CN116063159A - Method for producing hydroquinone by phenol hydroxylation - Google Patents
Method for producing hydroquinone by phenol hydroxylation Download PDFInfo
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- CN116063159A CN116063159A CN202310197136.5A CN202310197136A CN116063159A CN 116063159 A CN116063159 A CN 116063159A CN 202310197136 A CN202310197136 A CN 202310197136A CN 116063159 A CN116063159 A CN 116063159A
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- hydroquinone
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- hydrogen peroxide
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 23
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 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 15
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 ketone peroxide Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing hydroquinone by hydroxylation of phenol, which is characterized in that phenol is used as a raw material, hydrogen peroxide is used as an oxidant, a formed titanium-silicon molecular sieve is used as a catalyst in an internal and external multi-effect temperature-control reactor, and the method synthesizes the benzenediol in a compound solvent system. The method has the characteristics of high conversion rate of raw materials, high proportion of hydroquinone in the product and low tar content, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for producing hydroquinone by phenol hydroxylation.
Background
The benzenediol is used as an important chemical raw material and is widely applied to a plurality of fields of pesticide, medicine, photosensitive materials, rubber, dye, spice, fertilizer industry and the like. The traditional method for producing the benzenediol has a plurality of defects such as large pollution, low utilization rate and more side reactions; the method for synthesizing the benzene diphenol (catechol, hydroquinone) by phenol hydroxylation with hydrogen peroxide as an oxidant has the advantages of serious equipment corrosion, long reaction time, high reaction production cost, complex production process and the like, simple process flow, mild reaction conditions, low price of the hydrogen peroxide, no pollution caused by oxidation by-products, and becomes a research hot spot in the chemical industry field.
At present, in the global scope, a phenol hydroxylation reaction has a plurality of typical methods, rhone-Poulenc company takes HClO4 as a catalyst, H3PO4 as a cocatalyst, 70% hydrogen peroxide as an oxidant, inorganic acid has strong corrosiveness, and high-concentration hydrogen peroxide has high safety risk; the Ube method uses sulfuric acid, sulfate or pyrophosphoric acid as a catalyst, and uses 60% hydrogen peroxide and ketone to generate ketone peroxide as an oxidant to produce the benzenediol, and the method has complex flow and large phenol circulation quantity; the Brichima method uses a mixture of ferric salt and cobalt salt as a catalyst, 60% hydrogen peroxide as an oxidant, and adopts a homogeneous phase reaction, so that the catalyst is not easy to separate; the Enichem method adopts titanium-silicon molecular sieve TS-1, the catalyst separation is relatively easy, the reaction condition is mild, and the method is the most advanced industrial production method at present, but the problems of lower phenol conversion rate and hydroquinone selectivity and more byproducts and tar content exist at present.
The Jiangsu Sanjili company proposes a multistage combined reaction device for synthesizing the benzenediol by phenol hydroxylation in a patent CN 114307900A, so that the temperature controllability of the phenol hydroxylation reaction is increased, the material blockage is reduced, the safety performance of the device is enhanced, the production cost is reduced, the production efficiency is improved, but the ratio of hydroquinone to catechol in the product is low, and the economical efficiency is poor. The medical limited company of Jiangxi brothers proposes a method for synthesizing hydroquinone by phenol hydroxylation in a patent CN 112125786A, the phenol conversion rate of the method reaches about 25 percent, the ratio of the hydroquinone to catechol can reach about 2.5, the tar selectivity is about 20 percent, the method obviously improves the ortho-ratio selectivity, but there is a room for further improvement, and in addition, the tar selectivity is higher.
In order to overcome the defects of the prior art, the invention solves the problems of low phenol conversion rate, more byproducts and tar content, low ratio of hydroquinone to catechol in products, difficult control of the large reaction heat release process and the like in the existing industrialized reaction process, develops a composite solvent system, synthesizes the benzenediol by adopting an internal and external multi-effect temperature-control reactor, has the characteristics of good mass transfer and heat transfer efficiency, high raw material conversion rate, high hydroquinone proportion in products and low tar content, and can provide an important production path for the industrialized production of the benzenediol.
Disclosure of Invention
The invention aims to provide a method for producing hydroquinone by hydroxylation of phenol, which is characterized in that phenol is used as a raw material, hydrogen peroxide is used as an oxidant, a formed titanium-silicon molecular sieve is used as a catalyst in an internal and external multi-effect temperature-control reactor, and the benzenediol is synthesized in a compound solvent system. The method has the characteristics of good heat transfer efficiency, high raw material conversion rate, high hydroquinone proportion in the product and low tar content, and can provide an important production path for the industrialized production of the benzenediol.
Aiming at the problems of low phenol conversion rate and more byproducts and tar content in the prior art, the invention provides the internal and external multi-effect temperature control reactor for preparing the benzenediol by hydroxylation of the phenol, which is simple to operate, good in mass and heat transfer effect and capable of precisely controlling the temperature, low-temperature synthesis is realized, and the reaction temperature rise is controlled by controlling the dropping speed of the hydrogen peroxide in the reaction process, so that the side reaction and the tar are controlled while the high phenol conversion rate is achieved.
In order to solve the problems of low ratio of hydroquinone to catechol, low raw material conversion rate and high tar content in the existing products, a composite solvent system is developed, particularly in the presence of a protic solvent, OH groups of solvent molecules are easy to combine with titanium active sites in a TS-1 molecular sieve due to the hydrogen bonding action of the protic solvent, so that the volume of the titanium active sites is increased, and the phenol hydroxylation is more prone to occur in para position due to the steric hindrance effect. Meanwhile, a novel material of the formed titanium-silicon molecular sieve catalyst is developed, and partial or all crystal grains of the material are hollow, so that the mass transfer speed of raw materials and products can be remarkably improved, the phenol conversion rate is improved, and meanwhile, the production of byproducts and tar is reduced.
The technical scheme of the invention is as follows:
a method for producing hydroquinone by hydroxylation of phenol in a multi-effect temperature-controlled reactor from inside to outside, takes phenol as a raw material, hydrogen peroxide as an oxidant, takes a formed titanium-silicon molecular sieve as a catalyst, and synthesizes the benzenediol in a composite solvent system, which is characterized by comprising the following steps:
(1) The raw material phenol, the formed titanium-silicon molecular sieve catalyst and the composite solvent are fully mixed in an internal-external multi-effect temperature-control reactor according to a certain proportion.
(2) And starting an internal and external temperature control circulation system of the reactor, and controlling the temperature of materials in the reactor to the required experimental temperature.
(3) And uniformly dripping the prepared mixed solution of hydrogen peroxide and the composite solvent into the reactor at a certain speed, wherein the temperature rise of the reaction solution is strictly controlled in the dripping process. After the dripping is finished, the temperature is kept for a period of time, after the reaction is finished, the product is discharged from a discharge hole of the reactor, and then the solid-liquid separation is carried out to obtain the benzenediol product.
The inside of the inner and outer multi-effect temperature control reactors is provided with temperature control coils, and the outside of the inner and outer multi-effect temperature control reactors is provided with temperature control jackets.
The internal and external multi-effect temperature control reactor is provided with a spiral belt type stirring system, and the gap between the spiral belt type stirring system and the bottom of the stirring kettle is 3-50 mm.
The number of hydrogen peroxide charging ports of the inner and outer multi-effect temperature control reactors is 1-12.
The bottom of the hydrogen peroxide charging port of the inner and outer multi-effect temperature control reactor is provided with a liquid distributor.
The concentration of the hydrogen peroxide is 10% -70%.
The forming method of the formed titanium-silicon molecular sieve catalyst material is spray forming, extrusion forming or rolling ball forming.
The compound solvent system is two or more of a proton solvent or an aprotic solvent, preferably the proton solvent is compounded with the aprotic solvent.
The proton solvent is water, alcohol or acid, and the alcohol is monohydric alcohol, dihydric alcohol or trihydric alcohol.
The aprotic solvent is ketone, ether, dimethyl sulfoxide or 1,4 dioxane.
The certain proportion is phenol mass: catalyst mass: the mass of the composite solvent is = (1-5) 1 (1-3).
The temperature in the step (1) is between 20 ℃ below zero and 80 ℃.
The certain time in the step (2) is 0.5-50 h.
The temperature rise in step (3) is not more than 5 ℃, preferably 2 ℃, and the reaction time is 1 to 60 hours, preferably 3 to 15 hours.
Compared with the prior art, the invention has the following main characteristics:
1. the novel material of the formed titanium-silicon molecular sieve catalyst with a special structure is developed, and partial or all crystal grains of the material are hollow, so that the mass transfer speed of raw materials and products can be remarkably improved, the phenol conversion rate is improved, and meanwhile, the production of byproducts and tar is reduced.
2. The composite solvent system is developed, the ratio of hydroquinone to catechol in the product is obviously improved, and the economic value of the product is improved.
3. The internal and external multi-effect temperature control reactors are adopted to synthesize the benzenediol, so that the mass and heat transfer effect is good, the temperature can be precisely controlled, and the method has the characteristics of good mass and heat transfer efficiency, high raw material conversion rate, high hydroquinone proportion in the product and low tar content.
Drawings
Detailed Description
The present invention is described in detail below with reference to the following examples, which are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, within the scope of the present invention, should substitute or change the technical solution according to the present invention and the inventive concept thereof, to be encompassed within the scope of the present invention.
In the following examples and comparative examples, the concentration of hydrogen peroxide was analyzed by titration, the composition content of the product was analyzed by gas chromatography, the concentration of the components was quantified by an external standard method, and the tar content was calculated by a high temperature distiller, and the conversion rate, the para-ortho selectivity and the tar selectivity of hydrogen peroxide and phenol were calculated by the following formulas, respectively.
tar selectivity = mass of tar/mass of reacted phenol x 100%
C' H2O2 : is the initial concentration of hydrogen peroxide;
C H2O2 : the concentration of hydrogen peroxide in the reaction product;
C′ phenol (P) : is the initial concentration of phenol;
C phenol (P) : is the concentration of phenol in the reaction product;
n' hydroquinone (HQ) : the mole number of hydroquinone in the product;
n' Catechol : moles of catechol in the product;
n' converted phenol : moles of phenol converted;
example 1
Adding 32Kg of phenol, 48Kg of composite solvent and 30Kg of formed titanium-silicon molecular sieve catalyst into an internal and external multi-effect temperature-controlled reactor, wherein the mixed solvent comprises the following components: 1,4 dioxane mass: and (3) uniformly mixing methanol mass=1:1, starting a stirring system, starting an internal and external temperature control system, controlling the temperature to-10 ℃, discharging the reaction material after the hydrogen peroxide concentration is qualified after the reaction material reaches a set value, slowly dripping 300g of mixed solution of 50% hydrogen peroxide solution and 400g of composite solvent into the reactor from six feed inlets on the reactor, wherein the molar ratio of phenol to hydrogen peroxide is added according to the ratio of 2:1, introducing nitrogen in the reaction process, controlling the oxygen concentration in the reactor to be within 1000ppm through the flow rate of the nitrogen, and carrying out centrifugal separation to obtain the benzenediol product. The product composition was analyzed by gas chromatography, the conversion of phenol and hydrogen peroxide was calculated, and the o-selectivity and tar selectivity were compared, and the average value of the three sets of repeated data was taken and shown in table 1.
Example 2
Adding 32Kg of phenol, 48Kg of composite solvent and 30Kg of formed titanium-silicon molecular sieve catalyst into an internal and external multi-effect temperature-controlled reactor, wherein the mixed solvent comprises the following components: 1,4 dioxane mass: and (3) uniformly mixing acetone mass=1:1, starting a stirring system, starting an internal and external temperature control system, controlling the temperature to 0 ℃, discharging the reaction material after the hydrogen peroxide concentration is qualified after the material temperature reaches a set value, slowly dripping 300g of mixed solution of 50% hydrogen peroxide solution and 400g of composite solvent into the reactor from six feed inlets on the reactor, wherein the molar ratio of phenol to hydrogen peroxide is added according to the ratio of 2:1, introducing nitrogen in the reaction process, controlling the oxygen concentration in the reactor to be within 1000ppm through the flow rate of the nitrogen, and carrying out centrifugal separation to obtain the benzenediol product after the hydrogen peroxide concentration is qualified. The product composition was analyzed by gas chromatography, the conversion of phenol and hydrogen peroxide was calculated, and the o-selectivity and tar selectivity were compared, and the average value of the three sets of repeated data was taken and shown in table 1.
Example 3
Adding 32Kg of phenol, 48Kg of composite solvent and 30Kg of formed titanium-silicon molecular sieve catalyst into an internal and external multi-effect temperature-controlled reactor, wherein the mixed solvent comprises the following components: methanol mass: and (3) uniformly mixing acetone mass=1:1, starting a stirring system, starting an internal and external temperature control system, controlling the temperature to 10 ℃, discharging the reaction material after the hydrogen peroxide concentration is qualified after the material temperature reaches a set value, slowly dripping 300g of mixed solution of 50% hydrogen peroxide solution and 400g of composite solvent into the reactor from six feed inlets on the reactor, wherein the molar ratio of phenol to hydrogen peroxide is added according to the ratio of 2:1, introducing nitrogen in the reaction process, controlling the oxygen concentration in the reactor to be within 1000ppm through the flow rate of the nitrogen, and carrying out centrifugal separation to obtain the benzenediol product after the hydrogen peroxide concentration is qualified. The product composition was analyzed by gas chromatography, the conversion of phenol and hydrogen peroxide was calculated, and the o-selectivity and tar selectivity were compared, and the average value of the three sets of repeated data was taken and shown in table 1.
Comparative example 1
The procedure of example 1 was followed except that the solvent used was acetone as the sole solvent, and the reaction results obtained are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed except that the solvent used was methanol as the single solvent, and the reaction results obtained are shown in Table 1.
Comparative example 3
The procedure of example 1 was followed except that the reactor used was a conventional tank reactor, and the reaction results obtained are shown in Table 1.
TABLE 1 reaction results for different examples
Examples numbering | Phenol conversion/% | Para-ortho selectivity/% | Tar selectivity/% |
Example 1 | 40.5 | 14.5 | 17.2 |
Example 2 | 43.9 | 10.1 | 18.3 |
Example 3 | 44.1 | 3.8 | 18.9 |
Comparative example 1 | 39.2 | 0.7 | 17.1 |
Comparative example 2 | 39.5 | 0.8 | 17.5 |
Comparative example 3 | 36.9 | 10.6 | 21.5 |
Claims (10)
1. A method for producing hydroquinone by hydroxylation of phenol in a multi-effect temperature-controlled reactor from inside to outside, takes phenol as a raw material, hydrogen peroxide as an oxidant, takes a formed titanium-silicon molecular sieve as a catalyst, and synthesizes the benzenediol in a composite solvent system, which is characterized by comprising the following steps:
(1) Raw material phenol, a formed titanium-silicon molecular sieve catalyst and a composite solvent are mixed according to the mass of phenol: catalyst mass: the mass of the composite solvent= (1-5) 1, (1-3) fully mixing in an inner-outer multi-effect temperature-control reactor;
(2) Starting an internal and external temperature control circulation system of the reactor, and controlling the temperature of materials in the reactor to be between 20 ℃ below zero and 80 ℃;
(3) Hydrogen peroxide is added into the reactor within 0.5 to 50 hours, the reaction temperature rise is controlled in the adding process, and the reaction product is obtained after a period of reaction.
2. The method for producing more hydroquinone by hydroxylation of phenol as claimed in claim 1, wherein the inside and outside of the multi-effect temperature control reactor are provided with temperature control coils and temperature control jackets.
3. The method for producing more hydroquinone by hydroxylation of phenol as claimed in claim 1, wherein the internal and external multi-effect temperature-controlled reactors are provided with a ribbon stirring system.
4. The method for producing more hydroquinone by hydroxylation of phenol according to claim 3, wherein the gap between the ribbon stirring system and the bottom of the stirring kettle is 3-50 mm.
5. The method for producing more hydroquinone by hydroxylation of phenol according to claim 1, wherein the number of hydrogen peroxide charging ports of the inner and outer multi-effect temperature control reactors is 1-12.
6. The method for producing more hydroquinone by hydroxylation of phenol according to claim 1, wherein a liquid distributor is arranged at the bottom of a hydrogen peroxide charging port of the inner and outer multi-effect temperature-control reactors.
7. The method for producing more hydroquinone by hydroxylation of phenol according to claim 1, wherein the concentration of hydrogen peroxide is 10% -70%.
8. The method for producing more hydroquinone by hydroxylation of phenol as claimed in claim 1, wherein the forming method of the titanium-silicon molecular sieve catalyst material is spray forming, bar extrusion forming or rolling ball forming.
9. The method for producing hydroquinone by hydroxylation of phenol according to claim 1, wherein the compound solvent system is a combination of a protic solvent and an aprotic solvent; the protonic solvent is water, alcohol or acid, and the alcohol is monohydric alcohol, dihydric alcohol or trihydric alcohol; the aprotic solvent is ketone, ether, dimethyl sulfoxide or 1,4 dioxane.
10. The process for the production of hydroquinone by hydroxylation of phenol according to claim 1, characterized in that in step (3) the temperature rise is not greater than 5 ℃, preferably 2 ℃; the reaction time in step (3) is 1 to 60 hours, preferably 3 to 15 hours.
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Citations (7)
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CN1305982A (en) * | 2001-01-05 | 2001-08-01 | 刘希尧 | Process for preparing benzenediol by direct catalytic oxidization of phenol |
CN1410406A (en) * | 2001-09-29 | 2003-04-16 | 中国石油化工股份有限公司 | Preparation method of benzenediol |
CN103360220A (en) * | 2012-04-01 | 2013-10-23 | 中国石油化工股份有限公司 | Method for producing more hydroquinone |
CN103391912A (en) * | 2011-02-17 | 2013-11-13 | 罗地亚经营管理公司 | Method for the hydroxylation of phenols and phenol ethers |
CN111085265A (en) * | 2019-12-27 | 2020-05-01 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof |
CN112125786A (en) * | 2020-09-15 | 2020-12-25 | 江西兄弟医药有限公司 | Method for synthesizing hydroquinone by phenol hydroxylation |
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