CN112275296A - Preparation method of supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol - Google Patents

Preparation method of supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol Download PDF

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CN112275296A
CN112275296A CN202011171980.3A CN202011171980A CN112275296A CN 112275296 A CN112275296 A CN 112275296A CN 202011171980 A CN202011171980 A CN 202011171980A CN 112275296 A CN112275296 A CN 112275296A
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cyclohexanediol
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palladium
dehydrogenation
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蔡春
李观火
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • 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

Abstract

The invention discloses a preparation method of a supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol.Mixing acidified pretreated active carbon, palladium, soluble salt of cheap metal and stabilizer L-lysine, ultrasonically dispersing the formed suspension uniformly, stirring at room temperature for reaction, cooling to below 10 ℃ in an ice bath after the reaction is finished, and slowly dropwise adding NaBH into the reaction system4The aqueous solution reduces metal ions into metal simple substances to obtain the Pd-M/C catalyst. For the same reason, with Al2O3As a carrier, the same preparation steps can obtain Pd-M/Al2O3Catalyst, then Pd-M/Al modified with sodium salt2O3Pd-M/Al is obtained2O3(Na)A catalyst. The Pd-M/C catalyst prepared by the method can catalyze the dehydrogenation of 1, 2-cyclohexanediol to generate catechol at the temperature of 200-230 ℃, the conversion rate of the 1, 2-cyclohexanediol and the selectivity of the catechol can reach more than 90%, and Pd-M/Al can be added2O3(Na)The catalyst catalyzes the dehydrogenation of the 1, 2-cyclohexanediol to generate the 2-hydroxy-2-cyclohexene-1-ketone, the product yield is high, and the by-products are few.

Description

Preparation method of supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol
Technical Field
The invention relates to a preparation method of a supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol, belonging to the technical field of catalyst preparation.
Background
Catechol and 2-hydroxy-2-cyclohexene-1-ketone are important chemical raw materials, and have wide application in medicines, pesticides, spices and chemical additives. The main method for industrially producing catechol at present is a phenol hydrogen peroxide hydroxylation method, the method has low conversion rate of reaction raw materials and large consumption of hydrogen peroxide, and the product contains two isomers of catechol and hydroquinone, so that the separation difficulty of the product is large, and the development of the process is limited.
The researches on the preparation of catechol catalyst by dehydrogenation of 1, 2-cyclohexanediol have been researched by scholars at home and abroad. Japanese patent application JPS5867636A discloses a Pd-Te/C catalyst with potassium sulfate as co-catalyst, which is catalytically dehydrogenated with 10 wt.% 1, 2-cyclohexanediol in water at 300 ℃ in a hydrogen atmosphere, with a 1, 2-cyclohexanediol conversion of 64% and a catechol selectivity of 96% (). Chinese patent application CN1249962A uses granular activated carbon as carrier and impregnates PdCl2The Pd/C catalyst is prepared by the solution, catalytic dehydrogenation is carried out under the conditions of normal pressure, 330 ℃ and hydrogen atmosphere, the conversion rate of the 1, 2-cyclohexanediol is 96.0 percent, and the selectivity of the catechol is 85.0 percent. Bassus used Pt (5 wt.%)/C as the dehydrogenation catalyst, the yield of catechol was 78% (Bassus J. New journal of chemistry,1993,17(6): 413-420). The method for preparing catechol by dehydrogenating 1, 2-cyclohexanediol has high reaction temperature and certain danger by using hydrogen as a carrier gas.
The production method of 2-hydroxy-2-cyclohexene-1-ketone mainly uses cyclohexanone as raw material and adopts oxidant oxidation method. Tomboulian oxidizes cyclohexanone to produce 2-hydroxy-2-cyclohexen-1-one by using selenium dioxide, the yield of the product is about 60%, and the disadvantages are that selenium dioxide is expensive and highly toxic, and the selenium residue produced by the reaction is difficult to treat, causing serious environmental pollution (Journal of Organic Chemistry,1959,24: 1239-44). Horiuchi dissolves cyclohexanone in a mixed system of acetic acid and water, and then adds a certain amount of iodine as an oxidant and copper acetate as a catalyst to obtain a 40% yield of 2-hydroxy-2-cyclohexen-1-one product (Synthesis,1989,10: 785-6). Liuzong uses cyclohexanone as raw material and is subjected to silicon etherification, bromination and ferric trichloride oxidation to obtain 2-hydroxy-2-cyclohexene-1-ketone and cyclohexanedione, although selenium dioxide is not used, the reaction conditions are severe, a plurality of byproducts are produced, and the yield is low (Liuzong, perfume, essence and cosmetics, 1991).
Disclosure of Invention
The invention aims to provide a preparation method of a supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol comprises the following specific steps:
pre-treated activated carbon carrier or Al2O3Mixing a carrier, soluble salts of palladium and cheap metal and a stabilizer L-lysine, ultrasonically dispersing the formed suspension uniformly, stirring at room temperature for reaction, cooling to below 11 ℃ in an ice bath after the reaction is finished, and slowly dropwise adding NaBH into the reaction system4Reducing metal ions into metal simple substance with water solution, aging at room temperature, filtering, washing with water, washing with ethanol, and vacuum drying to obtain Pd-M/C catalyst or Pd-M/Al2O3Catalyst, Pd-M/Al2O3Soaking in sodium salt water solution, drying to obtain sodium modified Pd-M/Al2O3(Na)A catalyst; the pretreated activated carbon carrier is prepared by dispersing the activated carbon carrier in 11-31 wt.% nitric acid aqueous solution, stirring at 91-111 ℃, condensing and refluxing for 2-4 h, filtering, washing until the washing liquid is neutral, and dryingDrying to obtain the product; the cheap metal is nickel, copper or iron.
Preferably, the sonication time is 1.5h or more.
Preferably, the stirring reaction time is 2-4 h.
Preferably, the aging time is 12h or more.
Preferably, the concentration of the aqueous nitric acid solution is 20 wt.%.
Preferably, the sodium salt is selected from sodium sulfate, sodium carbonate or sodium bicarbonate, and Na and Al in the sodium salt2O3The mass ratio of (A) to (B) is 0.02-0.06: 1.
preferably, the impregnated Pd-M/Al is dried in an aqueous solution of sodium salt2O3The temperature of the catalyst is 100-120 ℃, and the time is more than 12 hours.
Preferably, the soluble salt of palladium is palladium chloride or palladium nitrate; the soluble salt of the inexpensive metal is selected from the group consisting of nitrate, sulfate, or halide.
Preferably, the molar ratio of palladium to the inexpensive metal is 1: 1-1: 6, more preferably 1: 4.
preferably, the concentration of L-lysine in the suspension is 2-4 wt.%.
Compared with the prior art, the invention has the following advantages:
the Pd-M/C catalyst prepared by the invention has high dispersity of metal nanoparticles on the surface, the average size is about 2nm, the smaller the size of the metal nanoparticles is, the higher the catalytic activity is, the catalyst can catalyze 1, 2-cyclohexanediol to dehydrogenate to generate catechol at 200-230 ℃, and the conversion rate of 1, 2-cyclohexanediol and the selectivity of catechol can both reach over 90%. Meanwhile, the catalyst has the advantages of good repeatability and easy separation when being used as a heterogeneous catalyst. Using Pd-M/Al2O3(Na)The catalyst catalyzes the dehydrogenation of the 1, 2-cyclohexanediol to generate the 2-hydroxy-2-cyclohexene-1-ketone, no toxic and harmful waste gas and waste residue is generated, the product yield is high, and the byproducts are few.
Drawings
FIG. 1 is a scheme of catechol1H NMR spectrum.
FIG. 2 shows catechol13C NMR spectrum.
FIG. 3 is a scheme showing 2-hydroxy-2-cyclohexen-1-one1H NMR spectrum.
FIG. 4 shows 2-hydroxy-2-cyclohexen-1-one13C NMR spectrum.
In the following examples, the reaction conditions for the dehydrogenation of 1, 2-cyclohexanediol were as follows: and reacting for 1-8 h at 200-230 ℃ in an Ar environment, wherein the molar weight of Pd in the supported Pd-M bimetallic catalyst is 0.2-0.5% of that of reactants.
The Pd-M/C catalyst catalyzes the dehydrogenation of the 1, 2-cyclohexanediol to obtain the product catechol. Pd-M/Al2O3(Na)The catalyst catalyzes the dehydrogenation of the 1, 2-cyclohexanediol to obtain a product 2-hydroxy-2-cyclohexene-1-ketone.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
1.Pd1Ni4/C20Preparation of the catalyst:
dispersing 1g of activated carbon into 20 wt.% nitric acid aqueous solution, stirring at 90 ℃, condensing and refluxing for 2h, filtering and washing until the washing liquid is neutral, and drying the solid at 120 ℃ for 12 h. 1g of pretreated C20Adding a carrier, 33.3mg of palladium chloride, 97.4mg of nickel chloride and 400mg of L-lysine into 20mL of deionized water, carrying out ultrasonic treatment for 0.5h, then transferring the carrier into a water bath kettle, stirring the carrier at room temperature for reaction for 2h, keeping the temperature at 10 ℃ by adopting an ice bath, slowly dropwise adding 5mL of sodium borohydride aqueous solution (0.3mol/L), continuously stirring the carrier for 2h, aging the carrier at room temperature for 12h after the reaction is finished, then washing the carrier with deionized water and ethanol for several times, and carrying out vacuum drying on the solid at 60 ℃ for 12h to obtain Pd1Ni4/C20A catalyst.
2.Pd1Ni4/C20The catalyst is used for catalyzing dehydrogenation of 1, 2-cyclohexanediol to prepare catechol:
(1) weighing 100mgPd1Ni4/C20Adding a catalyst and 10mmol of reactant 1, 2-cyclohexanediol into a reactor, stirring and reacting for 4 hours at 230 ℃ under an Ar gas environment, cooling to room temperature after the reaction is finished, analyzing the conversion rate of the 1, 2-cyclohexanediol to be 90.8% by gas chromatography,the catechol selectivity was 93.3%.
(2) Exactly the same as (1), except that 150mgPd was weighed1Ni4/C20The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 92.3%, and the selectivity of catechol was 91.0%.
(3) The same as (1) except that the reaction time was 8 hours, the conversion of 1, 2-cyclohexanediol was 95.8% and the selectivity to catechol was 85.4%.
(4) The same as (1) except that the reaction temperature was 200 ℃, the conversion of 1, 2-cyclohexanediol was 51.2% and the selectivity to catechol was 50.6%.
Example 2
The reaction procedure was exactly the same as in example 1, except that:
activated carbon pretreatment using 10 wt.% aqueous nitric acid to obtain Pd1Ni4/C10The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 84.1%, and the selectivity of catechol was 83.8%.
Example 3
The reaction procedure was exactly the same as in example 1, except that:
activated carbon pretreatment Pd was obtained using a 30 wt.% aqueous nitric acid solution1Ni4/C30The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 83.1%, and the selectivity of catechol was 82.0%.
Example 4
The reaction procedure was exactly the same as in example 1, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride and 24.4mg of nickel chloride to obtain Pd1Ni1/C20The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 83.1%, and the selectivity of catechol was 81.8%.
Example 5
The reaction procedure was exactly the same as in example 1, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride and 146.1mg of nickel chloride to obtain Pd1Ni6/C20The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 91.0%, and the selectivity of catechol was 84.5%.
Example 6
The reaction procedure was exactly the same as in example 1, except that:
the metal precursor used for the catalyst preparation was 33.3mg of palladium chloride, and 101.1mg of copper chloride gave Pd1Cu4/C20The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 88.8%, and the selectivity of catechol was 81.1%.
Example 7
The reaction procedure was exactly the same as in example 1, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride, and 121.9mg of ferric chloride to obtain Pd1Fe4/C20The conversion rate of the catalyst, 1, 2-cyclohexanediol, was 89.3%, and the selectivity of catechol was 79.5%.
Example 8
1.Pd1Ni4/Al2O3(Na)Preparation of the catalyst:
the reaction procedure was exactly the same as in example 1, except that:
conversion of catalyst support to Al2O3Obtaining Pd1Ni4/Al2O3123.4mg of sodium sulfate (m (Na): m (Al)2O3) 0.04: 1) the prepared aqueous solution is dipped and modified to obtain Pd1Ni4/Al2O3(Na)。
2.Pd1Ni4/Al2O3(Na)The catalyst is used for catalyzing 1, 2-cyclohexanediol to prepare 2-hydroxy-2-cyclohexene-1-ketone by dehydrogenation:
(1) weighing 100mgPd1Ni4/Al2O3(Na)Adding a catalyst and 10mmol of reactant 1, 2-cyclohexanediol into a reactor, stirring and reacting for 4 hours at 230 ℃ under an Ar gas environment, cooling to room temperature after the reaction is finished, and analyzing by gas chromatography that the conversion rate of the 1, 2-cyclohexanediol is 95.1% and the selectivity of the 2-hydroxy-2-cyclohexene-1-ketone is 86.4%.
(2) And (1)The same thing, except that 150mgPd was weighed1Ni4/Al2O3(Na)The conversion rate of the 1, 2-cyclohexanediol catalyst was 97.6%, and the selectivity of the 2-hydroxy-2-cyclohexen-1-one was 85.9%.
(3) The same as (1) except that the reaction time was 8 hours, the conversion of 1, 2-cyclohexanediol was 98.6% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 80.0%.
(4) The same as (1) except that the reaction temperature was 200 ℃, the conversion of 1, 2-cyclohexanediol was 41.2% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 60.6%.
Example 9
The reaction procedure was exactly the same as in example 8, except that:
Pd1Ni4/Al2O392.2mg of sodium carbonate (m (Na): m (Al)2O3) 0.04: 1) the prepared aqueous solution is subjected to immersion modification, the conversion rate of the 1, 2-cyclohexanediol is 90.1 percent, and the selectivity of the 2-hydroxy-2-cyclohexene-1-ketone is 75.3 percent.
Example 10
The reaction procedure was exactly the same as in example 8, except that:
Pd1Ni4/Al2O3using 185.3mg of sodium sulfate (m (Na): m (Al)2O3) 0.06: 1) the prepared aqueous solution is subjected to immersion modification, the conversion rate of the 1, 2-cyclohexanediol is 90.0 percent, and the selectivity of the 2-hydroxy-2-cyclohexene-1-ketone is 71.2 percent.
Example 11
The reaction procedure was exactly the same as in example 8, except that:
the metal precursor used for the catalyst preparation was 33.3mg of palladium chloride, and 101.1mg of copper chloride gave Pd1Cu4/Al2O3(Na)The conversion of 1, 2-cyclohexanediol was 90.4% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 70.7%.
Example 12
The reaction procedure was exactly the same as in example 8, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride, and 121.9mg of ferric chloride to obtain Pd1Fe4/Al2O3(Na)The conversion of 1, 2-cyclohexanediol was 91.2% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 73.9%.
Example 13
The reaction procedure was exactly the same as in example 8, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride and 24.1mg of nickel chloride to obtain Pd1Ni1/Al2O3(Na)The conversion of 1, 2-cyclohexanediol was 86.2% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 71.9%.
Example 14
The reaction procedure was exactly the same as in example 8, except that:
the metal precursor used for preparing the catalyst is 33.3mg of palladium chloride and 146.1mg of nickel chloride to obtain Pd1Ni6/Al2O3(Na)The conversion of 1, 2-cyclohexanediol was 95.6% and the selectivity of 2-hydroxy-2-cyclohexen-1-one was 75.9%.

Claims (10)

1. The preparation method of the supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol is characterized by comprising the following specific steps:
pre-treated activated carbon carrier or Al2O3Mixing a carrier, soluble salts of palladium and cheap metal and a stabilizer L-lysine, ultrasonically dispersing the formed suspension uniformly, stirring at room temperature for reaction, cooling to below 10 ℃ in an ice bath after the reaction is finished, and slowly dropwise adding NaBH into the reaction system4Reducing metal ions into metal simple substance with water solution, aging at room temperature, filtering, washing with water, washing with ethanol, and vacuum drying to obtain Pd-M/C catalyst or Pd-M/Al2O3Catalyst, Pd-M/Al2O3Soaking in sodium salt water solution, drying to obtain sodium modified Pd-M/Al2O3(Na)A catalyst; the pretreated activated carbon carrier is prepared by dispersing the activated carbon carrier in 10-30 wt.% of nitreStirring, condensing and refluxing for 2-4 h at 90-100 ℃ in an acid aqueous solution, filtering, washing until a washing solution is neutral, and drying to obtain the aqueous solution; the cheap metal is nickel, copper or iron.
2. The method according to claim 1, wherein the sonication time is 0.5h or more.
3. The preparation method according to claim 1, wherein the stirring reaction time is 2-4 hours, and the aging time is 12 hours or more.
4. The production method according to claim 1, wherein the concentration of the aqueous nitric acid solution is 20 wt.%.
5. The method according to claim 1, wherein the sodium salt is selected from sodium sulfate, sodium carbonate or sodium bicarbonate, and Na and Al in the sodium salt2O3The mass ratio of (A) to (B) is 0.02-0.06: 1.
6. the method of claim 1, wherein the step of drying the Pd-M/Al impregnated in the aqueous solution of sodium salt is carried out completely2O3The temperature of the catalyst is 100-120 ℃, and the time is more than 12 hours.
7. The method according to claim 1, wherein the soluble salt of palladium is palladium chloride or palladium nitrate; the soluble salt of the inexpensive metal is selected from the group consisting of nitrate, sulfate, or halide.
8. The method according to claim 1, wherein the molar ratio of palladium to the inexpensive metal is 1: 1-1: 6.
9. the method according to claim 1, wherein the molar ratio of palladium to the inexpensive metal is 1: 4.
10. the method according to claim 1, wherein the concentration of L-lysine in the suspension is 2 to 4 wt.%.
CN202011171980.3A 2020-10-28 2020-10-28 Preparation method of supported Pd-M bimetallic catalyst for dehydrogenation of 1, 2-cyclohexanediol Pending CN112275296A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1249962A (en) * 1998-10-07 2000-04-12 湖南化工研究院 Preparation and usage of catalyst for synthesizing o-dihydroxybenzene
CN109174120A (en) * 2018-09-06 2019-01-11 南京理工大学 Loading type Pd-Ni duplex metal nano granule catalyst and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1249962A (en) * 1998-10-07 2000-04-12 湖南化工研究院 Preparation and usage of catalyst for synthesizing o-dihydroxybenzene
CN109174120A (en) * 2018-09-06 2019-01-11 南京理工大学 Loading type Pd-Ni duplex metal nano granule catalyst and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIA-WEI ZHANG ET.AL: "Pd-Ni bimetallic nanoparticles supported on active carbon as an efficient catalyst for hydrodeoxygenation of aldehydes" *
裴松鹏;林陵;曾崇余;: "1,2-环己二醇脱氢制邻苯二酚镍基催化剂的研究" *

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Application publication date: 20210129