CN115069294B - Supported catalyst and application thereof in preparation of tert-butylhydroquinone - Google Patents

Supported catalyst and application thereof in preparation of tert-butylhydroquinone Download PDF

Info

Publication number
CN115069294B
CN115069294B CN202210797166.5A CN202210797166A CN115069294B CN 115069294 B CN115069294 B CN 115069294B CN 202210797166 A CN202210797166 A CN 202210797166A CN 115069294 B CN115069294 B CN 115069294B
Authority
CN
China
Prior art keywords
tert
catalyst
reaction kettle
butyl
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210797166.5A
Other languages
Chinese (zh)
Other versions
CN115069294A (en
Inventor
王新承
秦文立
黄龙
宋永吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Petrochemical Technology
Original Assignee
Beijing Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Petrochemical Technology filed Critical Beijing Institute of Petrochemical Technology
Priority to CN202210797166.5A priority Critical patent/CN115069294B/en
Publication of CN115069294A publication Critical patent/CN115069294A/en
Application granted granted Critical
Publication of CN115069294B publication Critical patent/CN115069294B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
    • C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a supported catalyst and application thereof. The invention adopts an impregnation method to load active components on a carrier molecular sieve or metal oxide, and the active components are roasted and then subjected to hydrogen reduction reaction to obtain the loaded catalyst. The supported catalyst prepared by the invention is prepared into an oxidation catalyst and a hydrogenation catalyst which are applied to preparing tert-butyl p-phenol, and the conversion rate of tert-butyl phenol and the yield and selectivity of tert-butyl p-phenol in the whole system are greatly improved by controlling the oxidation and hydrogenation conditions, so that the tert-butyl phenol in the preparation method can be completely converted, and the selectivity of tert-butyl p-phenol can reach 71-85%.

Description

Supported catalyst and application thereof in preparation of tert-butylhydroquinone
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a supported catalyst and application thereof in preparation of tert-butylhydroquinone.
Background
Tert-butylhydroquinone (TBHQ), also known as tert-butylhydroquinone, is an antioxidant. Because of good antioxidation, the product is widely applied to the industries of grease and grease-containing food at present, the stability of the food in the shelf life is increased, and meanwhile, the product has antioxidant capacity compared with ethoxy quiniline, BHA and the like as a safe and efficient edible grease antioxidant which is allowed to be used by the country; can also effectively inhibit the growth of bacteria microorganisms, and can greatly improve the antioxidant effect when being used together with BHT and BHA. In addition, the tert-butyl hydroquinone can be used as an antioxidant for rubber, plastics and the like. 2-tert-butylhydroquinone is used as a fine chemical product, the annual demand of China is close to 1000 tons, and the annual demand is on the trend of rising year after year, but because the production cost is high, many application markets are not completely opened, and most of the current application markets still depend on import.
In the published technology for preparing TBHQ, hydroquinone and tert-butyl alcohol are mainly used as raw materials, acid is used as a catalyst for catalytic reaction, and the obtained product is subjected to multiple separation and recrystallization, and finally purified to obtain the product tert-butyl hydroquinone.
GB761613 discloses a process for preparing TBHQ in a toluene-based solvent using sulfuric acid or phosphoric acid as a catalyst. WO9716402 alkylates with benzenesulfonic acid in gold methanol hydrate, although these processes are mature, the organic solvents used in these processes are prone to severe environmental pollution, the process cost is high, and solvent residues during purification are a problem.
CN112479828A discloses a preparation method of TBHQ, which comprises the steps of taking tert-butyl alcohol and hydroquinone as raw materials, taking sulfamic acid as a catalyst, reacting in a toluene or xylene solvent, adding ethanol after the reaction is finished, filtering to obtain a crude product, and further purifying to obtain a product TBHQ, wherein the sulfamic acid is heated to decompose to release oxides of nitrogen and sulfur, so that the environment is still threatened.
CN102173981A discloses a synthesis method of TBHQ, which takes hydroquinone as a raw material and macroporous sulfonic acid resin as a catalyst to react in a binary mixed solvent composed of hydrocarbon and ketone solvents, but the method does not investigate the activity of the catalyst in recycling.
CN108929200A discloses a method for catalytically synthesizing tert-butyl hydroquinone by using a polysulfonic acid ionic liquid as a catalyst, wherein the yield of the product is high, the ionic liquid catalyst can be separated and reused, but the preparation process of the ionic liquid is complicated, and the process cost is high.
At present, in order to meet the demand for increasing the demand of the tert-butylhydroquinone at home and abroad, the traditional synthesis process adopting liquid acid and other catalytic systems is gradually eliminated due to high process cost, poor product quality, high pollution and the like. The mixed metal salt system disclosed in patent CN109865521B, however, complicates the separation and purification of the product and is accompanied by the loss of the metal salt catalyst. Therefore, it is very important to develop a preparation method of tert-butyl hydroquinone with high efficiency, low cost, less by-products and catalyst reusability.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a supported catalyst and application thereof in preparing tert-butylhydroquinone.
Based on the purpose, the invention adopts the following technical scheme:
the invention provides a supported catalyst. The invention further provides an application of the supported catalyst in a process of preparing tert-butyl hydroquinone, in the application process, 2-tert-butyl phenol is used as a raw material, the supported catalyst is added, the concentration of tert-butyl hydroquinone in a substrate after reaction and the selectivity in the reaction process are greatly improved, by using the supported catalyst, the content of tert-butyl hydroquinone in the substrate after reaction reaches 75-90 wt%, and the selectivity in the reaction process reaches 71-85%.
The invention provides a supported catalyst in a first aspect, which comprises a carrier and an active component; wherein the carrier is a molecular sieve or a metal oxide, and the active component is Cu + 、Cu 2+ 、Ag + 、Fe 3+ 、Mg 2+ 、Cr 3+ 、Ni 2+ 、Zn 2+ 、Cd 2+ At least one of (1).
Preferably, the loading amount of the active component is 0.1wt% to 20wt%.
Preferably, the molecular sieve is at least one of ZSM-5, beta and MCM-41; the metal oxide is Al 2 O 3 、ZrO 2 、Nb 2 O 5 At least one of (1).
In a second aspect, the present invention provides the use of the supported catalyst of the first aspect in the preparation of tert-butylhydroquinone.
Preferably, the specific operation steps for preparing the tert-butylhydroquinone by using the supported catalyst are as follows: adding tert-butyl phenol, an organic solvent and an oxidation catalyst into a reaction kettle, and reacting in an oxygen atmosphere to generate an intermediate product, namely tert-butyl benzoquinone; adding the tert-butyl benzene diquinone, the organic solvent and the hydrogenation catalyst into a hydrogenation reaction kettle, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain a final product tert-butyl benzenediol; wherein the oxidation catalyst and the hydrogenation catalyst are both the supported catalyst of the first aspect, and the hydrogenation catalyst has a higher degree of reduction than the oxidation catalyst.
Preferably, the preparation method of the oxidation catalyst is as follows: loading the active component on a carrier molecular sieve or a metal oxide by adopting an impregnation method, roasting, and carrying out oxidation-reduction reaction with 5% hydrogen for 0.5-2h to obtain the oxidation catalyst.
Preferably, the preparation method of the hydrogenation catalyst comprises the following steps: loading active components on a carrier molecular sieve or a metal oxide by adopting an impregnation method, roasting, and carrying out redox reaction with hydrogen for 2-6h to obtain the hydrogenation catalyst.
More preferably, the impregnation method is an equal volume impregnation method.
Preferably, the amount of the oxidation catalyst is 1 to 50 weight percent of the mass of the tert-butyl phenol; the dosage of the hydrogenation catalyst is 1wt% -50wt% of the mass of the tert-butyl benzoquinone.
More preferably, the tert-butylphenol is 2-tert-butylphenol; the organic solvent is methanol, acetonitrile, ethyl formate, methyl acetate, ethyl acetate or diethyl ether.
Preferably, the mass ratio of the tert-butyl phenol to the organic solvent is 1 to (3-10). More preferably, the mass ratio of the tert-butyl phenol to the organic solvent is 1 (3-8); more preferably, the mass ratio of the tert-butyl phenol to the organic solvent is 1 (4-7); more preferably, the mass ratio of the tert-butyl phenol to the organic solvent is 1 (5-6); most preferably, the mass ratio of tert-butylphenol to organic solvent is 1.
Preferably, the specific steps of the reaction in the reaction kettle under an oxygen atmosphere are as follows: introducing oxygen into the closed reaction kettle, keeping the pressure in the reaction kettle at 0.5-2Mpa, heating to 30 ℃ under the stirring condition, and reacting for 3-12h. More preferably, the total volume of the various materials after being added into the reaction kettle is not more than 2/3 of the internal capacity of the reaction kettle.
More preferably, after the oxygen is introduced, the pressure in the reaction kettle is controlled to be 0.7-1.5MPa; more preferably, the pressure inside the reaction vessel after the introduction of oxygen is controlled to 0.5MPa, 0.8MPa or 1MPa.
More preferably, the stirring condition is magnetic stirring, the rotating speed of the magnetic stirring for the reaction is 500-1000r/min, and the stirring time is consistent with the reaction time; more preferably, the rotational speed of the magnetic stirring of the reaction is 700r/min, 800r/min or 900r/min.
More preferably, the reaction is kept for 6 to 10 hours in the reaction kettle under the condition of stirring and reacting; more preferably, the reaction is maintained for 8 hours while stirring.
More preferably, the reaction still further comprises a post-treatment step after the reaction in the reaction kettle, wherein the post-treatment step specifically comprises: after the reaction is finished, stopping stirring, pouring out materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as first filtrate; treating the obtained first filtrate by a rotary evaporator, removing the organic solvent, and carrying out gas stripping on the residual bottom materials by using water vapor to obtain an intermediate product, namely tert-butyl-p-phenylenediamine; wherein, the obtained first filter cake is recycled. More preferably, the organic solvent used in the washing is an organic solvent added into the reaction kettle for reaction.
More preferably, in the post-treatment process after the reaction in the reaction kettle, the filtration is carried out by using a sand core funnel, and the vacuum degree during the suction filtration operation is-0.1 MPa; the treatment condition of the rotary evaporator is 30 ℃ and the vacuum degree is-0.1 MPa; deionized water was added to the remaining bed material, and the mixture was heat stripped at 150 ℃.
More preferably, the yield of the intermediate product tert-butyl p-benzoquinone is 55-90%.
More preferably, the first filter cake can be directly added into the reaction system as a catalyst for recycling. More preferably, when the first cake is used as a catalyst, an appropriate amount of an oxidation catalyst may be added and used together, if necessary.
Preferably, the intermediate product tert-butyl benzene diquinone hydrogenation reaction step specifically comprises: adding the tert-butyl p-phenylenediamine, the organic solvent and the hydrogenation catalyst into a hydrogenation reaction kettle, sealing the hydrogenation reaction kettle, vacuumizing, introducing hydrogen, keeping the pressure in the hydrogenation reaction kettle at 0.5-3Mpa, heating to 80-110 ℃ under the stirring condition, and carrying out hydrogenation reaction.
More preferably, the hydrogenation catalyst is a deeply reduced supported catalyst; the hydrogenation catalyst is more reductive than the oxidation catalyst.
More preferably, the stirring condition is magnetic stirring, and the rotating speed of the magnetic stirring of the hydrogenation reaction is 900r/min; the temperature rise rate of the hydrogenation reaction kettle for carrying out hydrogenation reaction temperature rise is 10 ℃/min.
More preferably, the hydrogenation reaction kettle further comprises a post-treatment step after the hydrogenation reaction, wherein the post-treatment step specifically comprises: after the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain a crude product of the tert-butyl hydroquinone; wherein the content of the tert-butyl hydroquinone is 75wt% -90wt%. More preferably, the organic solvent used in the washing is an organic solvent added into the hydrogenation reaction kettle for reaction.
More preferably, the second filter cake can be used as a hydrogenation catalyst and directly added into the reaction system for recycling; and when the second filter cake is directly recycled, in order to prevent the catalyst from being deactivated, methanol is added in the recycling process to carry out regeneration treatment on the second filter cake.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the supported catalyst, disperses the active components of the catalyst on the carrier by taking the molecular sieve or the metal oxide as the carrier, can have catalytic oxidation and catalytic reduction performances through different treatment steps, and is a multifunctional catalyst. The load type catalyst reduces the loss of metal salt in the reaction process, greatly reduces the consumption of the metal salt, further saves the cost, combines the control of each condition in the reaction process and a large amount of experimental optimization, ensures that the whole reaction process obtains higher yield of a target product, namely tert-butyl hydroquinone (TBHQ), and greatly reduces side reactions. Meanwhile, the hydrogenation reaction enables the content of the target product tert-butyl hydroquinone in the crude product to reach 75-90 wt%, the content of the byproduct di-tert-butyl hydroquinone is controlled at an extremely low level, and the selectivity of the target product tert-butyl hydroquinone can reach 71-85% after the whole reaction process is finished.
(2) The invention adopts the supported catalyst, does not need to directly add metal salt in a reaction system, leads the separation process of the catalyst after the reaction to be simpler and more convenient, does not need to separate the metal salt, does not generate salt waste, improves the product purity and reduces the treatment cost of three wastes.
(3) The invention adopts 2-tert-butyl phenol as raw material, and greatly reduces the production cost compared with the prior synthesis technology.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
Example 1
This example provides an oxidation catalyst, which is prepared by the following steps: cu (NO) at a loading of 5wt% (compared to the mass of molecular sieve) 3 ） 2 Adding waterPreparing a 1mol/L solution, impregnating a ZSM-5 molecular sieve, heating to remove moisture, roasting at 550 ℃ for 4 hours, then reducing at 400 ℃ for 0.5 hour in a 5% hydrogen atmosphere, and reducing 2-valent copper ions into 1-valent cuprous ions to obtain the oxidation catalyst.
The embodiment provides a hydrogenation catalyst, which comprises the following specific preparation steps: taking Ni (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butylhydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the reaction kettle, maintaining the pressure in the reaction kettle at 1Mpa through the oxygen for 4 th time, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; treating the obtained first filtrate by a rotary evaporator to remove the organic solvent methanol, and then carrying out steam stripping on the residual substrate to obtain an intermediate product tert-butyl-p-benzoquinone with a reaction yield of 75%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C under-0.1 Mpa. The stripping conditions are as follows: after the methanol had evaporated completely, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; and closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotating speed of 900r/min, and carrying out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 71%.
Example 2
This example provides an oxidation catalyst, which is prepared by the following steps: cu (NO) at a loading of 5wt% 3 ） 2 Adding water to prepare 1mol/L solution, soaking Beta molecular sieve, heating to remove water, roasting at 550 ℃ for 4h, and then reducing at 400 ℃ for 0.5h in 5% hydrogen atmosphere to obtain the oxidation catalyst.
This example provides a hydrogenation catalyst, which includes the following specific steps: taking Ni (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a Beta molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butylhydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the kettle, maintaining the pressure in the kettle at 1Mpa by oxygen for 4 times, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; and treating the obtained first filtrate by using a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely tert-butyl-p-phenylenediamine, wherein the reaction yield is 77%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C and vacuum degree of-0.1 Mpa. The stripping conditions are as follows: after the methanol had completely evaporated, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; and closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotating speed of 900r/min, and carrying out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 73%.
Example 3
This example provides an oxidation catalyst, which is prepared by the following steps: cu (NO) at a loading of 5wt% 3 ） 2 Adding water to prepare a 1mol/L solution, soaking an MCM-41 molecular sieve, heating to remove moisture, roasting at 550 ℃, and then reducing for 0.5h at 400 ℃ in a 5% hydrogen atmosphere to obtain the oxidation catalyst.
The embodiment provides a hydrogenation catalyst, which comprises the following specific preparation steps: taking Ni (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a 1mol/L solution, soaking an MCM-41 molecular sieve, heating to remove moisture, roasting at 550 ℃ for 4 hours, and then reducing in a hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butylhydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the kettle, maintaining the pressure in the kettle at 1Mpa by oxygen for 4 times, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; and treating the obtained first filtrate by using a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely tert-butyl-p-phenylenediamine, wherein the reaction yield is 79%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C and vacuum degree of-0.1 Mpa. The stripping conditions are as follows: after the methanol had completely evaporated, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, and heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotation speed of 900r/min, so as to carry out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 76%.
Example 4
This example provides an oxidation catalyst, which is prepared by the following steps: cu (NO) at a loading of 5wt% 3 ） 2 、Cr(NO 3 ) 3 Adding water according to the mass ratio of 1: 1 to prepare a solution with the solute concentration of 1mol/L, impregnating a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4h, and then reducing at 400 ℃ for 0.5h in a 5% hydrogen atmosphere to obtain the oxidation catalyst.
The embodiment provides a hydrogenation catalyst, which comprises the following specific preparation steps: taking Ni (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butyl hydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the kettle, maintaining the pressure in the kettle at 1Mpa by oxygen for 4 times, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; treating the obtained first filtrate by a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely the tert-butyl p-benzoquinone, wherein the reaction yield is 90%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C and vacuum degree of-0.1 Mpa. The stripping conditions are as follows: after the methanol had evaporated completely, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-benzoquinone and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, and heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotation speed of 900r/min, so as to carry out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 85%.
Example 5
This example provides an oxidation catalyst, which is prepared by the following steps: cu (NO) at a loading of 5wt% 3 ） 2 、Zn（NO 3 ） 2 Adding water according to the mass ratio of 1: 1 to prepare a solution with the solute concentration of 1mol/L, impregnating a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4h, and then reducing at 400 ℃ for 0.5h in a 5% hydrogen atmosphere to obtain the oxidation catalyst.
The embodiment provides a hydrogenation catalyst, which comprises the following specific preparation steps: taking Ni (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butyl hydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the reaction kettle, maintaining the pressure in the reaction kettle at 1Mpa through the oxygen for 4 th time, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; and treating the obtained first filtrate by using a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely tert-butyl-p-phenylenediamine, wherein the reaction yield is 88%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C and vacuum degree of-0.1 Mpa. The stripping conditions are as follows: after the methanol had completely evaporated, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; and closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotating speed of 900r/min, and carrying out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 83%.
Example 6
This example provides an oxidation catalyst, which is prepared by the following steps: at a loading of 5wt%, cr (NO) 3 ） 3 、Zn（NO 3 ） 2 Adding water according to the mass ratio of 1: 1 to prepare a solution with the solute concentration of 1mol/L, impregnating a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4h, and then reducing at 400 ℃ for 0.5h in 5% hydrogen atmosphere to obtain the oxidation catalyst.
This example provides a hydrogenation catalyst, which was prepared by the following specific stepsComprises the following steps: taking Cu (NO) according to the loading of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butylhydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the kettle, maintaining the pressure in the kettle at 1Mpa by oxygen for 4 times, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; treating the obtained first filtrate by a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely the tert-butyl p-benzoquinone, wherein the reaction yield is 56%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C under-0.1 Mpa. The stripping conditions are as follows: after the methanol had evaporated completely, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; and closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotating speed of 900r/min, and carrying out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 51%.
Example 7
This example provides an oxidation catalyst, which is prepared by the following steps: at a loading of 5wt%, cr (NO) 3 ） 2 、Cd（NO 3 ） 2 Adding water according to the mass ratio of 1: 1 to prepare a solution with the solute concentration of 1mol/L, impregnating a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4h, and then reducing at 400 ℃ for 0.5h in 5% hydrogen atmosphere to obtain the oxidation catalyst.
The embodiment provides a hydrogenation catalyst, which comprises the following specific preparation steps: taking Cu (NO) according to the load of 5wt percent 3 ） 2 Adding water to prepare a solution with the concentration of 1mol/L, soaking a ZSM-5 molecular sieve, heating to remove water, roasting at 550 ℃ for 4 hours, and then reducing in hydrogen atmosphere at 400 ℃ for 2 hours to obtain the hydrogenation catalyst.
The embodiment provides an application of preparing tert-butylhydroquinone by using the oxidation catalyst and the hydrogenation catalyst, and the application process comprises the following steps:
(1) Weighing 1.5g of oxidation catalyst, adding the oxidation catalyst into a reaction kettle, and adding 15g of raw material 2-tert-butylphenol and 85g of organic solvent methanol into the reaction kettle, wherein the mass ratio of the raw material to the solvent is 1; the capacity of the reaction kettle is 200mL, and the total volume of the added materials is not more than 2/3 of the capacity of the reaction kettle.
(2) Closing the reaction kettle, sealing, introducing oxygen into the reaction kettle, introducing oxygen for 3 times to replace air in the kettle, maintaining the pressure in the kettle at 1Mpa by oxygen for 4 times, heating the reaction kettle to 30 ℃ under the condition of magnetic stirring, and keeping the reaction state for 8 hours while stirring.
(3) After the reaction is finished, stopping stirring, pouring out the materials in the reaction kettle, cooling to room temperature to form a suspension, and filtering the suspension to obtain a first filter cake; washing the first filter cake for at least 3 times by using methanol, and collecting filtrate obtained in the whole suction filtration process as first filtrate; and treating the obtained first filtrate by using a rotary evaporator to remove the organic solvent, and then carrying out steam stripping on the residual substrate to obtain an intermediate product, namely tert-butyl-p-phenylenediamine, wherein the reaction yield is 61%. Wherein, the first filter cake is recycled.
The conditions of the rotary evaporator are as follows: evaporating at 30 deg.C under-0.1 Mpa. The stripping conditions are as follows: after the methanol had evaporated completely, 100mL of deionized water was added and stripped at 150 ℃.
(4) Adding 15g of the obtained intermediate product tert-butyl p-phenylenediamine and 85g of solvent methanol into a hydrogenation reaction kettle, and adding 1.5g of hydrogenation catalyst; closing the hydrogenation reaction kettle, sealing, vacuumizing the hydrogenation reaction kettle, introducing hydrogen into the hydrogenation reaction kettle, controlling the pressure of the hydrogen in the kettle to be 0.8Mpa, and heating the hydrogenation reaction kettle to 80 ℃ at a programmed heating rate of 10 ℃/min under the magnetic stirring at a rotation speed of 900r/min, so as to carry out hydrogenation reaction for 3 hours.
(5) After the hydrogenation reaction is finished, pouring out the material in the hydrogenation reaction kettle, cooling to room temperature, and filtering to obtain a second filter cake; washing the second filter cake for at least 3 times by using an organic solvent, and collecting filtrate obtained in the whole suction filtration process as second filtrate; and treating the second filtrate by using a falling film evaporator, and removing the organic solvent to obtain the tert-butyl hydroquinone, wherein the selectivity of the tert-butyl hydroquinone is 57%.
In conclusion, the invention effectively overcomes the defects in the prior art and has high industrial utilization value. The above-described embodiments are intended to illustrate the substance of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention.

Claims (8)

1. The application of the supported catalyst in preparing the tert-butyl hydroquinone is characterized in that the specific operation steps of preparing the tert-butyl hydroquinone by using the supported catalyst are as follows: adding tert-butyl phenol, an organic solvent and an oxidation catalyst into a reaction kettle, and reacting in an oxygen atmosphere to generate an intermediate product, namely tert-butyl benzenediquinone; adding the tert-butyl benzene diquinone, an organic solvent and a hydrogenation catalyst into a hydrogenation reaction kettle, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain a final product tert-butyl benzene diphenol; wherein, the oxidation catalyst and the hydrogenation catalyst are both supported catalysts, and the reduction degree of the hydrogenation catalyst is higher than that of the oxidation catalyst;
the supported catalyst comprises a carrier and an active component; the carrier is a molecular sieve or a metal oxide, and the active component is Cu + 、Cu 2+ 、Ag + 、Fe 3+ 、Mg 2+ 、Cr 3+ 、Ni 2+ 、Zn 2+ 、Cd 2+ At least one of (1).
2. The use of the supported catalyst according to claim 1 in the preparation of tert-butylhydroquinone, wherein the loading of the active component is 0.1wt% to 20wt% of the mass of the support.
3. The use of the supported catalyst of claim 2 for the preparation of tert-butylhydroquinone, wherein the molecular sieve is at least one of ZSM-5, beta, MCM-41; the metal oxide is Al 2 O 3 、ZrO 2 、Nb 2 O 5 At least one of (a).
4. Use of the supported catalyst of claim 1, 2 or 3 in the preparation of tert-butylhydroquinone, characterized in that the oxidation catalyst is prepared by a process comprising: loading the active component on a carrier molecular sieve or a metal oxide by adopting an impregnation method, roasting, and carrying out oxidation-reduction reaction with 5% hydrogen for 0.5-2h to obtain an oxidation catalyst; the preparation method of the hydrogenation catalyst comprises the following steps: loading active components on a carrier molecular sieve or a metal oxide by adopting an impregnation method, roasting, and carrying out redox reaction with hydrogen for 2-6h to obtain the hydrogenation catalyst.
5. The use of the supported catalyst in the preparation of tert-butylhydroquinone according to claim 4, wherein the amount of the oxidation catalyst is 1-50 wt% of the mass of tert-butylphenol; the dosage of the hydrogenation catalyst is 1wt% -50wt% of the mass of the tert-butyl benzoquinone.
6. The use of the supported catalyst of claim 1 in the preparation of tert-butyl hydroquinone, wherein said tert-butyl phenol is 2-tert-butyl phenol; the organic solvent is methanol, acetonitrile, ethyl formate, methyl acetate, ethyl acetate or diethyl ether; the mass ratio of the tert-butyl phenol to the organic solvent is 1: 3-10; the mass ratio of the tert-butyl benzoquinone to the organic solvent is 1: 3-10.
7. The use of the supported catalyst in the preparation of tert-butylhydroquinone according to claim 1, wherein the reaction in the reaction kettle is carried out in an oxygen atmosphere by the specific steps of: introducing oxygen into the closed reaction kettle, keeping the pressure in the reaction kettle at 0.5-2Mpa, heating to 30 ℃ under the stirring condition, and reacting for 3-12h.
8. The use of the supported catalyst in the preparation of tert-butylhydroquinone according to claim 1, wherein the specific steps of the hydrogenation reaction of tert-butylbenzenediquinone in a hydrogen atmosphere are as follows: and (3) sealing the hydrogenation reaction kettle, vacuumizing, introducing hydrogen, keeping the pressure in the hydrogenation reaction kettle at 0.5-3Mpa, heating to 80-110 ℃ under the stirring condition, and carrying out hydrogenation reaction.
CN202210797166.5A 2022-07-08 2022-07-08 Supported catalyst and application thereof in preparation of tert-butylhydroquinone Active CN115069294B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210797166.5A CN115069294B (en) 2022-07-08 2022-07-08 Supported catalyst and application thereof in preparation of tert-butylhydroquinone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210797166.5A CN115069294B (en) 2022-07-08 2022-07-08 Supported catalyst and application thereof in preparation of tert-butylhydroquinone

Publications (2)

Publication Number Publication Date
CN115069294A CN115069294A (en) 2022-09-20
CN115069294B true CN115069294B (en) 2023-04-14

Family

ID=83258155

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210797166.5A Active CN115069294B (en) 2022-07-08 2022-07-08 Supported catalyst and application thereof in preparation of tert-butylhydroquinone

Country Status (1)

Country Link
CN (1) CN115069294B (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08176043A (en) * 1994-12-26 1996-07-09 Honshu Chem Ind Co Ltd Method for simultaneously producing high-purity 2-t-butylhydroquinone and 2,5-di-t-butylhydroquinone
EP0812816A4 (en) * 1995-01-20 1998-04-29 Seiko Kagaku Kabushiki Kaisha Process for producing quinones
CN101973858A (en) * 2010-10-11 2011-02-16 浙江大学 Method for synthesizing tert-butylated hydroxyanisole through solid-liquid-phase reaction
CN104190465B (en) * 2014-09-05 2016-08-24 福州大学 A kind of photocatalyst of the molecular sieve carried metal-oxide of SAPO-5
CN106866345B (en) * 2015-12-12 2020-06-02 中国科学院大连化学物理研究所 Method for preparing JP-10 aviation fuel from furfuryl alcohol
CN107252688A (en) * 2017-05-15 2017-10-17 北京石油化工学院 A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application
CN109865521B (en) * 2019-03-20 2020-04-28 北京化工大学 Mixed metal catalyst for preparing tert-butylhydroquinone and preparation method of tert-butylhydroquinone
CN111068770A (en) * 2019-12-14 2020-04-28 陕西煤业化工技术研究院有限责任公司 Supported catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, and preparation method and application thereof
CN111099996A (en) * 2019-12-28 2020-05-05 太仓运通新材料科技有限公司 Preparation method of tert-butyl acrylate

Also Published As

Publication number Publication date
CN115069294A (en) 2022-09-20

Similar Documents

Publication Publication Date Title
CN112341312A (en) Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin
CN115069294B (en) Supported catalyst and application thereof in preparation of tert-butylhydroquinone
CN113893880A (en) Preparation method and application of MIL-125(Ti) catalyst
EP3463658B1 (en) Process for preparing a catalyst and use thereof
CN111116444B (en) Process for synthesis of caprolactam
CN113070096A (en) Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof
CN112387280A (en) Method for preparing isopentenal by oxidizing enol
CN114621097B (en) Method for preparing 2, 4-difluoroaniline by catalytic hydrogenation of 2, 4-difluoronitrobenzene
CN109865521B (en) Mixed metal catalyst for preparing tert-butylhydroquinone and preparation method of tert-butylhydroquinone
CN101564691B (en) Method for preparing 4,4-diaminodiphenylether and a preparation method of hydrogenation catalyst used therein
KR100995465B1 (en) A Catalyst For Putifying 2,6-Naphthalene Dicarboxylic Acid, A Method For Preparing Thereof And Purifying Process Using The Catalyst
CN114618573B (en) Embedded Ni-based catalyst, preparation method and application
CN112121848B (en) Modified hierarchical pore molecular sieve catalyst, preparation method thereof and production method of 3-methyl-2-butene-1-ol
CN115591562A (en) Black phosphorus modified copper-based catalyst and new application thereof in organic matter hydrogenation reduction reaction
CN111499858B (en) Refining method of high-viscosity polymer crude product
CN101817727A (en) Treatment method of front cut fractions during production process of o-phenyl phenol
CN113354510B (en) Phenol selective hydrogenation method on Na modified NiCo catalyst
CN110885062B (en) Pretreatment method of 2-alkyl anthraquinone working solution and production method of hydrogen peroxide
CN115055187B (en) Copper doped beta-Bi 2 O 3 Preparation method of crystal catalyst and benzene series wastewater purification method
CN117049763B (en) Method for degrading sludge organic matters by wet oxidation technology
CN115532223B (en) Adsorbent for removing thiophenic sulfur and preparation method and application thereof
CN114832782B (en) Deoxidizing adsorbent for Fischer-Tropsch light distillate oil adsorption-rectification coupling technology and preparation method thereof
CN114702373B (en) Method for preparing acetal by molecular sieve reaming adsorption of lanthanide series trimellitic salt catalyst
CN115504877A (en) Method for purifying pyromellitic formic acid
CN111992208B (en) Preparation method of organic alcohol treated propane dehydrogenation catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant