CN113292395A - Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed - Google Patents

Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed Download PDF

Info

Publication number
CN113292395A
CN113292395A CN202110616568.6A CN202110616568A CN113292395A CN 113292395 A CN113292395 A CN 113292395A CN 202110616568 A CN202110616568 A CN 202110616568A CN 113292395 A CN113292395 A CN 113292395A
Authority
CN
China
Prior art keywords
catalyst
carbon
hydroquinone
carrier
auxiliary agent
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.)
Granted
Application number
CN202110616568.6A
Other languages
Chinese (zh)
Other versions
CN113292395B (en
Inventor
黄家辉
任周
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202110616568.6A priority Critical patent/CN113292395B/en
Publication of CN113292395A publication Critical patent/CN113292395A/en
Application granted granted Critical
Publication of CN113292395B publication Critical patent/CN113292395B/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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • 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
    • C07C2601/14—The ring being saturated

Abstract

The invention provides a high-surface-area porous-structure inorganic carbon carrier loaded Ni-based catalyst for preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone and a preparation method thereof. The catalyst comprises a main active component, an auxiliary agent and a carrier or the main active component and the carrier. The carrier is inorganic carbon carrier, or is treated by acid or alkali; the main active component is Ni, the content of Ni is 0.01-50.0 wt% of the weight of the catalyst, and the content of other auxiliary agents is 0-10.0 wt% of the catalyst; ni and an auxiliary agent are loaded on an inorganic carbon carrier by means of impregnation and the like, and the main active component is highly dispersed in the carrier. In a fixed bed reactor, hydroquinone can be converted into 1, 4-cyclohexanediol with high activity and high selectivity under the action of certain temperature and pressure and the catalyst.

Description

Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed
Technical Field
The invention belongs to the technical field of hydrogenation of heterogeneous catalysts, and particularly relates to an inorganic carbon carrier-loaded Ni-based catalyst and application thereof in a reaction for preparing 1, 4-cyclohexanediol from hydroquinone through heterogeneous hydrogenation.
Background
The 1, 4-cyclohexanediol is an important fine chemical and an intermediate, and is widely applied to the fields of pesticides, organic synthesis, new materials of liquid crystals and the like. At present, the method is mainly used for synthesizing inositol phospho-kinase inhibitors, benzotriazol medicaments, succinyl sulphathiazole, HMGCoA reductase, tetracyanoquinodimethane and the like. The spectrally pure 1, 4-cyclohexanediol as a new material monomer can be used for synthesizing liquid crystal materials, biological controller markers, organic electric materials and the like. At present, with the improvement of national economy and the continuous progress of science and technology, the application field of the 1, 4-cyclohexanediol is wider and wider.
The synthesis method of 1, 4-cyclohexanediol generally adopts hydroquinone as a raw material and adopts a catalytic benzene ring hydrogenation mode. In the fifties of the twentieth century, Adkins and the like use W-6Raney Ni catalyst, ethanol as solvent and hydroquinone as raw material to hydrogenate to obtain a cis-trans isomer mixture of 1, 4-cyclohexanediol, and start the research of the 1, 4-cyclohexanediol. At present, catalysts for preparing 1, 4-cyclohexanediol by hydrogenating hydroquinone mainly comprise Raney Ni and Ru supported catalysts.
The Ru-based catalyst mainly comprises diatomite and a molecular sieve (ZSM-5 and Y-type are main materials), but the catalyst generally has the problem of high cyclohexanol selectivity, because Ru species easily break C-O bonds, the selectivity is poor, and the selectivity of 1, 4-cyclohexanediol is generally 70-80%. 201019100011.6 to supercritical CO2Taking Ru/C as a reaction medium, and reacting hydroquinone with hydrogen to generate the 1, 4-cyclohexanediol, wherein the selectivity is only about 80 percent. In the process of the Raney Ni catalyst, the activity is relatively poor, but the selectivity of the 1, 4-cyclohexanediol of the catalyst can reach more than 96 percent, and a large amount of alkali species is generally required to be added to improve the catalytic performance, so the problem of environmental pollution is aggravated by the addition of the alkali species. 200710061447.X and 200510112194.5 disclose that Raney Ni catalyst can catalyze hydrogenation of hydroquinone to prepare 1, 4-cyclohexanediol under certain temperature and pressure conditions by using water and alkali solution as solvent. At present, most of catalysts are applied to a kettle type reactor and a kettle type reaction system, the problems of poor operation continuity, complicated separation operation and the like are solved, and the application of the hydroquinone hydrogenation process to a continuously operated fixed bed system is the key point for simplifying the production process and promoting industrializationMeans are provided. On the other hand, since the selectivity of the Ru-based catalyst is poor, and the Ru species are expensive, and the Raney Ni catalyst generally requires the addition of an alkali species to cause serious environmental pollution, it is important to develop and design an inexpensive Ni-based hydrogenation catalyst for preparing 1, 4-cyclohexanediol from hydroquinone, which is another critical problem.
The inorganic carbon carrier loaded Ni-based catalyst for the reaction of preparing the 1, 4-cyclohexanediol by the selective hydrogenation of the heterogeneous hydroquinone has important significance for improving the selectivity and the production efficiency of the 1, 4-cyclohexanediol and reducing the cost.
Disclosure of Invention
The invention aims to provide a large-surface-area porous-structure inorganic carbon carrier loaded Ni-based catalyst for preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone and a preparation method thereof. The inorganic carbon carrier loaded Ni-based catalyst has large specific surface area and excellent thermal stability, so that the catalyst can meet the requirement of preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone under the heterogeneous catalysis condition. The inorganic carbon carrier loaded Ni-based catalyst shows high hydrogenation activity and 1, 4-cyclohexanediol selectivity.
The technical scheme of the invention is as follows:
the catalyst is used for the reaction of preparing 1, 4-cyclohexanediol by selectively hydrogenating hydroquinone, and comprises a main active component, an auxiliary agent and a carrier or a main active component and a carrier, wherein the main active component is Ni; the auxiliary agent is one of Na, Mg, Al, Ca and Fe; the carrier is inorganic carbon; the Ni accounts for 0.01-50.0 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 0-10.0 wt% of the total mass of the catalyst.
Based on the scheme, preferably, the Ni accounts for 0.1-10.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-5.0 wt% of the total mass of the catalyst.
Based on the scheme, preferably, the Ni accounts for 0.1-5.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-3.0 wt% of the total mass of the catalyst.
Based on the above scheme, preferably, the inorganic carbon isThe activated carbon has a porous structure, and is one or a mixture of coconut shell carbon and apricot shell carbon; the activated carbon is subjected to acid treatment or alkali treatment before use, and the pore volume range of the treated activated carbon is 0.1-10.0 cm3The pore diameter is 0.2-70.0 nm, the specific surface area is 20-2000 m2/g。
Based on the scheme, preferably, the acid is one of sulfuric acid, nitric acid and phosphoric acid, the concentration of acid species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH is washed to be unchanged after the treatment; the alkali is one of potassium hydroxide, sodium hydroxide and cesium hydroxide, the concentration of alkali species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is unchanged after the treatment.
Based on the scheme, preferably, the hydrogenation reaction is carried out in a fixed bed reactor; the material of the reactor is 316L; the reaction temperature is 80-300 ℃, and preferably 100-200 ℃; the reaction pressure is 0.2-6.0 MPa, preferably 1.5-3.0 MPa.
Based on the scheme, preferably, in the hydrogenation reaction, the reaction raw material is hydroquinone solution, the solvent is one of water, isopropanol, ethanol, methanol and acetone, and the concentration of the hydroquinone solution is 0.01g/100g to 30g/100g, preferably 1g/100g to 15g/100 g; according to the volume space velocity of the reaction liquid of 0.1-500 h-1Preferably 1 to 10 hours-1；H2The molar ratio of hydroquinone to hydroquinone is 4000-3, preferably 100-1.
Based on the scheme, the catalyst is preferably subjected to H before use2Prereduction activation or no activation, H2The conditions for pre-reduction activation are as follows: GHSV of 2000--1，H2And (3) raising the temperature from room temperature to 200-700 ℃ at the temperature raising rate of 1-10 ℃/min under the atmosphere of 0.1-4.0 MPa, and keeping for 1-5 h to obtain the activated inorganic carbon carrier supported Ni-based catalyst.
Based on the above scheme, preferably, the catalyst is prepared by the following steps: dissolving a Ni metal precursor and an auxiliary agent precursor in water, soaking the obtained solution on an inorganic carbon carrier in an isometric manner or excessively, evaporating the solvent in a water bath at 30-80 ℃, drying in an oven at 100-150 ℃ for 5-15 h, and roasting at 200-800 ℃ for 2-8 h under the protection of Ar to obtain the catalyst.
Based on the above scheme, preferably, the Ni metal precursor is Ni (NO)3)2·6H2O、NiCl2·6H2O、NiSO4·6H2One or more than two of O; the precursor of the auxiliary agent is NaNO3、NaCl、Mg(NO3)2、MgCl2、Al(NO3)3、AlCl3、Ca(NO3)2、CaCl2、Fe(NO3)3One or two or more of them.
The invention has the beneficial effects that:
compared with the existing kettle type hydrogenation technology of Raney Ni and Ru-based catalysts for hydrogenation of supported hydroquinone, the hydrogenation technology of the inorganic oxide supported Ni-based catalyst has the advantages that the selectivity of 1, 4-cyclohexanediol is good, the hydrogenation activity is high, a synergistic effect exists between alkali metal species and Ni components, the selectivity and the activity of the catalyst can be effectively improved by adding the alkali metal species auxiliary agent component, the process is environment-friendly, a continuous fixed bed system is efficiently used, the cost is greatly reduced, and the like.
Detailed Description
The following examples illustrate but do not limit the invention claimed, and the starting materials used in the following examples are all conventional products available on the market, unless otherwise specified.
Example 1
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-1. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.20g MgCl2Dissolve in 6.0g of water. Then 3g of acid-washed activated carbon-1 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-1 loaded Ni-Mg-based catalyst, which is recorded as Ni-Mg/acid-washed activated carbon-1.
Example 2
0.29g of NiCl was weighed2·6H2O and 0.10g NaNO3Then dissolved in 10.0g of water. Then 3g of apricot shell carbon was impregnated. Evaporating the solvent in water bath at 50 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the apricot shell carbon-loaded Ni-Na-based catalyst which is marked as Ni-Na/apricot shell carbon.
Example 3
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated phosphoric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-2. 0.29g of NiSO was weighed4·6H2O and 0.10g NaCl were dissolved in 6.3g water. Then 3g of acid-washed activated carbon-2 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-2 loaded Ni-Na-based catalyst, which is recorded as Ni-Na/acid-washed activated carbon-2.
Example 4
Weighing 10.0g of apricot shell carbon, adding 20mL of concentrated sulfuric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying, wherein the mark is acid-washing active carbon-3. 0.58g of NiSO was weighed out4·6H2O and 0.20g Mg (NO)3)2Then dissolved in 10.0g of water. Then 3g of acid-washed activated carbon-3 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-3 loaded Ni-Mg-based catalyst, which is recorded as Ni-Mg/acid-washed activated carbon-3.
Example 5
Weighing 10.0g of apricot shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying, wherein the mark is acid-washing active carbon-4. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.35gAl (NO)3)3Then dissolved in 10.0g of water. Then 3g of acid-washed activated carbon-4 was impregnated. Evaporating the solvent in 70 ℃ water bath, drying in a drying oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-4 loaded Ni-Al-based catalyst, which is recorded as Ni-A1/acid-washed activated carbon-4.
Example 6
Weighing 10.0g of coconut shell charcoal, adding 20mL of 10mol/L NaOH solution, heating to 40 ℃ for 10h, washing to be neutral, and drying to record as alkaline washing activated carbon-5. Weigh 0.58gNi (NO)3)2·6H2O and 0.75g Ca (NO)3)2Then dissolved in 10.0g of water. Then 3g of alkaline washing activated carbon5. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the alkali washing activated carbon-5 loaded Ni-Ca-based catalyst which is marked as Ni-Ca/alkali washing activated carbon-5.
Example 7
Weighing 10.0g of coconut shell charcoal, adding 20mL of 10mol/L KOH solution, heating to 40 ℃ for 10h, washing to be neutral, and drying to record as alkaline washing activated carbon-6. Weighing 1.16gNi (NO)3)2·6H2O and 0.45g CaCl2Then dissolved in 10.0g of water. Then 3g of alkali washing activated carbon-6 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the alkali washing activated carbon-6 loaded Ni-Ca-based catalyst which is marked as Ni-Ca/alkali washing activated carbon-6.
Example 8
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-1. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.20g Fe (NO)3)3Dissolve in 6.0g of water. Then 3g of acid-washed activated carbon-1 was impregnated. Evaporating the solvent in 70 ℃ water bath, drying in a drying oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-1 loaded Ni-Fe-based catalyst, which is recorded as Ni-Fe/acid-washed activated carbon-7.
Example 9
0.29g of Ni (NO) was weighed3)2·6H2Dissolved in 3.3g of water. Then 3g of coconut shell charcoal was impregnated. Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the coconut shell carbon-loaded Ni-based catalyst which is marked as Ni/coconut shell carbon.
Example 10
0.29g of Ni (NO) was weighed3)2·6H2Dissolved in 3.3g of water. Then 3g of apricot shell carbon was impregnated. Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the apricot shell carbon-loaded Ni-based catalyst which is marked as Ni/apricot shell carbon.
Application example
The catalysts prepared in the above examples and comparative examples were used for the isopropanol solution of hydroquinone and H2Preparation of 1, 4-rings as starting materialsReaction of hexanediol.
Activation of the catalyst: GHSV of 6000h in the reactor before the catalyst is used-1In-situ reduction activation is carried out in a flow under the conditions: 0.1MPa, H2And heating to 500 ℃ from room temperature at the speed of 10 ℃/min, and keeping for 3 hours to obtain the activated inorganic oxide supported Ni-based catalyst.
The activated catalyst was used in the above reaction, and the specific reaction conditions of each example and comparative example were as follows:
the reaction conditions are as follows: 160 ℃, 3.0MPa, H2The molar ratio of hydroquinone is 10: 1, and the LHSV of hydroquinone solution is 9h-1The catalyst volume was 0.2 mL.
And (3) performing off-line analysis on the liquid phase product, and analyzing the contents of hydroquinone and 1, 4-cyclohexanediol by using a DB-1701 capillary chromatographic column and a FID detector.
Using the inorganic carbon supported Ni-based catalysts prepared in the above examples and comparative examples, 1, 4-cyclohexanediol was prepared according to the above procedure, and the hydroquinone conversion and 1, 4-cyclohexanediol selectivity are shown in Table 1.
TABLE 1 summary of the results of the selective hydrogenation of hydroquinone to 1, 4-cyclohexanediol in the examples and comparative examples
Figure BDA0003096975180000071
Figure BDA0003096975180000081
The results show that: comparison of examples 1 to 10 shows that Ni (NO) is added3)2·6H2O is a precursor and Mg (NO)3)2The catalyst used as the precursor of the auxiliary agent is better than other catalysts in both the hydrogenation activity of hydroquinone and the selectivity of 1, 4-cyclohexanediol.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. The application of the inorganic carbon carrier loaded Ni-based catalyst is characterized in that: the catalyst is used for the reaction of preparing 1, 4-cyclohexanediol by selectively hydrogenating hydroquinone, and comprises a main active component, an auxiliary agent and a carrier or a main active component and a carrier, wherein the main active component is Ni; the auxiliary agent is one of Na, Mg, Al, Ca and Fe; the carrier is inorganic carbon; the Ni accounts for 0.01-50.0 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 0-10.0 wt% of the total mass of the catalyst.
2. Use according to claim 1, characterized in that: the Ni accounts for 0.1-10.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-5.0 wt% of the total mass of the catalyst.
3. Use according to claim 2, characterized in that: the Ni accounts for 0.1-5.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-3.0 wt% of the total mass of the catalyst.
4. Use according to claim 1, characterized in that: the inorganic carbon is activated carbon with a porous structure, and the activated carbon is one or a mixture of coconut shell carbon and apricot shell carbon; the activated carbon is subjected to acid treatment or alkali treatment before use, and the pore volume range of the treated activated carbon is 0.1-10.0 cm3The pore diameter is 0.2-70.0 nm, the specific surface area is 20-2000 m2/g。
5. Use according to claim 4, characterized in that: the acid is one of sulfuric acid, nitric acid and phosphoric acid, the concentration of acid species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is unchanged after the treatment; the alkali is one of potassium hydroxide, sodium hydroxide and cesium hydroxide, the concentration of alkali species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is unchanged after the treatment.
6. Use according to claim 1, characterized in that: the hydrogenation reaction is carried out in a fixed bed reactor; the reaction temperature is 80-300 ℃, and preferably 100-200 ℃; the reaction pressure is 0.2-6.0 MPa; preferably 1.5 to 3.0 MPa.
7. Use according to claim 1, characterized in that: the reaction raw material of the hydrogenation reaction is hydroquinone solution, the solvent is one of water, isopropanol, ethanol, methanol and acetone, and the concentration of the hydroquinone solution is 0.01g/100 g-30 g/100g, preferably 1g/100 g-15 g/100 g; according to the volume space velocity of the reaction liquid of 0.1-500 h-1Preferably 1 to 10 hours-1；H2The molar ratio of hydroquinone to hydroquinone is 4000-3, preferably 100-1.
8. Use according to claim 1, characterized in that: the catalyst is activated or not activated before use, and the activation conditions are as follows: GHSV of 2000--1，H2And (3) raising the temperature from room temperature to 200-700 ℃ at the temperature raising rate of 1-10 ℃/min under the atmosphere of 0.1-4.0 MPa, and keeping for 1-5 h to obtain the activated inorganic carbon carrier supported Ni-based catalyst.
9. Use according to claim 1, characterized in that: the catalyst is prepared by the following steps: dissolving a Ni metal precursor and an auxiliary agent precursor in water, soaking the obtained solution on an inorganic carbon carrier in an isometric manner or excessively, evaporating the solvent in a water bath at 30-80 ℃, drying in an oven at 100-150 ℃ for 5-15 h, and roasting at 200-800 ℃ for 2-8 h under the protection of Ar to obtain the catalyst.
10. Use according to claim 9, characterized in that: the Ni metal precursor is Ni (NO)3)2·6H2O、NiCl2·6H2O、NiSO4·6H2One or more than two of O; the precursor of the auxiliary agent is NaNO3、NaCl、Mg(NO3)2、MgCl2、Al(NO3)3、AlCl3、Ca(NO3)2、CaCl2、Fe(NO3)3One or two or more of them.
CN202110616568.6A 2021-06-02 2021-06-02 Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed Active CN113292395B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110616568.6A CN113292395B (en) 2021-06-02 2021-06-02 Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110616568.6A CN113292395B (en) 2021-06-02 2021-06-02 Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed

Publications (2)

Publication Number Publication Date
CN113292395A true CN113292395A (en) 2021-08-24
CN113292395B CN113292395B (en) 2022-07-19

Family

ID=77326847

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110616568.6A Active CN113292395B (en) 2021-06-02 2021-06-02 Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed

Country Status (1)

Country Link
CN (1) CN113292395B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055883A (en) * 2012-12-28 2013-04-24 浙江大学 Supported nickel-based catalyst and its preparation method and use
US20170189891A1 (en) * 2014-05-28 2017-07-06 The Board Of Regents For Oklahoma State University System and method of producing a char support nickel catalyst for use in syngas production
CN107486191A (en) * 2016-06-12 2017-12-19 中国科学院大连化学物理研究所 A kind of iridium based catalyst of acid treatment high-area carbon load and its preparation method and application
CN109759084A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 Catalyst and its preparation and application for methanol vapor-phase carbonylation methyl acetate
US20190374934A1 (en) * 2016-12-22 2019-12-12 IFP Energies Nouvelles Method for the hydrogenation of aromatics using a nickel-based catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103055883A (en) * 2012-12-28 2013-04-24 浙江大学 Supported nickel-based catalyst and its preparation method and use
US20170189891A1 (en) * 2014-05-28 2017-07-06 The Board Of Regents For Oklahoma State University System and method of producing a char support nickel catalyst for use in syngas production
CN107486191A (en) * 2016-06-12 2017-12-19 中国科学院大连化学物理研究所 A kind of iridium based catalyst of acid treatment high-area carbon load and its preparation method and application
US20190374934A1 (en) * 2016-12-22 2019-12-12 IFP Energies Nouvelles Method for the hydrogenation of aromatics using a nickel-based catalyst
CN109759084A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 Catalyst and its preparation and application for methanol vapor-phase carbonylation methyl acetate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUOYI BAI 等: "Continuous hydrogenation of hydroquinone to 1,4-cyclohexanediol over alkaline earth metal modified nickel-based catalysts", 《CATALYSIS COMMUNICATIONS》 *
吴文海: "镍基催化剂上氯代芳香族化合物加氢脱氯降解研究", 《中国科学院研究生院博士学位论文》 *
王洪军 等: "对苯二酚催化加氢制备1,4-环己二醇的研究", 《分子催化》 *

Also Published As

Publication number Publication date
CN113292395B (en) 2022-07-19

Similar Documents

Publication Publication Date Title
CN101693201B (en) Mesopore carbon load nickel hydrogenation catalyst and preparation method thereof
CN108393092B (en) Preparation method of catalyst for preparing secondary amine by nitrile compound hydrogenation, product and application thereof
CN109894154A (en) A kind of copper-based MOF is carbonized derivative catalysis material and its preparation method and application
CN109046430A (en) Nitrogen-dopped activated carbon supported palladium-iron catalyst and its application for benzophenone catalytic hydrogenation synthesis benzhydrol
CN101966456A (en) Hydrogenation catalyst and preparation method of 4,4'-diamino-dicyclohexyl methane
CN109529946A (en) A kind of method that solid-carrying type Cu-Ni bimetallic catalyst and its catalysis furfural complete hydrogenation prepare tetrahydrofurfuryl alcohol
CN109225342A (en) The preparation method and application of the ruthenium-based catalytic agent carrier of Hydrophilic modification for partial hydrogenation of benzene, carrier modification method and catalyst
CN101185904A (en) Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof
CN109174091A (en) A kind of Ru-Rh/C bimetallic catalyst and its preparation method and application
CN107362797A (en) Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized
CN110028382A (en) A method of preparing sorbierite
CN111167515B (en) Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof
WO2019200778A1 (en) Catalyst for preparing pyridine base from synthetic gas, preparation method therefor and use thereof
CN108970632A (en) A kind of load type bimetal catalyst and preparation method thereof efficiently synthesizing DBE
CN113292395B (en) Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed
CN109320398A (en) A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation
JP2023533579A (en) Process for preparing copper-based hydrogenation catalysts, catalysts prepared therewith and uses
JP2004500236A (en) Catalyst for hydrogenating unsaturated hydrocarbons
CN100415367C (en) Method for preparing nano metal palladium/supporter catalyst
CN114939438B (en) Method for selective hydrogenation of olefinic unsaturated carbonyl compound and catalyst thereof
WO2023134779A1 (en) Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol
CN103894232A (en) Catalyst for synthesizing methyl formate by formylating methyl nitrite, preparation method and application of catalyst
CN113649049A (en) Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof
CN115487821A (en) Application of inorganic oxide supported multi-metal catalyst in catalyzing hydroquinone or bisphenol A hydrogenation reaction
CN114621060B (en) Method for preparing hydroquinone by p-benzoquinone hydrogenation

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