CN116354793A - Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst - Google Patents

Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst Download PDF

Info

Publication number
CN116354793A
CN116354793A CN202111633912.9A CN202111633912A CN116354793A CN 116354793 A CN116354793 A CN 116354793A CN 202111633912 A CN202111633912 A CN 202111633912A CN 116354793 A CN116354793 A CN 116354793A
Authority
CN
China
Prior art keywords
ionic liquid
anthraquinone
bimetallic
catalyst
hydrogenation reaction
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.)
Pending
Application number
CN202111633912.9A
Other languages
Chinese (zh)
Inventor
李韡
张金利
李晓燕
王福迎
李晓蕾
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.)
Tianjin University
Original Assignee
Tianjin University
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 Tianjin University filed Critical Tianjin University
Priority to CN202111633912.9A priority Critical patent/CN116354793A/en
Publication of CN116354793A publication Critical patent/CN116354793A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses an anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst, which comprises the following steps: step 1, placing a reduced catalyst and anthraquinone working solution in a reactor, and replacing gas in the reactor with hydrogen before reaction, wherein the catalyst comprises a catalyst carrier, and a metal palladium compound, an auxiliary metal compound and an ionic liquid which are loaded on the catalyst carrier, and the auxiliary metal compound is yttrium metal compound or zinc metal compound; step 2, the temperature in the reactor to be reacted is increased to the working temperature, and H is introduced 2 Keeping the pressure in the reaction kettle stable at the working pressure, and continuously stirring until the reaction is completed; and step 3, adding a mixed solution of phosphoric acid and deionized water after the reaction is finished, introducing oxygen to fully oxidize the mixed solution, and extracting to obtain a system containing hydrogen peroxide. The method can prepare high-concentration H 2 O 2 。

Description

Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst
Technical Field
The invention relates to the technical field of anthraquinone hydrogenation reaction, in particular to an anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst.
Background
Hydrogen peroxide (H) 2 O 2 ) As a clean chemical product, the fiber-washing agent is widely applied to aspects of fiber bleaching, organic synthesis, environmental protection and the like. In recent years, with the application in the processes of propylene epoxidation to prepare propylene oxide, green caprolactam synthesis and the like, the domestic hydrogen peroxide industry is brought into a new development opportunity. In industry, H 2 O 2 The anthraquinone method is usually adopted for preparation, and the total amount of the anthraquinone is more than 95 percent. In the process, the catalytic hydrogenation of 2-ethyl anthraquinone (2-eAQ) to 2-ethyl hydroanthraquinone is a core step, and the commonly used catalyst is palladium aluminum oxide catalyst (Pd/Al 2 O 3 ) How to increase the activation ability of two carbonyl groups (c=o) in the catalyst activation 2-eAQ to increase hydrogenation efficiency and selectivity is one of the important points of current research.
Single metal Pd/Al prepared by the prior art 2 O 3 Has the defects of low dispersivity and insufficient catalytic performance. The palladium-based catalyst is the most commonly used catalyst for anthraquinone hydrogenation reaction, but has the problems of low hydrogenation efficiency, poor stability and the like. The scholars at home and abroad increase Pd/gamma-Al by adding auxiliary agent (second metal or third metal), modifying carrier and adjusting preparation method 2 O 3 Catalytic performance of the catalyst. However, there are problems such as large Pd metal particles, poor dispersibility, weak interaction between the active ingredient and the carrier, which results in low productivity and limitation of high concentration of H 2 O 2 (50%) production of the product.
Disclosure of Invention
The invention aims to provide an anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst aiming at the problems existing in the production process of hydrogen peroxide products in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
an anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst comprises the following steps:
step 1, placing a reduced catalyst and anthraquinone working solution in a reactor, and replacing gas in the reactor with hydrogen before reaction, wherein the catalyst comprises a catalyst carrier, and a metal palladium compound, an auxiliary metal compound and an ionic liquid which are loaded on the catalyst carrier, and the auxiliary metal compound is yttrium metal compound or zinc metal compound;
step 2, the temperature in the reactor to be reacted is increased to the working temperature, and H is introduced 2 Keeping the pressure in the reaction kettle stable at the working pressure, and continuously stirring until the reaction is completed;
and step 3, adding a mixed solution of phosphoric acid and deionized water after the reaction is finished, introducing oxygen to fully oxidize the mixed solution, and extracting to obtain a system containing hydrogen peroxide.
In the technical scheme, in the step 2, after the temperature in the reactor is raised to 60-80 ℃ and stabilized, the rotating speed of the reactor is raised to 800-1500rpm, and H is introduced 2 Keeping the pressure in the reaction kettle to be stable at 0.2-0.6MPa; the reaction time is 10-60min.
In the above technical solution, in the step 1, the catalyst is reduced by a hydrogen-argon mixture, sodium borohydride, ascorbic acid, hydrazine hydrate, formaldehyde, methanol or sodium citrate, preferably, by a hydrogen-argon mixture.
In the above technical scheme, the anthraquinone working solution in the step 1 is a working solution obtained by dissolving 2-ethyl anthraquinone in a mixed solvent of 1,2, 4-trimethylbenzene and tri (2-ethylhexyl) phosphate.
In the technical scheme, in the step 1, the concentration of the 2-ethyl anthraquinone in the anthraquinone working solution is 100-200g/L.
In the above technical scheme, in the step 3, in the mixed solution of phosphoric acid and deionized water, the volume ratio of phosphoric acid to deionized water is (2-5): 20, the concentration of phosphoric acid is 2-8mol/L.
In the above technical scheme, the ratio of the mass parts of the reduced catalyst in the step 1 to the volume parts of the anthraquinone working solution is (0.3-1.0): (0.03-0.12), wherein the unit of the mass parts is g, and the unit of the volume parts is L.
In the above technical scheme, the catalyst carrier in the step 1 is a porous solid material carrier, preferably γ -Al 2 O 3 SBA-15 molecular sieves, silica, titania or carbon materials, more preferably, the catalyst support is gamma-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Further, gamma-Al 2 O 3 Has a specific surface area of 50-500m 2 And/g, the pore diameter is 5-20nm.
In the technical scheme, the metal palladium compound is sodium tetrachloropalladate, palladium chloride, palladium acetate, palladium nitrate, palladium acetylacetonate, diamminedichloropalladium, ammonium tetrachloropalladate or tetraamminepalladium nitrate;
in the above technical solution, the yttrium metal compound is yttrium nitrate, yttrium sulfate, yttrium carbonate or yttrium bromide, preferably yttrium nitrate;
the zinc metal compound is zinc nitrate, zinc chloride, zinc sulfate, zinc sulfide, preferably zinc nitrate.
In the technical scheme, the ionic liquid is 1-butyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole acetate, 1-butyl sulfonic acid-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole methylsulfonate or 1-butyl-3-methylimidazole dihydrogen phosphate.
In the technical scheme, based on the mass of the catalyst carrier, the ratio of the load of the metal palladium compound calculated by palladium, the load of the auxiliary metal compound calculated by auxiliary metal and the load of the ionic liquid is (0.1-1): (0.1-1): (2-10), wherein the load is the mass percent of the substance to the carrier.
Compared with the prior art, the invention has the beneficial effects that:
1. the method can prepare high-concentration H 2 O 2 (50%) of the product, effectively improve H 2 O 2 The quality and the production efficiency of the product.
2. In the bimetallic-ionic liquid supported catalyst, the size of the nano particles is limited in the metal nano particle forming process through the unique space limiting action, electrostatic action and interaction between the ionic liquid and metal of the ionic liquid, so that the metal nano particles are stabilized, the dispersity of the metal nano particles is improved, and the aggregation phenomenon is reduced.
3. The geometry and the electronic effect of the active component of the catalyst are improved by adding a second metal (a metal zinc compound or a metal Y compound), so that the catalytic efficiency of the palladium metal nano particles is improved. Meanwhile, the ionic liquid interacts with the catalyst carrier, so that the interaction between the palladium nano metal and the catalyst carrier is enhanced, the problem that active components of the catalyst are easy to run off in the use process is solved, and the stability of the palladium metal catalyst is improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
According to the load amount listed in table 1, the measured sodium chloropalladate, the auxiliary metal and the ionic liquid impregnating solution are dispersed and mixed to obtain an ionic liquid-bimetallic impregnating solution; the auxiliary metal is Zn or Y, and gamma-Al is used as the auxiliary metal 2 O 3 Adding the carrier into the mixed impregnating solution, stirring at 45 ℃ for 1.5h, aging at 45 ℃ and standing for 3h, filtering and washing, and drying in an oven at 80 ℃ for 12h to obtain the supported ionic liquid bimetallic catalyst.
Reducing the catalyst at 150 ℃ for 4 hours at a heating rate of 5 ℃/min with 10% H 2 90% Ar mixture.
The reduced catalyst is used for carrying out anthraquinone hydrogenation reaction and carrying out activity evaluation, and the specific steps are as follows:
step 1, placing 0.6g of reduced catalyst and 60mL of anthraquinone working solution in a kettle reactor, and replacing gas in the reaction kettle with hydrogen for 5 times before reaction, wherein the anthraquinone working solution is a 2-ethylanthraquinone solution with the concentration of 120g/L, and the solvent in the 2-ethylanthraquinone solution is a mixed solvent of 1,2, 4-trimethylbenzene and tri (2-ethylhexyl) phosphate;
step 2, waiting for the temperature in the reaction kettleAfter the temperature is raised to 60 ℃ and stabilized, the rotating speed of the reaction kettle is raised to 1000rpm, and H is introduced 2 The pressure in the reaction kettle is kept stable at 0.3MPa;
step 3, after reacting for 15min, stopping stirring, opening the reaction kettle, placing 2mL of the reacted working solution into a separating funnel, adding a mixed solution of 2mL of phosphoric acid and 20mL of deionized water into the separating funnel, and then introducing oxygen into the solution in the separating funnel to fully oxidize the solution, wherein the concentration of the phosphoric acid is 5mol/L;
and 4, oxidizing for 30min, extracting, transferring a water layer containing hydrogen peroxide in a separating funnel into the separating funnel, flushing with deionized water for 3 times, adding 5mL of sulfuric acid, and titrating and analyzing the amount of hydrogen peroxide in the water phase with calibrated potassium permanganate, wherein the concentration of the sulfuric acid is 3mol/L, and the concentration of the potassium permanganate is 0.0235mol/L.
The evaluation results of the hydrogenation efficiency of the auxiliary metal species (M), the ionic liquid species and 15min in the catalyst are shown in the following Table 1.
Table 1 examples 1-10 supported ionic liquid bimetallic catalyst and anthraquinone hydrogenation efficiency thereof
Examples Load (wt%) Ionic liquid species Hydrogen efficiency (g/L)
Example 1 Pd＝0.3，Y＝0.7，IL＝4 1-butyl-3-methylimidazole bisulfate 9.8
Example 2 Pd＝0.3，Y＝0.3，IL＝4 1-butyl-3-methylimidazole bisulfate 7.4
Example 3 Pd＝0.3，Y＝1.0，IL＝4 1-butyl-3-methylimidazole bisulfate 6.7
Example 4 Pd＝0.3，Zn＝0.7，IL＝4 1-butyl-3-methylimidazole bisulfate 8.0
The presence of Y improves the particle dispersity of the metal active component Pd, so that the active component Pd has more surface active centers, and the hydrogenation efficiency is improved. In addition, Y or Zn can form a complex with the imidazole ionic liquid, so that the surface acidity of the carrier is improved, the adsorption of anthraquinone molecules is facilitated, and the hydrogenation efficiency is improved.
The geometrical effect exists between Pd and Zn, which increases the number of isolated Pd atoms and is beneficial to Pd to be uniformly dispersed in Al 2 O 3 A surface; electron transfer exists between Pd and Zn, and Pd is improved 0 The content of the species improves the H 2 Is beneficial to improving hydrogenation efficiency.
Under the reaction conditions, as shown in comparative examples 1-9 below, the geometric effect or electronic effect of other metals and Pd is not obvious, and the addition of the auxiliary metal may mask the active site and increase the difficulty of combining with anthraquinone molecules, so that the hydrogenation efficiency is not high.
Comparative examples 1 to 9
The hydrogenation efficiency was evaluated by replacing the metal Y or Zn with another metal in the same manner as in example 1, as shown in table 2 below.
Table 2 comparative examples 1-9 Supported ionic liquid bimetallic catalysts and anthraquinone hydrogenation efficiency thereof
Comparative example Load (wt%) Auxiliary metal M Ionic liquid species Hydrogen efficiency (g/L)
Comparative example 1 Pd＝0.3，M＝0.7，IL＝3 La 1-butyl-3-methylimidazole methylsulfonate 4.8
Comparative example 2 Pd＝0.3，M＝0.7，IL＝4 Fe 1-butyl-3-methylimidazole bisulfate 5.0
Comparative example 3 Pd＝0.3，M＝0.7，IL＝4 Mg 1-butyl-3-methylimidazole bisulfate 6.9
Comparative example 4 Pd＝0.3，M＝0.7，IL＝3 Ca 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt 3.1
Comparative example 5 Pd＝0.3，M＝0.7，IL＝3 Co 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt 2.8
Comparative example 6 Pd＝0.3，M＝0.7，IL＝3 W 1-butyl-3-methylimidazole bromide 5.1
Comparative example 7 Pd＝0.3，M＝0.7，IL＝3 Mo 1-butyl-3-methylimidazole bromide 5.6
Comparative example 8 Pd＝0.3，M＝0.7，IL＝4 Li 1-butyl-3-methylimidazole bisulfate 4.4
Comparative example 9 Pd＝0.3，M＝0.7，IL＝4 La 1-butyl-3-methylimidazole bisulfate 5.8
Comparative examples 10 to 14
According to the load amount listed in Table 3, the measured sodium chloropalladate, the additive metal and the ionic liquid impregnating solution are dispersed and mixed to obtain an ionic liquid-bimetallic impregnating solution; other method steps are the same as above. The hydrogenation efficiency of the catalyst for 15min was evaluated as shown in Table 3 below.
Table 3 comparative examples 10-14 catalysts and their anthraquinone hydrogenation efficiencies
Comparative example Load amount Auxiliary metal M Hydrogen efficiency (g/L)
Comparative example 10 Pd＝0.3，M＝0.7，IL＝0 Y 3.5
Comparative example 11 Pd＝0，M＝0.7，IL＝0 Y 0.1
Comparative example 12 Pd＝0，M＝0.7，IL＝0 Zn 0.2
Comparative example 13 Pd＝0.3，M＝0.7，IL＝0 Zn 5.6
Comparative example 14 Pd＝0.3，M＝0，IL＝0 - 4.8
Comparative examples 10-11 compared with example 1, the catalyst was significantly reduced in hydrogen efficiency by removing the ionic liquid or the ionic liquid and the metallic palladium, and comparative examples 12-13 compared with example 4, the catalyst was significantly reduced in hydrogen efficiency by removing the ionic liquid or the ionic liquid and the metallic palladium, and as can be seen from comparative example 14, the catalyst was significantly reduced in hydrogen efficiency by removing the auxiliary metal and the ionic liquid.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. An anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst is characterized by comprising the following steps:
step 1, placing a reduced catalyst and anthraquinone working solution in a reactor, and replacing gas in the reactor with hydrogen before reaction, wherein the catalyst comprises a catalyst carrier, and a metal palladium compound, an auxiliary metal compound and an ionic liquid which are loaded on the catalyst carrier, and the auxiliary metal compound is yttrium metal compound or zinc metal compound;
step 2, the temperature in the reactor to be reacted is increased to the working temperature, and H is introduced 2 Keeping the pressure in the reaction kettle stable at the working pressure, and continuously stirring until the reaction is completed;
and step 3, adding a mixed solution of phosphoric acid and deionized water after the reaction is finished, introducing oxygen to fully oxidize the mixed solution, and extracting to obtain a system containing hydrogen peroxide.
2. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein in step 1, the catalyst is reduced by means of a hydrogen-argon mixture, sodium borohydride, ascorbic acid, hydrazine hydrate, formaldehyde, methanol or sodium citrate, preferably by means of a hydrogen-argon mixture.
3. The anthraquinone hydrogenation reaction based on a bimetallic-ionic liquid supported catalyst according to claim 1, wherein the anthraquinone working solution in the step 1 is a working solution obtained by dissolving 2-ethyl anthraquinone in a mixed solvent of 1,2, 4-trimethylbenzene and tri (2-ethylhexyl) phosphate.
4. The bimetallic-ionic liquid supported catalyst-based anthraquinone hydrogenation reaction according to claim 1, wherein in step 1, the concentration of 2-ethyl anthraquinone in the anthraquinone working solution is 100-200g/L.
5. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein in step 2, after the temperature in the reactor is raised to 60-80 ℃ and stabilized, the reactor rotation speed is raised to 800-1500rpm, and H is introduced 2 Keeping the pressure in the reaction kettle to be stable at 0.2-0.6MPa; the reaction time is 10-60min.
6. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein in the step 3, the volume ratio of phosphoric acid to deionized water in the mixed solution of phosphoric acid and deionized water is (2-5): 20, the concentration of phosphoric acid is 2-8mol/L.
7. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein the ratio of the mass parts of the reduced catalyst to the volume parts of the anthraquinone working solution in step 1 is (0.3-1.0): (0.03-0.12), wherein the unit of the mass parts is g, and the unit of the volume parts is L.
8. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein the catalyst support in step 1 is a porous solid material support, preferably γ -Al 2 O 3 SBA-15 molecular sieves, silica, titania or carbon materials, more preferably, the catalyst support is gamma-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Further, gamma-Al 2 O 3 Has a specific surface area of 50-500m 2 And/g, the pore diameter is 5-20nm.
9. The anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst according to claim 1, wherein the metallic palladium compound is sodium tetrachloropalladate, palladium chloride, palladium acetate, palladium nitrate, palladium acetylacetonate, diamminedichloropalladium, ammonium tetrachloropalladate or tetraammine palladium nitrate;
the yttrium metal compound is yttrium nitrate, yttrium sulfate, yttrium carbonate or yttrium bromide, preferably yttrium nitrate;
the zinc metal compound is zinc nitrate, zinc chloride, zinc sulfate or zinc sulfide, preferably zinc nitrate;
the ionic liquid is 1-butyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole acetate, 1-butyl sulfonic acid-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole methylsulfonate or 1-butyl-3-methylimidazole dihydrogen phosphate.
10. The bimetallic-ionic liquid supported catalyst-based anthraquinone hydrogenation reaction according to claim 1, wherein the ratio of the loading of the metallic palladium compound in terms of palladium, the loading of the promoter metal compound in terms of promoter metal, the loading of the ionic liquid is (0.1-1) based on the mass of the catalyst support: (0.1-1): (2-10), wherein the load is the mass percent of the substance to the carrier.
CN202111633912.9A 2021-12-28 2021-12-28 Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst Pending CN116354793A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111633912.9A CN116354793A (en) 2021-12-28 2021-12-28 Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111633912.9A CN116354793A (en) 2021-12-28 2021-12-28 Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst

Publications (1)

Publication Number Publication Date
CN116354793A true CN116354793A (en) 2023-06-30

Family

ID=86915034

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111633912.9A Pending CN116354793A (en) 2021-12-28 2021-12-28 Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst

Country Status (1)

Country Link
CN (1) CN116354793A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071487A (en) * 2013-01-29 2013-05-01 中国天辰工程有限公司 Hydrogenation catalyst for anthraquinone process fixed bed and preparation method of hydrogenation catalyst
CN104549246A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Palladium-based hydrogenation catalyst and application of palladium-based hydrogenation catalyst to anthraquinone hydrogenation
CN109939678A (en) * 2019-02-14 2019-06-28 北京氦舶科技有限责任公司 A kind of monatomic palladium catalyst and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071487A (en) * 2013-01-29 2013-05-01 中国天辰工程有限公司 Hydrogenation catalyst for anthraquinone process fixed bed and preparation method of hydrogenation catalyst
CN104549246A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Palladium-based hydrogenation catalyst and application of palladium-based hydrogenation catalyst to anthraquinone hydrogenation
CN109939678A (en) * 2019-02-14 2019-06-28 北京氦舶科技有限责任公司 A kind of monatomic palladium catalyst and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FUYING WANG, ET AL.: "Intensifying strategy of ionic liquids for Pd-based catalysts in anthraquinone hydrogenation", CATALYSIS SCIENCE & TECHNOLOGY, vol. 12, 21 December 2021 (2021-12-21), pages 1766 - 1776 *
丁彤 等: "过渡金属对Pd/γ-Al2O3催化剂活性的影响", 催化学报, vol. 23, no. 3, 31 December 2002 (2002-12-31), pages 227 - 230 *

Similar Documents

Publication Publication Date Title
CN1031927C (en) Carrier catalyst, process for preparation and use
CN102218345B (en) Catalyst for synthesizing vinylacetate and preparation method thereof
CN109939676A (en) Monatomic palladium catalyst and its preparation and the application in selective hydrogenation of acetylene
CN109603819B (en) Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof
CN103028398B (en) Method for preparing palladium carbon catalyst for hydrogenation and refining of crude terephthalic acid
CN109939675A (en) A kind of preparation and application of noble metal catalyst
CN101612580A (en) A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof
CN111437812A (en) Noble metal catalyst and preparation method and application thereof
CN117380183B (en) Preparation method and application of supported palladium nanoparticle catalyst
CN110314685B (en) Preparation method of core-shell structure catalyst for low-temperature catalytic oxidation of toluene
CN115608414A (en) Supported ionic liquid nano metal catalyst and preparation method and application thereof
CN116354793A (en) Anthraquinone hydrogenation reaction based on bimetallic-ionic liquid supported catalyst
CN113275002A (en) C/MoO2Porous photocatalyst and preparation method and application thereof
CN102371182B (en) Catalyst for synthesizing acetate propylene ester and preparation method thereof
EP3321249B1 (en) Method for producing acrylic acid
CN112246240B (en) Preparation and application of dimethyl carbonate catalyst
CN115611239B (en) Anthraquinone hydrogenation reaction method
CN110903175B (en) By using Au/alpha-Fe2O3Method for recycling volatile organic compounds by nanosheet catalyst
CN112191244A (en) Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation
CN112742422A (en) Supported catalyst and application thereof in selective hydrogenation of quinoline compounds
CN116550383B (en) Preparation method of unsaturated acetate and catalyst thereof
CN111420656A (en) Catalyst for preparing isooctanoic acid by selective oxidation of isooctanol and preparation method thereof
KR102220225B1 (en) A catalyst for preparing H2O2 and regenerating working solution and a method therefor
CN116440937B (en) Simple preparation method and application of hydrogenation catalyst carrier
CN110302781B (en) Catalyst and preparation method thereof

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