CN116408086A - Preparation method of catalyst for preparing 1, 3-propylene glycol by high-selective hydrogenation of glycidol - Google Patents

Preparation method of catalyst for preparing 1, 3-propylene glycol by high-selective hydrogenation of glycidol Download PDF

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CN116408086A
CN116408086A CN202310335454.3A CN202310335454A CN116408086A CN 116408086 A CN116408086 A CN 116408086A CN 202310335454 A CN202310335454 A CN 202310335454A CN 116408086 A CN116408086 A CN 116408086A
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mof
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glycidol
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鲁新环
石从兴
张望
夏清华
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Hubei University
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Abstract

The invention discloses a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps: 1) Preparing a CoNi-MOF material through mixed solvent thermal crystallization reaction or further preparing M-MOF/MOx through loading the CoNi-MOF material by oxide; 2) And carrying out pyrolysis treatment on the material to obtain a CoNi@C catalyst derived from CoNi-MOF or a M@C/MOx catalyst derived from M-MOF/MOx. The catalyst is applied to catalyzing selective hydrogenation reaction of epoxypropanol, and the preparation method of the catalyst is simple and easy to operate, low in cost, high in hydrogenation reaction conversion rate and good in product selectivity, and is applied to catalyzing selective hydrogenation reaction of epoxypropanol to prepare the 1, 3-propanediol compound, so that the conversion rate of a substrate and the selectivity of a target product are greatly improved.

Description

Preparation method of catalyst for preparing 1, 3-propylene glycol by high-selective hydrogenation of glycidol
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a preparation method of a catalyst for preparing 1, 3-propanediol by high-selectivity hydrogenation of glycidol.
Background
Epoxy compounds are a very important class of organic chemical raw materials and intermediates. The compound has a ternary oxygen ring structure in the molecule, and under the action of an acidic or basic catalyst, the ternary oxygen ring is easy to open, and can be subjected to addition reaction with various nucleophilic substances such as water, alcohol, amine, ammonia, phenol or carboxylic acid, so that the compound has wide application. Among them, epoxypropanol (also called glycidol, abbreviated as GLD) has a simple glycerol skeleton and a special structure and functional group, and thus has a wide application prospect in organic synthesis. The 1, 3-propanediol is an important chemical raw material, has important application in medicine, food, cosmetics and organic synthesis, can be used as solvent, antifreeze, emulsifier, plasticizer, detergent, preservative, lubricant and the like, and has wide application prospect.
There are many methods for synthesizing 1, 3-propanediol, mainly ethylene oxide hydroformylation, acrolein hydration, acetal, glycerol hydrolysis, biomass fermentation, and the like. The industrialized production method is mainly an acrolein hydration hydrogenation method, an ethylene oxide hydroformylation method and a biological fermentation method. The intermediate products 3-hydroxy propanal related to the acrolein hydration hydrogenation method and the ethylene oxide hydroformylation method are unstable in substance, are easy to generate acetal, are unfavorable for separation, and the subsequent product purification process needs to evaporate a large amount of water, so that the energy consumption is high; the biological fermentation method has slow reaction, low production efficiency and many impurities, cannot be used for large-scale production, and is difficult to purify the product. The selective hydrogenation of the glycerol is used for preparing the 1, 3-propanediol, the production process is simple, and a new way is provided for the 1, 3-propanediol and the synthesis. In general, the hydrogenolysis of glycerol to propylene glycol is carried out by a dehydration-hydrogenation route, which is a process comprising the step of adding a metal for hydrogenationAnd a catalytic reaction system consisting of an acidic catalyst for dehydration. However, in addition to the formation of 1, 3-propanediol during the glycerol hydrogenolysis reaction, other byproducts such as 1, 2-propanediol are also produced and the 1, 2-propanediol continues to be hydrogenated to produce n-propanol and isopropanol. Thus, the catalytic performance of the catalysts for preparing 1, 3-propanediol by hydrogenolysis of glycerol is still to be further improved. Patent CN111333488A discloses a method for preparing 1, 3-propanediol from glycerol as a raw material using a loop reactor. The method takes glycerin as raw material and takes Pt/WO 3 /Al 2 O 3 Is prepared by hydrogenation reaction in a loop reactor as a catalyst. The method can improve the utilization rate of the catalyst, but has complex process, and is not beneficial to industrial production. Patent CN115594565a discloses a process for preparing 1, 3-propanediol by hydrogenating glycerol, which adopts a venturi reactor for reaction and is matched with a membrane separation process, and uses a noble metal-based catalyst, wherein the active component of the catalyst is Ru, pd, pt or Rh, and although the continuous production of 1, 3-propanediol can be realized, by-products (n-propanol and isopropanol) are required to be added in the reaction to inhibit the production of 1, 2-propanediol in the reaction process, thereby improving the selectivity of 1, 3-propanediol, but the reaction and separation process are more complex. Patent CN115445652A discloses a catalyst for preparing 1, 3-propanediol by selective hydrogenation of glycerin, a preparation method and application thereof, wherein the catalyst comprises the following metal active components in percentage by mass: (0.05-2.5) Pt and a metal M, wherein the metal M is selected from one or more of Au, ru, pd, cu, ni; the conversion rate of the catalyst prepared by the process for catalyzing glycerol is mostly lower than 80%, the selectivity of the product 1, 3-propanediol is lower than 55%, and the overall balance economic benefit is poor.
At present, few reports on the direct selective hydrogenation of glycidol to 1, 3-propanediol are made as a raw material. Aiming at the technical defects existing in the prior art, a catalyst with low raw material cost and simple preparation steps needs to be developed, so that the catalyst has good catalytic hydrogenation performance on epoxypropanol and high selectivity on the product 1, 3-propanediol under the mild reaction condition.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a preparation method of a catalyst for preparing 1, 3-propanediol by high-selectivity hydrogenation of epoxypropanol, wherein the catalyst is M@C-x derived from M-MOF or M@C/MOx derived from M-MOF/MOx loaded by oxide, and the catalyst has the outstanding characteristics of simple preparation method, easy operation and excellent catalytic performance, and can be used for preparing 1, 3-propanediol compounds by high-selectivity hydrogenation of epoxypropanol. The method comprises the steps of obtaining an M-MOF material through a mixed solvent thermal crystallization method, and preparing a M@C-x catalyst through pyrolysis treatment; or the M-MOF material is loaded on an oxide carrier to obtain the M-MOF/MOx, and then the catalyst M@C/MOx is prepared through pyrolysis treatment. And the obtained catalyst is applied to the preparation of 1, 3-propylene glycol by catalyzing the high-selectivity hydrogenation of glycidol, so that the reaction condition is relatively mild, and the conversion rate is relatively high.
The technical scheme of the invention is as follows: the preparation method of the catalyst for preparing the 1, 3-propanediol by high-selectivity hydrogenation of the glycidol is characterized by comprising the following steps:
1) Placing metal salt comprising cobalt salt and nickel salt into a container, sequentially adding DMF, water and ethanol as mixed solvents, and fully stirring and dissolving to obtain solution A;
2) Placing terephthalic acid into a polytetrafluoroethylene lining, sequentially adding DMF, water and ethanol as mixed solvents, and fully stirring and dissolving to obtain a solution B;
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2-6 hours at normal temperature, filling the lining into a reaction kettle, crystallizing at 100-180 ℃ for 12-72 hours, taking out the reaction kettle, ageing at room temperature for 2-3 days, purifying and drying after the reaction is finished to obtain an M-MOF material;
4) And (3) performing direct pyrolysis treatment or thermal pyrolysis treatment carried on the oxide carrier on the M-MOF to obtain the catalyst.
In the invention, M-MOF is used for direct pyrolysis treatment to obtain M-MOF derived nano M@C-x catalyst; and loading the M-MOF on an oxide carrier MOx to obtain an M-MOF/MOx material, and performing thermal decomposition treatment to obtain the M-MOF/MOx-derived nano M@C/MOx catalyst.
Preferably, in the step 1), the cobalt salt is selected from one of cobalt nitrate and cobalt acetate, and the nickel salt is selected from one of nickel nitrate and nickel acetate; the molar ratio of cobalt salt to nickel salt in the metal salt is 1-4: 1 to 4.
Preferably, the mixed solvent in the step 1) and the mixed solvent in the step 2) are prepared from DMF, water and ethanol according to a volume ratio of 3:1:1, wherein the concentration of metal salt in the solution A is 0.1-0.2 mol/L, and the concentration of terephthalic acid in the solution B is 0.1-0.2 mol/L.
Preferably, in step 3), the purification treatment specifically comprises: washing the obtained filter cake with ethanol for 3-5 times, washing with DMF for 3-5 times, and filtering to collect the filter cake; the drying treatment is specifically as follows: vacuum drying at 90-100 deg.c for 8-12 hr to obtain M-MOF material.
Preferably, in the step 3), the crystallization reaction temperature is 150-170 ℃, and the crystallization reaction time is 24-72 h.
Preferably, the specific steps of the pyrolysis treatment in the step 4) include: putting the mixture into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300-600 ℃ and the pyrolysis treatment time is 1-2 h. In step 4), the M-MOF material or the M-MOF/MOx material is subjected to the same pyrolysis treatment to obtain M-MOF-derived M@C-x or M-MOF/MOx-derived M@C/MOx. Further, the pyrolysis treatment temperature is 300-500 ℃.
Preferably, the step of supporting the M-MOF material on the oxide support in the step 4) includes: dispersing M-MOF material into water, adding oxide carrier MOx selected from gamma-Al 2 O 3 、SiO 2 The mass of the M-MOF material accounts for 7-10% of the sum of the mass of the M-MOF material and the mass of the oxide carrier MOx; fully stirring, carrying out load reaction for 10-12 h at 80-90 ℃, then carrying out rotary evaporation of water from the reaction solution, and carrying out vacuum drying for 8-12 h at 90-100 ℃ to finish load.
The invention also provides a catalyst which is prepared by the preparation method of the catalyst for preparing 1, 3-propanediol by high-selective hydrogenation of any epoxypropanol.
The invention also provides application of the catalyst, and the catalyst is used for catalyzing high-selectivity hydrogenation of glycidol to prepare 1, 3-propanediol.
Preferably, the method for preparing the 1, 3-propylene glycol by high-selectivity hydrogenation of the epoxypropanol comprises the following steps: adding catalyst, epoxypropanol and solvent into batch pressure reactor, using H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 1-3.0 MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to enable the hydrogenation reaction temperature to be 90-130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 3-6 h, so that the 1, 3-propanediol compound is obtained. Further, the hydrogenation reaction temperature is preferably 110 to 130 ℃.
Preferably, the catalyst is used in an amount of 1.0 to 10.0mg of catalyst per 1mmol of glycidol; the mass fraction of the epoxypropanol in the reaction liquid is 5-30%; the reaction solvent is selected from one of methanol, ethanol, isopropanol and tetrahydrofuran which all contain 3.0mg/L NaOH. The reaction liquid is a mixture of epoxypropanol and solvent, and the catalyst is solid and is not dissolved in the reaction liquid.
Preferably, 1.0 to 10.0mg of M-MOF derived M@C-x catalyst is used per 1mmol of glycidol.
Preferably, 5.0 to 10.0mg of M-MOF/MOx derived M@C/MOx catalyst is used per 1mmol of glycidol.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the invention takes cheap metal cobalt salt, nickel salt and ligand terephthalic acid as raw materials, prepares M-MOF material through mixed solvent thermal crystallization reaction, obtains nano CoNi@C catalyst directly through pyrolysis treatment, and applies the nano CoNi@C catalyst to the reaction of preparing 1, 3-propanediol compound through high selective hydrogenation of glycidol. At present, reports on selective hydrogenation of glycidol to prepare 1, 3-propanediol are less, the catalyst adopted by the method disclosed by the technology is low in price, the production cost can be obviously reduced, the hydrogenation reaction conversion rate is high, the product selectivity is good, and positive technical reference is provided for the development of the field.
Secondly, the M-MOF/MOx prepared by the invention is a composite material prepared by loading the M-MOF on the oxide MOx, so that the M@C/MOx catalyst derived from the composite material has high metal dispersity, and the high exposed metal active site is favorable for the diffusion of reactant molecules and product molecules and the formation of intermediates in the catalytic reaction process, thereby providing an ideal reaction place for the catalytic reaction. The preparation method with low cost, simple synthesis and good reproducibility is beneficial to the large-scale application of the cobalt-nickel catalyst in the selective hydrogenation of the glycidol compound.
Thirdly, the method for producing the 1, 3-propanediol compound according to the steps has the advantages of simple process, low cost of catalyst, high catalytic activity and high selectivity of target products, the conversion of the epoxypropanol can reach 100%, the selectivity of the product 1, 3-propanediol also reaches 94.3%, and the generation of hydrogenation products 1, 2-propanediol is greatly reduced. Compared with the prior art, the catalyst for preparing the 1, 3-propylene glycol by selectively hydrogenating the glycidol provided by the invention adopts the bimetallic active component with specific content, realizes better overall interaction, has higher stability, keeps higher catalytic activity and selectivity on a high-concentration glycidol solution, and is suitable for preparing the 1, 3-propylene glycol by hydrogenating the glycidol.
Drawings
FIG. 1 shows the selective hydrogenation reaction process of glycidol;
FIG. 2 is a Co produced in example 1 of the present invention 1 Ni 1 -MOF and Co 1 Ni 1 X-ray diffraction pattern of @ C-300;
FIG. 3 shows Co prepared in example 1, example 2, comparative example 2 and comparative example 3 of the present invention 1 Ni 1 -MOF、Co 4 Ni 1 Scanning electron microscopy of MOF, co-MOF and Ni-MOF;
FIG. 4 is a graph showing the results of the catalytic hydrogenation reactions of example 1 and comparative example 1, comparative example 2, comparative example 3 and comparative example 4 according to the present invention.
Detailed Description
The invention is illustrated in further detail by the following specific examples.
Example 1
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total mass of 5mmol and the molar ratio of 1:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF material.
4) And carrying out pyrolysis treatment on the CoNi-MOF material to obtain the CoNi@C nano catalyst derived from the CoNi-MOF material. Co is to be 1 Ni 1 Placing the MOF material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2 hours, so as to obtain Co 1 Ni 1 -MOF-derivatized nano Co 1 Ni 1 Catalyst @ C-300.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing high-selectivity hydrogenation of glycidol by using a nano CoNi@C catalyst derived from CoNi-MOF comprises the following steps: co (Co) 1 Ni 1 -MOF derived Co 1 Ni 1 50mg of catalyst @ C-300, 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH) were charged into a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to 130 ℃ for 5h of hydrogenation reaction, and the selective hydrogenation reaction of the glycidol is carried outTo obtain the 1, 3-propanediol compound.
Example 2
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt nitrate and nickel nitrate with the total mass of 5mmol and the molar ratio of 4:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 15mL of DMF, 5mL of water and 5mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.2 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring at normal temperature for 6 hours, loading the lining into a reaction kettle, carrying out static crystallization reaction at 170 ℃ for 24 hours, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 4 Ni 1 -MOF material.
4) And carrying out pyrolysis treatment on the CoNi-MOF material to obtain the CoNi@C nano catalyst derived from the CoNi-MOF material. Putting the CoNi-MOF material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 400 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 4 Ni 1 -MOF-derivatized nano Co 4 Ni 1 Catalyst @ C-400.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing high-selectivity hydrogenation of glycidol by using a nano CoNi@C catalyst derived from CoNi-MOF comprises the following steps: co (Co) 4 Ni 1 -MOF derived Co 4 Ni 1 20mg of catalyst @ C-400, 6.75mmol of glycidol, 9.5g of solvent ethanol (containing 3.0mg/L NaOH) were added to a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 2.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to enable the hydrogenation reaction temperature to be 110 ℃, and the selective hydrogenation reaction of the glycidol is carried out for 6 hours to obtain the 1, 3-propanediol compound.
Example 3
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt nitrate and nickel acetate with the total mass of 5mmol and the molar ratio of 1:4 in a 100mL beaker, sequentially adding 15mL of DMF, 5mL of water and 5mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.2 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring at normal temperature for 3 hours, loading the lining into a reaction kettle, carrying out static crystallization reaction at 150 ℃ for 48 hours, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 4 -MOF material.
4) And carrying out pyrolysis treatment on the CoNi-MOF material to obtain the CoNi@C nano catalyst derived from the CoNi-MOF material. Co is to be 1 Ni 4 Placing the MOF material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 500 ℃ and the pyrolysis treatment time is 1h, so as to obtain Co 1 Ni 4 -MOF-derivatized nano Co 1 Ni 4 Catalyst @ C-500.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing high-selectivity hydrogenation of glycidol by using a nano CoNi@C catalyst derived from CoNi-MOF comprises the following steps: co (Co) 1 Ni 4 -MOF derived Co 1 Ni 4 50mg of catalyst @ C-500, 10.0mmol of glycidol, 9.26g of solvent isopropanol (containing 3.0mg/L NaOH) were charged to a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 1.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to ensure that the hydrogenation reaction temperature is 120 ℃, and the selective hydrogenation reaction of glycidol is carried out for 4 hours to obtain the 1, 3-propanediol compound.
Example 4
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt nitrate and nickel nitrate with the total mass of 5mmol and the molar ratio of 1:2 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 4 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 24 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Buchner funnel after the reaction is finished, washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 2 -MOF material.
4) And carrying out pyrolysis treatment on the CoNi-MOF material to obtain the CoNi@C nano catalyst derived from the CoNi-MOF material. Co is to be 1 Ni 2 Placing the MOF material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2 hours, so as to obtain Co 1 Ni 2 -MOF-derivatized nano Co 1 Ni 2 Catalyst @ C-300.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing high-selectivity hydrogenation of glycidol by using a nano CoNi@C catalyst derived from CoNi-MOF comprises the following steps: co (Co) 1 Ni 2 -MOF derived Co 1 Ni 2 80mg of catalyst @ C-300, 27.0mmol of glycidol, 8.0g of solvent tetrahydrofuran (containing 3.0mg/L NaOH) were charged into a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 3 hours to obtain the 1, 3-propanediol compound.
Example 5
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt nitrate and nickel nitrate with the total mass of 5mmol and the molar ratio of 2:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 24 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Buchner funnel after the reaction is finished, washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 2 Ni 1 -MOF material.
4) And carrying out pyrolysis treatment on the CoNi-MOF material to obtain the CoNi@C nano catalyst derived from the CoNi-MOF material. Co is to be 2 Ni 1 -placing MOF material into vacuumIntroducing 30% hydrogen nitrogen into a tubular furnace for pyrolysis treatment at 350 ℃ for 2h to obtain Co 2 Ni 1 -MOF-derivatized nano Co 2 Ni 1 Catalyst @ C-350.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing high-selectivity hydrogenation of glycidol by using a nano CoNi@C catalyst derived from CoNi-MOF comprises the following steps: co (Co) 2 Ni 1 -MOF derived Co 2 Ni 1 101mg of catalyst @ C-300, 40.5mmol of glycidol, 7.0g of solvent methanol (containing 3.0mg/L NaOH) were charged to a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
Example 6
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmol and the molar ratio of 1:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF material.
4) The Co to be obtained 1 Ni 1 MOF material 0.3g was dispersed in 50mL of water, 2.7g of gamma-Al was added 2 O 3 The oxide carrier is fully stirred, then is loaded and reacted for 10 hours at 90 ℃, then the reaction liquid is distilled off in a rotary way to remove water, and vacuum drying is carried out for 8 hours at 100 ℃ to obtain Co 1 Ni 1 -MOF/Al 2 O 3 Material (Co) 1 Ni 1 -MOF on oxide support gamma-Al 2 O 3 Is 10 percent of the load); then Co is added 1 Ni 1 -MOF/Al 2 O 3 And (3) carrying out pyrolysis treatment on the material: co is to be 1 Ni 1 -MOF/Al 2 O 3 Placing the material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 1 Ni 1 -MOF/Al 2 O 3 Derivatized Co 1 Ni 1 @C/Al 2 O 3 A catalyst.
(2)Co 1 Ni 1 -MOF/Al 2 O 3 Derivatized Co 1 Ni 1 @C/Al 2 O 3 The method for preparing the 1, 3-propanediol compound by catalyzing the high-selectivity hydrogenation of the glycidol by the catalyst comprises the following steps: co (Co) 1 Ni 1 -MOF/Al 2 O 3 Derivatized Co 1 Ni 1 @C/Al 2 O 3 67.5mg of catalyst, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and H is used 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 6 hours to obtain the 1, 3-propanediol compound.
Example 7
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmol and the molar ratio of 1:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 60 hours at 160 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF material.
4) The Co to be obtained 1 Ni 1 MOF material 0.21g was dispersed in 50mL of water, 2.79g of SiO was added 2 The oxide carrier is fully stirred, then is loaded and reacted for 10 hours at 90 ℃, then the reaction liquid is distilled off in a rotary way to remove water, and vacuum drying is carried out for 8 hours at 100 ℃ to obtain Co 1 Ni 1 -MOF/SiO 2 Material (Co) 1 Ni 1 MOF on oxide support SiO 2 Is 7 percent loaded); then Co is added 1 Ni 1 -MOF/SiO 2 And (3) carrying out pyrolysis treatment on the material: co is to be 1 Ni 1 -MOF/SiO 2 Placing the material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 1 Ni 1 -MOF/SiO 2 Derivatized Co 1 Ni 1 @C/SiO 2 A catalyst.
(2)Co 1 Ni 1 -MOF/SiO 2 Derivatized Co 1 Ni 1 @C/SiO 2 The method for preparing the 1, 3-propanediol compound by catalyzing the high-selectivity hydrogenation of the glycidol by the catalyst comprises the following steps: co (Co) 1 Ni 1 -MOF/SiO 2 Derivatized Co 1 Ni 1 @C/SiO 2 135mg of catalyst, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and H is used 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to ensure that the hydrogenation reaction temperature is 120 ℃, and the selective hydrogenation reaction of the glycidol is carried out for 6 hours to obtain the 1, 3-propanediol compound.
Example 8
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmol and the molar ratio of 4:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 24 hours at 170 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 4 Ni 1 -MOF material.
4) The Co to be obtained 4 Ni 1 MOF material 0.3g was dispersed in 50mL of water, 2.7g of gamma-Al was added 2 O 3 The oxide carrier is fully stirred, then is loaded and reacted for 10 hours at 90 ℃, then the reaction liquid is distilled off in a rotary way to remove water, and vacuum drying is carried out for 8 hours at 100 ℃ to obtain Co 4 Ni 1 -MOF/Al 2 O 3 Material (Co) 4 Ni 1 -MOF on oxide support gamma-Al 2 O 3 Is 10 percent of the load); then Co is added 4 Ni 1 -MOF/Al 2 O 3 And (3) carrying out pyrolysis treatment on the material: co is to be 4 Ni 1 -MOF/Al 2 O 3 Placing the material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 350 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 4 Ni 1 -MOF/Al 2 O 3 Derivatized Co 4 Ni 1 @C/Al 2 O 3 A catalyst.
(2)Co 4 Ni 1 -MOF/Al 2 O 3 Derivatized Co 4 Ni 1 @C/Al 2 O 3 The method for preparing the 1, 3-propanediol compound by catalyzing the high-selectivity hydrogenation of the glycidol by the catalyst comprises the following steps: co (Co) 4 Ni 1 -MOF/Al 2 O 3 Derivatized Co 4 Ni 1 @C/Al 2 O 3 135mg of catalyst, 27mmol of glycidol and 8.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and H is used 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 6 hours to obtain the 1, 3-propanediol compound.
As can be seen from the hydrogenation course of the epoxypropanol of FIG. 1, if a highly selective 1, 3-propanediol is desired, the epoxypropanol is subjected to an anti-Mahalanobis hydrogenation course. The nano CoNi@C catalyst derived from CoNi-MOF developed by us has good catalytic activity in examples 1-8, the conversion rate of glycidol is more than 85%, the selectivity of target product 1, 3-propanediol is more than 70%, and especially Co 1 N 1 -MOF derived Co 1 Ni 1 The catalyst @ C-300 can convert 100% of glycidol, and the selectivity of the product 1, 3-propanediol is as high as 94.3%.
Table 1 shows the reaction conditions and the hydrogenation results for the different catalysts according to examples 1 to 8
Figure BDA0004156367210000151
Examples 9 to 12
Examples 9 to 12 were the same as example 1 except that the "crystallization temperature" in the following step 3) was different, and the results are shown in the following table.
The catalysts Co prepared in examples 9-12 were accurately weighed 1 Ni 1 @C-300 (50 mg) and 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH), 130℃reaction temperature, H 2 The reaction was carried out for 5 hours at a pressure of 3.0MPa to give 1, 3-propanediol, the results of which are shown in Table 2 below:
TABLE 2
Figure BDA0004156367210000152
Figure BDA0004156367210000161
Examples 13 to 16
The results are shown in the following table for example 1 except that examples 13 to 16 are different from the "crystallization time" in the following step 3).
The catalysts Co prepared in examples 13 to 16 were accurately weighed 1 Ni 1 @C-300 (50 mg) and 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH), 130℃reaction temperature, H 2 The reaction was carried out for 5 hours at a pressure of 3.0MPa to give 1, 3-propanediol, the results of which are shown in Table 3 below:
TABLE 3 Table 3
Figure BDA0004156367210000162
Examples 17 to 19
The results are shown in the following table for example 1 except that examples 17 to 19 are different from the "pyrolysis temperature" in the following step 4).
The catalysts Co prepared in examples 17 to 19 were accurately weighed 1 Ni 1 @C-x (50 mg) and 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH), 130℃reaction temperature, H 2 The reaction was carried out for 5 hours at a pressure of 3.0MPa to give 1, 3-propanediol, the results of which are shown in Table 4 below:
TABLE 4 Table 4
Figure BDA0004156367210000163
Figure BDA0004156367210000171
Examples 20 to 23
The results are shown in the following table in example 1 except that examples 20 to 23 are different from the "reaction temperature" in the hydrogenation in the following step (2).
The catalysts Co prepared in examples 20 to 23 were accurately weighed 1 Ni 1 @C-300 (50 mg) and 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH), H 2 The reaction was carried out for 5 hours at a pressure of 3.0MPa to give 1, 3-propanediol, the results of which are shown in Table 5 below:
TABLE 5
Figure BDA0004156367210000172
Examples 24 to 26
The results are shown in the following table in examples 24 to 26 except that "the addition amount of glycidol and the addition amount of methanol as a solvent" are different from those of example 1.
The catalysts Co prepared in examples 24 to 26 were accurately weighed 1 Ni 1 @C-300 (50 mg) and glycidol, solvent methanol (containing 3.0mg/L NaOH), 130℃reaction temperature, H 2 The reaction was carried out for 5 hours at a pressure of 3.0MPa to give 1, 3-propanediol, the results of which are shown in Table 6 below:
TABLE 6
Figure BDA0004156367210000173
Figure BDA0004156367210000181
Comparative example 1
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmoL and the molar ratio of 1:1 in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF material.
(2) The method for preparing the 1, 3-propanediol compound by selectively hydrogenating the catalytic hydrogenated epoxypropanol by directly using the CoNi-MOF material as a catalyst comprises the following steps: co (Co) 1 Ni 1 50mg of MOF material, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added to a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
Comparative example 2
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Weighing cobalt nitrate with the mass of 5mmoL in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain single metal Co-MOF material.
4) And carrying out pyrolysis treatment on the single-metal Co-MOF material to obtain the Co@C catalyst derived from the Co-MOF material. Putting the Co-MOF material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2 hours, and obtaining the single-metal Co-MOF derived Co@C-300 catalyst.
(2) A method for preparing a 1, 3-propanediol compound by selectively hydrogenating catalytic hydrogenation epoxypropanol by using a monometal Co-MOF derived Co@C catalyst comprises the following steps: 50mg of a monometal Co-MOF derived Co@C-300 catalyst, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and the mixture is reacted with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5h to obtain 1, 3-propylene glycolAn alcohol compound.
Comparative example 3
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Weighing nickel nitrate with the mass of 5mmoL in a 100mL beaker, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, sequentially adding 30mL of DMF, 10mL of water and 10mL of ethanol to form a mixed solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain monometal Ni-MOF material.
4) And carrying out pyrolysis treatment on the monometal Ni-MOF material to obtain the Ni@C catalyst derived from the Ni-MOF. And (3) putting the Ni-MOF material into a vacuum tube furnace, introducing nitrogen with the content of 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃, and the pyrolysis treatment time is 2 hours, so that the single-metal Ni-MOF derived Ni@C-300 catalyst is obtained.
(2) A method for preparing a 1, 3-propanediol compound by catalytic selective hydrogenation of glycidol using a monometal Ni-MOF derived ni@c catalyst comprising the steps of: 50mg of a monometal Ni-MOF derived Ni@C-300 catalyst, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and the mixture is reacted with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to 130 ℃ for 5h of reaction to select the epoxypropanolHydrogenation reaction to obtain 1, 3-propanediol compound.
Comparative example 4
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which is shown in figure 1 and comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total mass of 5mmoL and the molar ratio of 1:1 in a 100mL beaker, adding 50mL of DMF as a solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, adding 50mL of DMF solvent, and fully stirring and dissolving to obtain solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF-I material.
4) Pyrolysis treatment is carried out on the CoNi-MOF-I material, and the nano CoNi@C-I catalyst derived from the CoNi-MOF-I material is obtained. Co is to be 1 Ni 1 Placing the MOF-I material into a vacuum tube furnace, introducing nitrogen with 30% hydrogen content for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 1 Ni 1 -MOF-I derivatized nano Co 1 Ni 1 Catalyst @ C-300-I.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing selective hydrogenation of glycidol by using a nano CoNi@C-I catalyst derived from CoNi-MOF-I comprises the following steps: co (Co) 1 Ni 1 -MOF-I derived Co 1 Ni 1 50mg of catalyst @ C-300-I, 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH) were charged into a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
Comparative example 5
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmoL and the molar ratio of 1:1 into a 100mL beaker, adding 50mL of water as a solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, adding 50mL of water as a solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room temperature aging treatment for 2 days, carrying out suction filtration by adopting a Bush funnel after the reaction is finished, respectively washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF-II material.
4) And carrying out pyrolysis treatment on the CoNi-MOF-II material to obtain the nano CoNi@C-II catalyst derived from the CoNi-MOF-II material. Co is to be 1 Ni 1 Placing the MOF-II material into a vacuum tube furnace, introducing nitrogen with 30% hydrogen content for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2h, and obtaining Co 1 Ni 1 -MOF-II derivatized nano Co 1 Ni 1 Catalyst @ C-300-II.
(2) A method for preparing a 1, 3-propanediol compound by catalyzing selective hydrogenation of glycidol by using a nano CoNi@C-II catalyst derived from CoNi-MOF-II comprises the following steps: co (Co) 1 Ni 1 -MOF-II derived Co 1 Ni 1 50mg of @ C-300-II catalyst,13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and H is used 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
Comparative example 6
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Respectively weighing cobalt acetate and nickel nitrate with the total material amount of 5mmoL and the molar ratio of 1:1 in a 100mL beaker, adding 50mL of ethanol as a solvent, and fully stirring and dissolving to obtain a solution A (the concentration of metal salt in the solution A is 0.1 mol/L);
2) Weighing 5mmol of terephthalic acid in a polytetrafluoroethylene lining, adding 50mL of ethanol as a solvent, and fully stirring and dissolving to obtain a solution B (the concentration of terephthalic acid in the solution B is 0.1 mol/L);
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2 hours at normal temperature, loading the lining into a reaction kettle, carrying out static crystallization reaction for 48 hours at 150 ℃, taking out the reaction kettle, carrying out room-temperature aging treatment for 2 days, carrying out suction filtration by adopting a suction filtration funnel after the reaction is finished, washing filter cakes obtained by suction filtration with ethanol for 3 times, washing with DMF for 3 times, and filtering to collect filter cakes; the drying treatment is specifically as follows: vacuum drying at 100deg.C for 8 hr to obtain Co 1 Ni 1 -MOF-III material.
4) And carrying out pyrolysis treatment on the CoNi-MOF-III material to obtain the nano CoNi@C-III catalyst derived from the CoNi-MOF-III material. Co is to be 1 Ni 1 Placing the MOF-III material into a vacuum tube furnace, introducing nitrogen with 30% hydrogen content for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2h to obtain Co 1 Ni 1 -MOF-III derivatized nano Co 1 Ni 1 Catalyst @ C-300-III.
(2) CoNi-MOF-III derived nano CoNi@C-III catalyst for catalysisA process for the selective hydrogenation of epoxidized glycidol to produce a 1, 3-propanediol compound comprising the steps of: co (Co) 1 Ni 1 -MOF-III derived Co 1 Ni 1 50mg of catalyst @ C-300-III, 13.5mmol of glycidol, 9.0g of solvent methanol (containing 3.0mg/L NaOH) were charged into a batch autoclave with H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
Comparative example 7
(1) The invention provides a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-selectivity hydrogenation of glycidol, which comprises the following steps:
1) Weighing nickel nitrate with a mass of 5mmoL in a 100mL beaker, adding 50mL of water as a solvent, stirring thoroughly, dissolving, and adding 3g of gamma-Al 2 O 3 Carrying out load reaction for 3 hours at 90 ℃ under 700W microwave auxiliary heating, and then carrying out rotary evaporation of water from the reaction liquid, wherein the drying treatment comprises the following steps: vacuum drying at 100deg.C for 8 hr to obtain 10% Ni-Al 2 O 3 A material.
2) 10% Ni-Al 2 O 3 The material is subjected to pyrolysis treatment to obtain 10 percent of Ni/Al 2 O 3 A hydrogenation catalyst. 10% Ni-Al 2 O 3 Putting the material into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300 ℃ and the pyrolysis treatment time is 2 hours, and obtaining 10% Ni-Al 2 O 3 Derivatized 10% Ni-Al 2 O 3 A catalyst.
(2)10％Ni-Al 2 O 3 Derivatized 10% Ni-Al 2 O 3 The method for preparing the 1, 3-propanediol compound by catalyzing selective hydrogenation of glycidol by using the catalyst comprises the following steps: 10% Ni-Al 2 O 3 Derivatized 10% Ni-Al 2 O 3 50mg of catalyst, 13.5mmol of glycidol and 9.0g of solvent methanol (containing 3.0mg/L of NaOH) are added into a batch pressure reactor, and H is used 2 Air in the reaction kettle is replaced3 times, then, fill with H 2 The hydrogen pressure in the reaction kettle reaches 3.0MPa, magnetic stirring (rotating speed 400 rpm/min) is started, the reaction kettle is heated to make the hydrogenation reaction temperature be 130 ℃, and the selective hydrogenation reaction of glycidol is carried out for 5 hours to obtain the 1, 3-propanediol compound.
As shown in FIG. 4, the catalyst Co prepared according to the present invention is compared with comparative examples 1, 2, 3, 4, 5, 6 and 7 1 Ni 1 The catalytic activity of @ C-300 is significantly higher than that of the precursor Co prepared in comparative example 1 1 Ni 1 MOF material, catalyst Co@C-300 prepared by adopting single metal cobalt salt in comparative example 2, catalyst Ni@C-300 prepared by adopting single metal nickel salt in comparative example 3, and catalyst Co prepared by adopting single solvent DMF in comparative example 4 1 Ni 1 MOF-I, comparative example 5 catalyst Co prepared with Single solvent Water 1 Ni 1 Catalyst Co prepared with Single solvent ethanol for MOF-II, comparative example 6 1 Ni 1 MOF-III and 10% Ni-Al prepared with Mono-metallic Nickel salt in comparative example 7 2 O 3 Catalyst, thus hydrogenation catalyst Co prepared by crystallization of mixed solvent 1 Ni 1 The @ C-300 catalyst is an effective catalyst for the preparation of the glycidol selective hydrogenation product 1, 3-propanediol compound.
And (3) performance detection:
x-ray diffraction
X-ray diffraction on a Rigaku D/MAX-IIIC X-ray diffractometer (CuK. Alpha:
Figure BDA0004156367210000251
Figure BDA0004156367210000252
) The measurement was performed. Grinding the sample fully, taking about 20-25 mg of sample into a tablet press, and feeding the sample into a tablet press at 500-600 kg/cm 2 Pressing into a sheet under pressure.
As can be seen from FIG. 2, co prepared in example 1 of the present invention 1 Ni 1 The XRD spectrum line of the MOF has a characteristic diffraction peak of the CoNi-MOF, and diffraction peaks with the 2 theta of 5-40 degrees in the figure are skeleton characteristic diffraction peak data of the CoNi-MOF; co described above 1 Ni 1 Co prepared by pyrolysis treatment of-MOF 1 Ni 1 At C-300 catalyst, small diffraction peak with 2 theta 8.9 deg. is attributed to residual small amount of CoNi-MOF after pyrolysis, diffraction peaks with 2 theta 44.4 deg., 51.5 deg. and 76.0 deg. are attributed to Co and Ni 111 respectively]Co and Ni [200 ]]And Co and Ni [220 ]]And (3) crystal plane diffraction. Description of Co after heat treatment of example 1 1 Ni 1 Most of the cobalt and nickel ions of the @ C-300 catalyst sample were reduced to atomic cobalt and nickel.
Scanning electron microscope image
The scanning electron microscope was used for measurement on a JSM6510LV scanning electron microscope manufactured by japan electronics company. The scan voltage was 30kV.
As can be seen from FIG. 3, co prepared in example 1 of the present invention 1 Ni 1 The MOF material is a flower-shaped crystal material formed by orderly stacking sheets, and a single sheet exposes more metal active sites, so that the diffusion of reactant molecules and product molecules in the catalytic reaction process and the formation of intermediates are facilitated, and an ideal reaction place is provided for the catalytic reaction; co prepared in example 2 4 Ni 1 The MOF has a part of the crystalline material of the flower type, but of different sizes, and in addition has a part of the distribution of the unshaped material; the Co-MOF prepared in comparative example 2 was not a flower-type crystalline material, whereas the Ni-MOF prepared in comparative example 3 had crystals stacked in layers, but the crystals were irregular.

Claims (10)

1. The preparation method of the catalyst for preparing the 1, 3-propanediol by high-selectivity hydrogenation of the glycidol is characterized by comprising the following steps:
1) Placing metal salt comprising cobalt salt and nickel salt into a container, sequentially adding DMF, water and ethanol as mixed solvents, and fully stirring and dissolving to obtain solution A;
2) Placing terephthalic acid into a polytetrafluoroethylene lining, sequentially adding DMF, water and ethanol as mixed solvents, and fully stirring and dissolving to obtain a solution B;
3) Adding the solution A and the solution B into a polytetrafluoroethylene lining to obtain a mixed solution C, stirring for 2-6 hours at normal temperature, filling the lining into a reaction kettle, crystallizing at 100-180 ℃ for 12-72 hours, taking out the reaction kettle, ageing at room temperature for 2-3 days, purifying and drying after the reaction is finished to obtain an M-MOF material;
4) And (3) performing direct pyrolysis treatment or thermal pyrolysis treatment carried on the oxide carrier on the M-MOF to obtain the catalyst.
2. The method for preparing the catalyst for preparing the 1, 3-propanediol by high selective hydrogenation of the glycidol according to claim 1, wherein in the step 1), cobalt salt is selected from one of cobalt nitrate and cobalt acetate, and nickel salt is selected from one of nickel nitrate and nickel acetate; the molar ratio of cobalt salt to nickel salt in the metal salt is 1-4: 1 to 4.
3. The method for preparing the catalyst for preparing the 1, 3-propanediol by high selective hydrogenation of the glycidol according to claim 1, wherein the mixed solvent in the step 1) and the mixed solvent in the step 2) are prepared from DMF, water and ethanol according to the volume ratio of 3:1:1, wherein the concentration of metal salt in the solution A is 0.1-0.2 mol/L, and the concentration of terephthalic acid in the solution B is 0.1-0.2 mol/L.
4. The method for preparing the catalyst for preparing 1, 3-propanediol by high selective hydrogenation of epoxypropanol according to claim 1, wherein in the step 3), the purification treatment is specifically: washing the obtained filter cake with ethanol for 3-5 times, washing with DMF for 3-5 times, and filtering to collect the filter cake; the drying treatment is specifically as follows: vacuum drying at 90-100 deg.c for 8-12 hr to obtain M-MOF material.
5. The method for preparing the catalyst for preparing 1, 3-propanediol by high selective hydrogenation of epoxypropanol according to claim 1, wherein the specific steps of said pyrolysis treatment in step 4) comprise: putting the mixture into a vacuum tube furnace, introducing nitrogen with 30% of hydrogen for pyrolysis treatment, wherein the pyrolysis treatment temperature is 300-600 ℃ and the pyrolysis treatment time is 1-2 h.
6. High selective hydrogenation of glycidol according to claim 1 or 5The preparation method of the 1, 3-propanediol catalyst is characterized in that the step of loading the M-MOF material on the oxide carrier in the step 4) comprises the following steps: dispersing M-MOF material into water, adding oxide carrier MOx selected from gamma-Al 2 O 3 、SiO 2 The mass of the M-MOF material accounts for 7-10% of the sum of the mass of the M-MOF material and the mass of the oxide carrier MOx; fully stirring, carrying out load reaction for 10-12 h at 80-90 ℃, then carrying out rotary evaporation of water from the reaction solution, and carrying out vacuum drying for 8-12 h at 90-100 ℃ to finish load.
7. The catalyst is characterized in that the catalyst is prepared by the preparation method of the catalyst for preparing 1, 3-propanediol by high-selective hydrogenation of epoxypropanol in any one of claims 1-6.
8. Use of the catalyst according to claim 7 for catalyzing the highly selective hydrogenation of glycidol to produce hydrogenated product 1, 3-propanediol.
9. The use of the catalyst according to claim 8, wherein the process for the preparation of 1, 3-propanediol by the high selectivity hydrogenation of glycidol comprises the steps of:
adding catalyst, epoxypropanol and solvent into batch pressure reactor, using H 2 3 times of air in the reaction kettle is replaced, and then H is filled in 2 The hydrogen pressure in the reaction kettle reaches 1-3.0 MPa, magnetic stirring is started, the reaction kettle is heated to enable the hydrogenation reaction temperature to be 90-130 ℃, and the selective hydrogenation reaction of the glycidol is carried out for 3-6 hours, so that the 1, 3-propanediol compound is obtained.
10. The use of a catalyst according to claim 9, wherein the catalyst is used in an amount of 1.0 to 10.0mg of catalyst per 1mmol of glycidol; the mass fraction of the epoxypropanol in the reaction liquid is 5-30%; the reaction solvent is selected from one of methanol, ethanol, isopropanol and tetrahydrofuran which all contain 3.0mg/L NaOH.
CN202310335454.3A 2023-03-28 2023-03-28 Preparation method of catalyst for preparing 1, 3-propylene glycol by high-selective hydrogenation of glycidol Pending CN116408086A (en)

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