CN115385778A - Method for synthesizing benzenediol by phenol hydroxylation - Google Patents
Method for synthesizing benzenediol by phenol hydroxylation Download PDFInfo
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- CN115385778A CN115385778A CN202211008185.1A CN202211008185A CN115385778A CN 115385778 A CN115385778 A CN 115385778A CN 202211008185 A CN202211008185 A CN 202211008185A CN 115385778 A CN115385778 A CN 115385778A
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- molecular sieve
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- titanium silicalite
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 10
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 claims abstract description 60
- 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 60
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 25
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 238000009718 spray deposition Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 5
- -1 aliphatic amines Chemical class 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 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
- 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
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 238000010438 heat treatment 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
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of hydroquinone synthesis, and particularly relates to a method for synthesizing hydroquinone through phenol hydroxylation. The method comprises the following steps: s1, selecting a titanium silicalite molecular sieve as a catalyst bed layer; s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor; s3, allowing a methanol solution of phenol and hydrogen peroxide to enter a catalyst bed layer to obtain a crude product; and S4, rectifying and purifying the crude product to obtain hydroquinone and catechol products. The conversion per pass of the phenol can be 20-33%, and the selectivity of the benzenediol can reach 90-95%; meanwhile, hydroquinone: the catechol ratio is 2.5-3.5, which is much higher than the prior art level; and through the fixed bed continuous process, the effective utilization rate of hydrogen peroxide reaches 75-85%, and the waste of raw materials is effectively reduced.
Description
Technical Field
The invention belongs to the technical field of hydroquinone synthesis. More particularly relates to a method for synthesizing benzenediol by phenol hydroxylation.
Background
The benzenediol (comprising hydroquinone and pyrocatechol) is an important chemical raw material and has wide application fields. Hydroquinone, also known as hydroquinone, is widely used as a developer in the light-sensitive industry, and also as an anticoagulant for petroleum, a catalytic desulfurizer, and the like. Hydroquinone is an important raw material for anthraquinone dyes and azo dyes; is also an important raw material of an antioxidant of essence and grease; it is used as an antioxidant and an inhibitor of autoxidation due to its easy reaction with peroxygenated radicals; in addition, hydroquinone and alkyl compounds thereof are also used as polymerization inhibitors for storage and transportation of monomers. Pyrocatechol, also known as pyrocatechol, is used in the industries of medicine, pesticides, spices, photography, resins, coatings and the like. Guaiacol prepared from catechol is an important raw material for producing vanillin; tert-butyl catechol 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 fibers.
In the prior art, the preparation method of the benzenediol is many. In recent years, the method for preparing the benzenediol by oxidizing phenol with hydrogen peroxide and hydroxylating the phenol is concerned by relevant experts and scholars because the process is simple and three wastes are not discharged, and the selection of the catalyst and the optimization of the benzenediol preparation process are particularly important because the benzenediol generated by oxidizing the phenol is easier to oxidize than the phenol.
The titanium silicalite molecular sieve catalyst makes the reaction of preparing benzenediol by oxidizing phenol with hydrogen peroxide more advanced than the prior transition metal salt catalyst, and has the remarkable characteristics that: under the appropriate reaction conditions, the titanium silicalite molecular sieve has good catalytic performance for the selective oxidation of phenol, can effectively avoid the deep oxidation of benzenediol, and the catalyst can be repeatedly used. However, only the france lona-planck company, the italian einy company and the japanese ministry of japan are successful in industrialization at present, but the molecular sieve has high cost, strict equipment requirement, high catalyst recovery requirement, high dehydration energy consumption due to the use of low-concentration hydrogen peroxide, complicated intermittent operation of a slurry bed, severe working environment and serious influence on the technical competitiveness, so the molecular sieve is not completely universal in other countries. Furthermore, hydroquinone is much more expensive than catechol, so ortho-contrast is also an economically important indicator for phenol hydroxylation.
CN112125786A discloses a method for synthesizing hydroquinone by hydroxylation of phenol, which comprises the steps of carrying out hydroxylation reaction on phenol and hydrogen peroxide in a system of solvent and acidic reagent under the action of TS-1 catalyst to synthesize hydroquinone; the specific method comprises the following steps: (1) Adding the TS-1 catalyst, phenol, a solvent and an acidic reagent into a four-neck flask, performing circulating cooling reflux, continuously stirring, and heating to raise the temperature; (2) Then adding 30% or 50% hydrogen peroxide dropwise, and carrying out heat preservation reaction after the dropwise addition is finished to obtain hydroquinone. The method can obviously improve the proportion of hydroquinone in the product generated by hydroxylation of phenol, and reduce the content of the generated by-products and tar.
CN201210489440.9, CN201410520453.7, CN201310342500.9, etc. all disclose preparation methods of titanium-silicon molecular sieve catalysts, but all have the problems of low single-pass conversion, poor selectivity of benzenediol, low p/o-dihydroxybenzene ratio, short service life of the catalyst, etc.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings of the prior art and provides a method for synthesizing benzenediol by phenol hydroxylation. The method comprises the following steps: s1, selecting a titanium silicalite molecular sieve as a catalyst bed layer; s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor; s3, allowing a methanol solution of phenol and hydrogen peroxide to enter a catalyst bed layer to obtain a crude product; s4, rectifying and purifying the crude product to obtain hydroquinone and catechol products. The conversion per pass of the phenol can be 20-33%, and the selectivity of the benzenediol can reach 90-95%; meanwhile, hydroquinone: the catechol ratio is 2.5-3.5, which is much higher than the prior art level; and through the fixed bed continuous process, the effective utilization rate of hydrogen peroxide reaches 70-80%, and the waste of raw materials is effectively reduced.
The invention aims to provide a method for synthesizing hydroquinone by hydroxylating phenol.
The above purpose of the invention is realized by the following technical scheme:
the preparation method of the benzenediol comprises the following steps:
s1, selecting a titanium silicalite molecular sieve as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, allowing a methanol solution of phenol and hydrogen peroxide to enter a catalyst bed layer to obtain a crude product;
s4, rectifying and purifying the crude product to obtain hydroquinone and catechol products.
Preferably, the preparation method of the titanium silicalite molecular sieve in the step S1 is that silica sol, organic amine, surfactant and silane coupling agent are uniformly mixed to form a mixture; uniformly mixing the titanium silicalite molecular sieve with the mixture to form slurry, and finally carrying out spray forming on the slurry to obtain a catalyst intermediate; and mixing the obtained catalyst intermediate with water, then carrying out pretreatment, filtering, drying and roasting to obtain the microsphere titanium silicalite molecular sieve catalyst.
Preferably, in the S1 step preparation method of the titanium silicalite molecular sieve, the organic amine is one of aliphatic amines, the surfactant is a nonionic surfactant, and the silane coupling agent is KH792, DL602 or a mixture of the two in any proportion.
Preferably, siO in silica sol 2 Organic amine: surfactant (B): the molar ratio of the silane coupling agent is 1: 0.08-0.12:0.1-0.12:0.2-0.8.
Preferably, siO in silica sol 2 Organic amine: surfactant (B): the molar ratio of the silane coupling agent is 1: 0.08-0.10:0.1-0.11:0.5-0.6.
6. The production method according to claim 3, characterized in that: in the preparation method of the titanium-silicon molecular sieve in the step S1, the organic amine is one of diethylamine, tripropylamine and n-butylamine, and the surfactant is linear 8-carbon octanol polyoxyethylene ether, linear 8-carbon isooctanol polyoxyethylene ether or a mixture of the two in any proportion.
Preferably, in the S1 step titanium silicalite molecular sieve preparation method, siO in the mixture 2 The weight ratio of the titanium-silicon molecular sieve to the titanium-silicon molecular sieve is 0.6-0.7: 1, and the titanium-silicon molecular sieve is a molecular sieve containing framework titanium.
Preferably, in the preparation method of the titanium silicalite molecular sieve in the step S1, the obtained catalyst intermediate is mixed with water according to the weight ratio of 1: 10-12, then the mixture is treated for 8-10 hours at the temperature of 120-140 ℃ and under the hydrothermal pressure condition of the catalyst intermediate, and the microsphere titanium silicalite molecular sieve catalyst is obtained after filtration, drying and roasting for 20-25 hours at the temperature of 700-750 ℃.
Preferably, the molar ratio of phenol to hydrogen peroxide is 1-5:1, wherein the mass concentration of phenol is 15-30%, and the reaction condition of the methanol solution of phenol and hydrogen peroxide entering a catalyst bed layer is that20-90 ℃, 0.1-4MPa and the space velocity of phenol is 0.05-4h -1 And the reaction is continuously carried out under the condition.
10. The method of claim 9, wherein: the reaction conditions of the methanol solution of the phenol and the hydrogen peroxide entering the catalyst bed layer are that the temperature is between 75 and 80 ℃, the pressure is between 0.8 and 1.2MPa, and the space velocity of the phenol is between 0.1 and 0.2h -1 。
The invention has the following beneficial effects:
1. the conversion per pass of the phenol can reach 20-33%, and the selectivity of the benzenediol can reach 90-95%; meanwhile, hydroquinone: the catechol ratio is 2.5-3.5, which is much higher than the prior art level;
2. according to the invention, through a fixed bed continuous process, the effective utilization rate of hydrogen peroxide reaches 75-85%, and the waste of raw materials is effectively reduced;
3. according to the invention, the surfactant and the silane coupling agent are added in the preparation process to be matched with each other, the surfactant and the silane coupling agent are interacted, and the catalyst prepared by combining a specific preparation method has a proper pore volume, so that the carbon deposition resistance of the catalyst is obviously improved, the catalyst has a long-period reaction life, the service life of the catalyst is more than or equal to 2000h, and the catalyst cost is reduced.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
0.1mol of silica sol, 0.01mol of diethylamine, 0.004mol of linear 8-carbon octanol polyoxyethylene ether, 0.006mol of linear 8-carbon isooctanol polyoxyethylene ether, 0.03mol of silane coupling agent KH792 and 0.02mol of silane coupling agent DL 602; mixing uniformly to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium-silicon molecular sieve to the titanium-silicon molecular sieve is 0.63: 1, and finally the slurry is preparedSpray forming the solution to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 10, then treating for 8 hours at 120 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 2
Uniformly mixing 0.1mol of silica sol, 0.01mol of diethylamine, 0.01mol of linear 8-carbon octanol polyoxyethylene ether, 0.03mol of silane coupling agent KH792 and 0.02mol of silane coupling agent DL602 to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium silicon molecular sieve to the slurry is 0.63: 1, and finally the slurry is sprayed and formed to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 10, then treating for 8 hours at 120 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 3
Uniformly mixing 0.1mol of silica sol, 0.01mol of diethylamine, 0.01mol of linear 8-carbon isooctanol polyoxyethylene ether and 0.05mol of silane coupling agent KH792 to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium silicon molecular sieve to the titanium silicon molecular sieve is 0.63: 1, and finally, the slurry is subjected to spray forming to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 10, then treating for 8 hours at 120 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 4
Uniformly mixing 0.1mol of silica sol, 0.01mol of diethylamine, 0.004mol of linear chain 8-carbon octanol polyoxyethylene ether, 0.006mol of linear chain 8-carbon isooctanol polyoxyethylene ether and 0.05mol of silane coupling agent KH792 to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium silicon molecular sieve to the titanium silicon molecular sieve is 0.63: 1, and finally, the slurry is subjected to spray forming to obtain a catalyst intermediate; in the obtained catalystMixing the intermediate with water according to the weight ratio of 1: 10, then processing for 8 hours at 120 ℃ and under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 5
0.1mol of silica sol, 0.01mol of diethylamine, 0.004mol of linear 8-carbon octanol polyoxyethylene ether, 0.006mol of linear 8-carbon isooctanol polyoxyethylene ether and 0.05mol of silane coupling agent DL 602; mixing uniformly to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium silicon molecular sieve to the slurry is 0.63: 1, and finally the slurry is sprayed and formed to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 10, then treating for 8 hours at 120 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 6
Uniformly mixing 0.1mol of silica sol, 0.01mol of diethylamine, 0.01mol of linear chain 8-carbon octanol polyoxyethylene ether and 0.05mol of silane coupling agent KH792 to form a mixture; uniformly mixing the mixture with Ti-MWW to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium silicon molecular sieve to the titanium silicon molecular sieve is 0.62: 1, and finally, the slurry is sprayed and formed to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 10, then treating for 8 hours at 120 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 22 hours at 730 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Example 7
Uniformly mixing 0.2mol of silica sol, 0.02mol of tripropylamine, 0.022mol of linear 8-carbon isooctyl alcohol polyoxyethylene ether and 0.06mol of silane coupling agent DL602 to form a mixture; uniformly mixing the mixture with Ti-Beta to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium-silicon molecular sieve to the titanium-silicon molecular sieve is 0.64: 1, and finally, the slurry is subjected to spray forming to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 12, and then treating the mixture at 140 ℃ under the hydrothermal pressure conditionFiltering and drying the mixture for 10 hours, and roasting the mixture for 25 hours at 750 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Comparative example 1
Uniformly mixing 0.2mol of silica sol, 0.02mol of tripropylamine and 0.082mol of linear chain 8-carbon isooctanol polyoxyethylene ether to form a mixture; uniformly mixing the mixture with Ti-Beta to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium-silicon molecular sieve to the titanium-silicon molecular sieve is 0.64: 1, and finally, the slurry is subjected to spray forming to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 12, then treating for 10 hours at 140 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 25 hours at 750 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
Comparative example 2
Uniformly mixing 0.2mol of silica sol, 0.02mol of tripropylamine and 0.082mol of silane coupling agent DL602 to form a mixture; uniformly mixing the mixture with Ti-Beta to form slurry, wherein SiO in the mixture 2 The weight ratio of the titanium-silicon molecular sieve to the titanium-silicon molecular sieve is 0.64: 1, and finally, the slurry is subjected to spray forming to obtain a catalyst intermediate; mixing the obtained catalyst intermediate with water according to the weight ratio of 1: 12, then treating for 10 hours at 140 ℃ under the hydrothermal pressure condition, filtering, drying, and roasting for 25 hours at 750 ℃ to obtain the microsphere titanium silicalite molecular sieve catalyst.
The molecular sieve catalysts prepared in examples 1-6 were tested as follows:
1kg of catalyst was charged to a fixed bed reactor, phenol: hydrogen peroxide (30%) =3, phenol concentration is 22wt%, solvent is methanol, materials are mixed, and the airspeed of phenol is 0.2h through a high-pressure pump after the materials are mixed -1 The flow rate of the catalyst enters a reaction system (a catalyst bed layer), and the reaction system enters a receiving bottle after reaction; the crude product is rectified and purified to obtain a product a (hydroquinone and catechol), tail gas is discharged into the atmosphere after secondary absorption, and the temperature and the pressure of a reaction system are 80 ℃ and 1.0MPa.
The molecular sieve catalysts prepared in example 7 and comparative examples 1-2 were tested as follows:
1kg of catalyst B was charged to a fixed bed reactor, phenol:hydrogen peroxide (30%) =2 (mol ratio), phenol concentration is 23wt%, the solvent is methanol, and the materials are mixed and then pumped by a high pressure pump at the phenol airspeed of 1.5h -1 The flow rate of the catalyst enters a reaction system (a catalyst bed layer), and the reaction product enters a receiving bottle after reaction; the crude product is rectified and purified to obtain a product b (hydroquinone and catechol), tail gas is discharged into the atmosphere after secondary absorption, and the temperature of a reaction system is 80 ℃ and the pressure is 1.0MPa.
The specific test results of examples 1-7 and comparative examples 1-2 are shown in Table 1:
TABLE 1
As can be seen from Table 1, the preparation process of the invention has excellent conversion rate, selectivity, i.e., p/catechol ratio, and relatively long service life of hydrogen peroxide and catalyst.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method for synthesizing benzenediol by phenol hydroxylation is characterized by comprising the following steps: the method comprises the following steps:
s1, selecting a titanium silicalite molecular sieve as a catalyst bed layer;
s2, filling the catalyst bed layer prepared in the step S1 into a fixed bed reactor;
s3, allowing a methanol solution of phenol and hydrogen peroxide to enter a catalyst bed layer to obtain a crude product;
and S4, rectifying and purifying the crude product to obtain hydroquinone and catechol products.
2. The production method according to claim 1, characterized in that: the preparation method of the titanium silicalite molecular sieve in the step S1 comprises the steps of uniformly mixing silica sol, organic amine, a surfactant and a silane coupling agent to form a mixture; uniformly mixing the titanium silicalite molecular sieve with the mixture to form slurry, and finally carrying out spray forming on the slurry to obtain a catalyst intermediate; and mixing the obtained catalyst intermediate with water, then carrying out pretreatment, filtering, drying and roasting to obtain the microsphere titanium silicalite molecular sieve catalyst.
3. The production method according to claim 2, characterized in that: in the preparation method of the titanium-silicon molecular sieve in the step S1, the organic amine is one of aliphatic amines, the surfactant is a nonionic surfactant, and the silane coupling agent is KH792, DL602 or a mixture of the two in any proportion.
4. The production method according to claim 2, characterized in that: siO in silica sol 2 Organic amine: surfactant (B): the molar ratio of the silane coupling agent is 1: 0.08-0.12:0.1-0.12:0.2-0.8.
5. The method of claim 4, wherein: siO in silica Sol 2 Organic amine: surfactant (b): the molar ratio of the silane coupling agent is 1: 0.08-0.10:0.1-0.11:0.5-0.6.
6. The production method according to claim 3, characterized in that: in the preparation method of the titanium-silicon molecular sieve in the step S1, the organic amine is one of diethylamine, tripropylamine and n-butylamine, and the surfactant is linear 8-carbon octanol polyoxyethylene ether, linear 8-carbon isooctanol polyoxyethylene ether or a mixture of the two in any proportion.
7. The production method according to claim 2, characterized in that: in the preparation method of the titanium silicalite molecular sieve in the S1 step, siO in the mixture 2 The weight ratio of the titanium silicalite molecular sieve to the titanium silicalite molecular sieve is 0.6-0.7: 1, and the titanium silicalite molecular sieve is a molecular sieve containing framework titanium.
8. The method of claim 2, wherein: in the preparation method of the titanium silicalite molecular sieve in the step S1, the obtained catalyst intermediate is mixed with water according to the weight ratio of 1: 10-12, then the mixture is treated for 8-10 hours at the temperature of 120-140 ℃ and under the hydrothermal pressure condition of the catalyst intermediate, and the microsphere titanium silicalite molecular sieve catalyst is obtained after filtration, drying and roasting for 20-25 hours at the temperature of 700-750 ℃.
9. The method of claim 1, wherein: the molar ratio of phenol to hydrogen peroxide is 1-5:1, wherein the mass concentration of the phenol is 15-30%, the reaction conditions of the phenol and the methanol solution of hydrogen peroxide entering a catalyst bed layer are 20-90 ℃, 0.1-4MPa and the airspeed of the phenol is 0.05-4h -1 And the reaction is continuously carried out under the condition.
10. The method of claim 9, wherein: phenol and H 2 O 2 The reaction conditions of the methanol solution entering the catalyst bed layer are 75-80 ℃, 0.8-1.2MPa and the space velocity of phenol is 0.1-0.2h -1 。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116063159A (en) * | 2023-03-03 | 2023-05-05 | 湖南长炼新材料科技股份公司 | Method for producing hydroquinone by phenol hydroxylation |
CN116102405A (en) * | 2023-03-06 | 2023-05-12 | 沈阳开拓利思科技有限公司 | Method for preparing benzenediol |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10291948A (en) * | 1997-04-18 | 1998-11-04 | Mitsubishi Gas Chem Co Inc | Production of dihydric phenols |
CN101371989A (en) * | 2007-08-22 | 2009-02-25 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve catalyst as well as preparation method and use thereof |
CN112717998A (en) * | 2021-01-19 | 2021-04-30 | 中国科学院大连化学物理研究所 | High-activity phenol hydroxylation titanium silicalite molecular sieve catalyst and preparation method thereof |
CN112774726A (en) * | 2020-12-29 | 2021-05-11 | 上海华谊新材料有限公司 | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof |
CN114345404A (en) * | 2021-12-28 | 2022-04-15 | 万华化学集团股份有限公司 | Phenol hydroxylation catalyst and preparation method thereof, and phenol hydroxylation method |
-
2022
- 2022-08-22 CN CN202211008185.1A patent/CN115385778B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10291948A (en) * | 1997-04-18 | 1998-11-04 | Mitsubishi Gas Chem Co Inc | Production of dihydric phenols |
CN101371989A (en) * | 2007-08-22 | 2009-02-25 | 中国石油化工股份有限公司 | Titanium silicon molecular sieve catalyst as well as preparation method and use thereof |
CN112774726A (en) * | 2020-12-29 | 2021-05-11 | 上海华谊新材料有限公司 | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof |
CN112717998A (en) * | 2021-01-19 | 2021-04-30 | 中国科学院大连化学物理研究所 | High-activity phenol hydroxylation titanium silicalite molecular sieve catalyst and preparation method thereof |
CN114345404A (en) * | 2021-12-28 | 2022-04-15 | 万华化学集团股份有限公司 | Phenol hydroxylation catalyst and preparation method thereof, and phenol hydroxylation method |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116063159A (en) * | 2023-03-03 | 2023-05-05 | 湖南长炼新材料科技股份公司 | Method for producing hydroquinone by phenol hydroxylation |
CN116102405A (en) * | 2023-03-06 | 2023-05-12 | 沈阳开拓利思科技有限公司 | Method for preparing benzenediol |
CN116102405B (en) * | 2023-03-06 | 2024-05-17 | 沈阳开拓利思科技有限公司 | Method for preparing benzenediol |
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