CN116253619A - Preparation method of benzenediol - Google Patents
Preparation method of benzenediol Download PDFInfo
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- CN116253619A CN116253619A CN202310204383.3A CN202310204383A CN116253619A CN 116253619 A CN116253619 A CN 116253619A CN 202310204383 A CN202310204383 A CN 202310204383A CN 116253619 A CN116253619 A CN 116253619A
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- roasting
- phenol
- salt
- catalyst bed
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 103
- 239000000047 product Substances 0.000 claims abstract description 75
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 55
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000001291 vacuum drying Methods 0.000 claims abstract description 19
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 150000001844 chromium Chemical class 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 10
- 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 10
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 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 6
- 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 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 description 11
- 238000011068 loading method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 photographic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of benzenediol. The method comprises the following steps: s1, preparing a supported catalyst bed; s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor; s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product; s4, rectifying and purifying the crude product to obtain hydroquinone and catechol; the preparation method of the supported catalyst comprises the following steps: (1) Ultrasonically dispersing titanium-silicon molecular sieve, diatomite and sodium silicate into deionized water to form slurry; then spraying granulation and roasting are carried out to obtain a product A; (2) Then adding the product A into a mixed acid solution, stirring for reaction, filtering, washing, vacuum drying and roasting to obtain a product B; (3) And ultrasonically dispersing the product B, copper salt, cerium salt and chromium salt into deionized water, drying and roasting to obtain the supported catalyst. The catalyst of the invention has excellent conversion rate, yield and service life.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering. More particularly, to a method for preparing the benzenediol.
Background
The benzenediol (including hydroquinone and catechol) is an important chemical raw material and has wide application field. Hydroquinone, also known as hydroquinone, is used in the photosensitive industry in large amounts as a developer, as well as a petroleum anticoagulant, catalytic desulfurization agent, and the like. Hydroquinone is an important raw material for anthraquinone dyes and azo dyes; is also an important raw material of the antioxidant of essence and grease; are used as antioxidants and inhibitors of autoxidation due to their easy reaction with peroxidized radicals; in addition, hydroquinone and its alkyl compounds are used as polymerization inhibitors for monomer storage and transportation. Catechol, also known as pyrocatechol, is used in the pharmaceutical, pesticide, fragrance, photographic, resin, paint, etc. industries. Guaiacol prepared from catechol is an important raw material for vanillin production; tert-butylcatechol, prepared from catechol, is a polymerization inhibitor for butadiene and styrene; the synthetic resin obtained by polycondensation of catechol and various aldehydes can improve the stability of nylon fiber.
In the prior art, the preparation methods of the benzenediol are numerous. In recent years, the method for preparing the benzenediol by oxidizing and hydroxylating the phenol with the hydrogen peroxide is focused by related expert students because of simple process and no three-waste emission, and the benzenediol generated by oxidizing the phenol is easier to oxidize than the phenol, so the selection of the catalyst and the optimization of the benzenediol preparation process are particularly important.
CN101204667B discloses a metal modified FSM-16 molecular sieve catalyst and its use in the reaction of phenol and hydrogen peroxide to synthesize benzenediol, the metal used is one or more of iron, copper, manganese, chromium, tungsten, molybdenum, cobalt, vanadium and titanium. The preparation method comprises the following steps: adding the sodium silicate layer into an aqueous solution containing metal salt, regulating the pH value by using acid, stirring for a period of time, and filtering. The filter cake is transferred to an aqueous solution containing a templating agent. Stirring for a period of time, regulating the pH value by acid, stirring for a period of time, filtering, drying and calcining to obtain the catalyst. The catalyst has simple preparation method and low cost. In the reaction of catalyzing phenol and hydrogen peroxide to synthesize the benzenediol, the conversion rate of the obtained phenol on the catalyst Fe-FSM-16 is 27.8 percent, the total selectivity of the diphenol is 96.4 percent, and the result is comparable with a TS-1 molecular sieve.
CN107597173B discloses a catalyst for synthesizing benzenediol by phenol hydroxylation and a preparation method thereof, wherein the catalyst comprises: component A: a molecular sieve carrier; the molecular sieve carrier is one of TS-1 or S-1; component B: one or more of calcium, manganese, zirconium, magnesium, cerium, tin, cadmium, molybdenum and vanadium; wherein each of the metals in the component B is supported on the framework structure of the component a in the form of an oxide; the weight ratio of the components B based on the weight of the metal oxide is as follows: oxide of component b= (75-98): (2-25). The catalyst disclosed by the invention has the advantages that the active components are uniformly distributed, the conversion rate of phenol and the selectivity of the benzene diphenol are both higher when the benzene diphenol is prepared by catalyzing the phenol, the stability is high, and the catalyst can be reused.
CN115448818A discloses a process for preparing benzenediol. The method takes the byproduct component alpha, alpha-dimethylbenzyl alcohol of the propylene oxide process by the cumene co-oxidation method as a raw material, and prepares the benzenediol (containing hydroquinone, catechol and resorcinol) through the steps of hydroxylation, oxidation and pyrolysis.
However, the existing preparation process conditions have the problems of low single pass conversion rate, poor selectivity of the benzenediol, low para/catechol ratio, short service life of the catalyst and the like.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the prior art and provide a preparation method of the benzenediol. The method comprises the following steps: s1, preparing a supported catalyst bed; s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor; s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product; s4, rectifying and purifying the crude product to obtain hydroquinone and catechol; the preparation method of the supported catalyst comprises the following steps: (1) Ultrasonically dispersing titanium-silicon molecular sieve, diatomite and sodium silicate into deionized water to form slurry; then spraying granulation and roasting are carried out to obtain a product A; (2) Then adding the product A into a mixed acid solution, stirring for reaction, filtering, washing, vacuum drying and roasting to obtain a product B; (3) And ultrasonically dispersing the product B, copper salt, cerium salt and chromium salt into deionized water, drying and roasting to obtain the supported catalyst. The catalyst of the invention has excellent conversion rate, yield and service life.
The invention aims to provide a preparation method of benzenediol.
The above object of the present invention is achieved by the following technical scheme:
a method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain hydroquinone and catechol;
the preparation method of the supported catalyst comprises the following steps:
(1) Ultrasonically dispersing titanium-silicon molecular sieve, diatomite and sodium silicate into deionized water to form slurry; then spraying granulation and roasting are carried out to obtain a product A;
(2) Then adding the product A into a mixed acid solution, stirring for reaction, filtering, washing, vacuum drying and roasting to obtain a product B;
(3) And ultrasonically dispersing the product B, copper salt, cerium salt and chromium salt into deionized water, drying and roasting to obtain the supported catalyst.
Preferably, the reaction temperature of the aqueous solution of phenol and hydrogen peroxide entering the catalyst bed layer is 20-60 ℃; the pressure is 0.1-5MPa.
Preferably, the phenol has a space velocity of 0.1 to 2 hours -1 Phenol: the mole ratio of the hydrogen peroxide (30%) is as follows: 1-3:1, and the mass concentration of phenol is 6-8%.
Preferably, in the step (1), the mass ratio of the titanium silicon molecular sieve to the diatomite to the sodium silicate to the deionized water is 1:0.2-0.6:0.06-0.12:10-14; the roasting is carried out for 8-14 h at 600-800 ℃.
Preferably, in step (2), the mixed acid consists of hydrochloric acid and acetic acid.
Preferably, in the step (2), the mass ratio of the product A to the mixed acid solution is 1:5-9; in the mixed acid solution, the molar concentration of hydrochloric acid is 2-4 mmol/L, and the concentration of acetic acid is 1-3 mmol/L.
Preferably, in step (2), the stirring reaction is: stirring and reacting for 3-7 h at 80-120 ℃, wherein the vacuum drying is as follows: vacuum drying at 60-80 deg.c for 6-12 hr; the roasting is carried out for 4-6 hours at 500-600 ℃.
Preferably, in step (3), the product B, copper salt, cerium salt and chromium salt ratio is 10g: 2-4 mmol, 3-5 mmol and 1-3 mmol.
Preferably, in step (3), the copper salt is at least one of copper nitrate, copper chloride and copper acetate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the chromium salt is at least one of chromium nitrate, chromium chloride and chromium acetate.
Preferably, in step (3), the drying is: drying at 100-140 deg.c for 10-16 hr; the roasting is as follows: roasting at 500-600 deg.c for 8-14 hr.
The invention has the following beneficial effects:
(1) By adopting the composite carrier, the catalytic performance of the active component can be obviously improved, and the service life of the catalyst can be improved.
(2) Through the mixed acid treatment and the mutual matching of active components, the overall performance and the service life of the catalyst are improved.
(3) The preparation process is simple, low in cost and easy to obtain, and is favorable for industrial production.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate, 4mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Example 2
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 60 ℃; the pressure is 0.1MPa; (1 kg catalyst package)Filling amount), phenol space velocity 2h -1 Phenol: molar ratio of hydrogen peroxide (30%) =1:1, phenol mass concentration 8%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 6g of diatomite and 0.6g of sodium silicate are ultrasonically dispersed into 140g of deionized water to form slurry; then spray granulating, roasting at 800 ℃ for 8 hours to obtain a product A;
(2) 10g of product A are then added to 90g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 4mmol/L and the concentration of acetic acid being 1mmol/L. Stirring and reacting for 3 hours at 120 ℃, filtering, washing, vacuum drying for 6 hours at 80 ℃, and roasting for 4 hours at 600 ℃ to obtain a product B;
(3) 10g of the product B, 4mmol of copper chloride, 3mmol of cerium acetate and 3mmol of chromium nitrate are dispersed into 100mL of deionized water by ultrasonic, dried for 10h at 140 ℃ and roasted for 8h at 600 ℃ to obtain the supported catalyst.
Example 3
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 20 ℃; the pressure is 5MPa; (1 kg catalyst loading), phenol space velocity 0.1h -1 Phenol: molar ratio of hydrogen peroxide (30%) =3:1, phenol mass concentration 6%;
the preparation method of the supported catalyst comprises the following steps:
(1) Ultrasonically dispersing 10g of titanium silicalite molecular sieve, 2g of diatomite and 1.2g of sodium silicate into 100g of deionized water to form slurry; then spray granulating, roasting at 600 ℃ for 14h to obtain a product A;
(2) 10g of product A are then added to 50g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 2mmol/L and the concentration of acetic acid being 3mmol/L. Stirring at 80 ℃ for reaction for 7 hours, filtering, washing, vacuum drying at 60 ℃ for 12 hours, and roasting at 500 ℃ for 6 hours to obtain a product B;
(3) 10g of the product B, 2mmol of copper acetate, 5mmol of cerium nitrate and 1mmol of chromium chloride are dispersed in deionized water by ultrasonic, dried at 100 ℃ for 16h and roasted at 500 ℃ for 14h, thus obtaining the supported catalyst.
Comparative example 1
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) Ultrasonically dispersing 14g of titanium silicalite molecular sieve and 1g of sodium silicate into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate, 4mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 2
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) Ultrasonically dispersing 14g of diatomite and 1g of sodium silicate into 120g of deionized water to form a slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate, 4mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 3
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) Then adding 10g of the product A into 70g of hydrochloric acid solution, wherein the molar concentration of hydrochloric acid is 5mmol/L, stirring and reacting at 100 ℃ for 5h, filtering, washing, vacuum drying at 70 ℃ for 10h, and roasting at 550 ℃ for 5h to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate, 4mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 4
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) Then adding 10g of the product A into 70g of acetic acid solution, wherein the concentration of the acetic acid is 5mmol/L, stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying at 70 ℃ for 10h, and roasting at 550 ℃ for 5h to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate, 4mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 5
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 7mmol of copper nitrate and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 6
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 7mmol of cerium chloride and 2mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and roasted at 550 ℃ for 12h, so as to obtain the supported catalyst.
Comparative example 7
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate and 6mmol of cerium chloride are dispersed in 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h to obtain the supported catalyst.
Comparative example 8
A method for preparing benzenediol, comprising the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain the products of hydroquinone and catechol.
The reaction temperature is 40 ℃; the pressure is 2MPa; (1 kg catalyst loading), phenol space velocity 0.5h -1 Phenol: molar ratio of hydrogen peroxide (30%) =2:1, phenol mass concentration 7%;
the preparation method of the supported catalyst comprises the following steps:
(1) 10g of titanium silicalite molecular sieve, 4g of diatomite and 1g of sodium silicate are ultrasonically dispersed into 120g of deionized water to form slurry; then spray granulating, roasting at 700 ℃ for 12 hours to obtain a product A;
(2) 10g of product A are then added to 70g of a mixed acid solution consisting of hydrochloric acid and acetic acid, the molar concentration of hydrochloric acid being 3mmol/L and the concentration of acetic acid being 2mmol/L. Stirring and reacting for 5h at 100 ℃, filtering, washing, vacuum drying for 10h at 70 ℃, and roasting for 5h at 550 ℃ to obtain a product B;
(3) 10g of the product B, 3mmol of copper nitrate and 6mmol of chromium acetate are dispersed into 100mL of deionized water by ultrasonic, dried at 120 ℃ for 14h and baked at 550 ℃ for 12h, so as to obtain the supported catalyst.
Specific test results for examples 1-3 and comparative examples 1-8 are shown in Table 1:
TABLE 1
As can be seen from Table 1, the preparation method of the benzenediol has excellent selectivity and conversion rate, the utilization rate of hydrogen peroxide is relatively high, the service life of the catalyst is relatively long, and the preparation method has excellent application prospect.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of benzenediol is characterized in that: the method comprises the following steps:
s1, preparing a supported catalyst bed;
s2, filling the catalyst bed prepared in the step S1 into a fixed bed reactor;
s3, enabling an aqueous solution of phenol and hydrogen peroxide to enter a catalyst bed to obtain a crude product;
s4, rectifying and purifying the crude product to obtain hydroquinone and catechol;
the preparation method of the supported catalyst comprises the following steps:
(1) Ultrasonically dispersing titanium-silicon molecular sieve, diatomite and sodium silicate into deionized water to form slurry; then spraying granulation and roasting are carried out to obtain a product A;
(2) Then adding the product A into a mixed acid solution, stirring for reaction, filtering, washing, vacuum drying and roasting to obtain a product B;
(3) And ultrasonically dispersing the product B, copper salt, cerium salt and chromium salt into deionized water, drying and roasting to obtain the supported catalyst.
2. The method of manufacturing according to claim 1, characterized in that: the reaction temperature of the aqueous solution of phenol and hydrogen peroxide entering the catalyst bed layer is 20-60 ℃; the pressure is 0.1-5MPa.
3. The method of manufacturing according to claim 1, characterized in that: the space velocity of the phenol is 0.1 to 2h -1 Phenol: the mole ratio of the hydrogen peroxide (30%) is as follows: 1-3:1, and the mass concentration of phenol is 6-8%.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the mass ratio of the titanium silicalite molecular sieve to the diatomite to the sodium silicate to the deionized water is 1:0.2-0.6:0.06-0.12:10-14; the roasting is carried out for 8-14 h at 600-800 ℃.
5. The method of manufacturing according to claim 1, characterized in that: in step (2), the mixed acid consists of hydrochloric acid and acetic acid.
6. The method of claim 1 or 5, wherein: in the step (2), the mass ratio of the product A to the mixed acid solution is 1:5-9; in the mixed acid solution, the molar concentration of hydrochloric acid is 2-4 mmol/L, and the concentration of acetic acid is 1-3 mmol/L.
7. The method of claim 1 or 5, wherein: in step (2), the stirring reaction is: stirring and reacting for 3-7 h at 80-120 ℃, wherein the vacuum drying is as follows: vacuum drying at 60-80 deg.c for 6-12 hr; the roasting is carried out for 4-6 hours at 500-600 ℃.
8. The method of manufacturing according to claim 1, characterized in that: in step (3), the product B, copper salt, cerium salt and chromium salt ratio is 10g: 2-4 mmol, 3-5 mmol and 1-3 mmol.
9. The method of manufacturing according to claim 1, characterized in that: in the step (3), the copper salt is at least one of copper nitrate, copper chloride and copper acetate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the chromium salt is at least one of chromium nitrate, chromium chloride and chromium acetate.
10. The method of manufacturing according to claim 1, characterized in that: in step (3), the drying is: drying at 100-140 deg.c for 10-16 hr; the roasting is as follows: roasting at 500-600 deg.c for 8-14 hr.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003246761A (en) * | 2001-12-20 | 2003-09-02 | Ube Ind Ltd | Method for producing dihydric phenol |
CN101264453A (en) * | 2008-03-10 | 2008-09-17 | 华东理工大学 | Titanium-silicon molecular sieve/tripolite composite catalyst and preparation |
CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for producing benzenediol by oxygenizing phenyl hydrate with hydrogen peroxide at room temperature and preparation method thereof |
CN101786943A (en) * | 2010-02-25 | 2010-07-28 | 华东理工大学 | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction |
CN115368214A (en) * | 2022-08-22 | 2022-11-22 | 沈阳开拓利思科技有限公司 | Preparation method of benzenediol |
CN115385778A (en) * | 2022-08-22 | 2022-11-25 | 沈阳开拓利思科技有限公司 | Method for synthesizing benzenediol by phenol hydroxylation |
-
2023
- 2023-03-06 CN CN202310204383.3A patent/CN116253619A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003246761A (en) * | 2001-12-20 | 2003-09-02 | Ube Ind Ltd | Method for producing dihydric phenol |
CN101264453A (en) * | 2008-03-10 | 2008-09-17 | 华东理工大学 | Titanium-silicon molecular sieve/tripolite composite catalyst and preparation |
CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for producing benzenediol by oxygenizing phenyl hydrate with hydrogen peroxide at room temperature and preparation method thereof |
CN101786943A (en) * | 2010-02-25 | 2010-07-28 | 华东理工大学 | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction |
CN115368214A (en) * | 2022-08-22 | 2022-11-22 | 沈阳开拓利思科技有限公司 | Preparation method of benzenediol |
CN115385778A (en) * | 2022-08-22 | 2022-11-25 | 沈阳开拓利思科技有限公司 | Method for synthesizing benzenediol by phenol hydroxylation |
Non-Patent Citations (2)
Title |
---|
刘红等: "预处理对TS-1/硅藻土催化剂性能的影响", 无机化学学报, no. 11, 1 November 2003 (2003-11-01), pages 1202 - 1206 * |
杨云飞: "固定床反应器中TS-1/硅藻土催化苯酚的羟基化反应", 分子催化, vol. 21, 31 August 2007 (2007-08-31), pages 529 - 530 * |
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