ℃ for 5h to prepare the catalyst.
3. The steps are the same as the example 4, the fixed bed reactor operates and reacts for 200 hours, and then gas chromatography is adopted to detect that the content of 2, 6-dimethyl anisole in the reaction product is 0.055%.
Example 8
1. Adding 200g of chromium nitrate into 1200g of deionized water, adding 1.6g of zirconium nitrate, uniformly stirring, adjusting the pH value to 8 by using 21% ammonia water by mass fraction, adding 6g of alumina, stirring at normal temperature for 5h, filtering, washing, drying at 90 ℃ for 12h, and roasting at 250 ℃ for 5h in a nitrogen atmosphere to prepare the catalyst carrier.
2. Adding 100g of catalyst carrier into deionized water, adding 4g of phosphomolybdic acid, soaking at normal temperature for 2h, filtering, washing, drying at 80 ℃ for 12h, and then roasting at 350 ℃ for 5h to prepare the catalyst.
3. The steps are the same as the example 4, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.05 percent by adopting gas chromatography after the fixed bed reactor operates and reacts for 200 hours.
Example 9
1. Adding 200g of chromium sulfate into 1600g of deionized water, adding 2g of lanthanum nitrate, uniformly stirring, adjusting the pH value to 9 by using 21% ammonia water by mass fraction, adding 8g of alumina, stirring at normal temperature for 6h, filtering, washing, drying at 90 ℃ for 12h, and roasting at 250 ℃ for 6h in a nitrogen atmosphere to prepare the catalyst carrier.
2. Adding 100g of catalyst carrier into deionized water, adding 5g of silicotungstic acid, soaking at normal temperature for 2h, filtering, washing, drying at 80 ℃ for 12h, and then roasting at 400 ℃ for 8 to prepare the catalyst.
3. The steps are the same as the example 4, the content of 2, 6-dimethyl anisole in the reaction product is detected to be 0.063% by adopting gas chromatography after the fixed bed reactor operates and reacts for 200 hours.
Claims (9)
1. A method for catalytically recovering phenol in a process for synthesizing anisole by a methanol method is characterized by comprising the following steps:
(1) adding a chromium salt and a modifier into deionized water, adjusting the pH value to 7-9 by using ammonia water, adding alumina, stirring at normal temperature for 2-6 h, filtering, washing, drying at 80-100 ℃ for 10-12 h, and roasting at 200-250 ℃ for 3-6 h in a nitrogen atmosphere to prepare a catalyst carrier;
the mass ratio of the chromium salt to the modifier, the deionized water and the alumina is 1 (0.005-0.01): 4-8): 0.01-0.04), wherein the chromium salt is any one or more of chromium chloride, chromium nitrate and chromium sulfate, and the modifier is any one or more of cerium nitrate, zirconium nitrate and lanthanum nitrate;
(2) adding a catalyst carrier into deionized water, adding an active component, soaking at normal temperature for 1-3 h, filtering, washing, drying, and roasting at 250-400 ℃ for 4-8 h to prepare a catalyst;
the mass ratio of the catalyst carrier to the active component is 1 (0.01-0.05), wherein the active component is any one or more of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid;
(3) granulating and molding the catalyst into cylindrical particles with the diameter of 3-6 mm and the height of 3-6 mm, and filling the cylindrical particles into a fixed bed reactor; adding deionized water into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, heating to 60-120 ℃, and continuously passing through a fixed bed reactor, wherein the mass ratio of the 2, 6-dimethyl anisole to the deionized water is 1 (1.2-1.8), and the reaction is carried out under the conditions that the temperature is 60-120 ℃, the material residence time is 1-5 min, and the pressure is 0.1-3 MPa; after the reaction is finished, rectifying and separating the methanol, the water, the phenol and the 2, 6-dimethylphenol.
2. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1, which is characterized in that: in the step (1), the mass ratio of the chromium salt to the modifier, the deionized water and the aluminum oxide is 1 (0.007-0.008): (5-6): 0.02-0.03).
3. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1 or 2, which is characterized in that: in the step (1), the modifier is any one or two of cerium nitrate and zirconium nitrate.
4. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1, which is characterized in that: in the step (1), the mass fraction of the ammonia water is 15-21%.
5. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1, which is characterized in that: in the step (2), the mass ratio of the catalyst carrier to the active component is 1 (0.03-0.04).
6. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1 or 5, which is characterized in that: in the step (2), the active component is one or two of phosphotungstic acid and phosphomolybdic acid.
7. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1, which is characterized in that: in the step (2), roasting is carried out for 5-6 h at the temperature of 300-350 ℃.
8. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 1, which is characterized in that: in the step (3), deionized water is added into a mixture of phenol and 2, 6-dimethyl anisole recovered in a process of synthesizing anisole by carrying out gas phase reaction on phenol and methanol, the mixture is heated to 80-100 ℃ and then continuously passes through a fixed bed reactor, wherein the mass ratio of the 2, 6-dimethyl anisole to the deionized water is 1 (1.4-1.6).
9. The method for catalytically recovering phenol in the process of synthesizing anisole by a methanol method according to claim 8, which is characterized in that: in the step (3), the reaction is carried out at the temperature of 80-100 ℃, the material retention time of 2-3 min and the pressure of 1-2 MPa.
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