CN110465296B - Nickel-based glucose hydrogenation catalyst and preparation method thereof - Google Patents
Nickel-based glucose hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nickel-based glucose hydrogenation catalyst and a preparation method thereof. The catalyst consists of main active components of nickel and nickel oxide, an auxiliary agent, silicon oxide and zirconium oxide; the content of the main active component nickel is 3-40 wt%, and the content of nickel oxide is 35-72%; the content of the auxiliary agent is 0.1 to 10 weight percent; the content of silicon oxide is 10-39 wt%, and the balance is zirconium oxide; wherein the auxiliary agent is one or two of cobalt and iron. The invention adopts a microwave-assisted coprecipitation method to synthesize catalyst precursor slurry, and the glucose hydrogenation catalyst is prepared by further crystallizing the slurry, drying, roasting, reducing and passivating. The catalyst prepared by the invention has uniform particle size distribution, the average particle size is 7-15 mu m, and the catalyst is used for the glucose hydrogenation reaction, has high activity and is safe to use; the preparation method is simple to operate, good in repeatability of batch preparation and low in cost.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a novel nickel-based catalyst for preparing sorbitol by glucose hydrogenation and a preparation method thereof.
Background
Sorbitol is also called sorbitol, is an important raw material for pharmaceutical, chemical, light industry and food industry, and is widely applied in many fields. At present, the international production process of sorbitol mainly comprises a catalytic hydrogenation method, an electrolytic oxidation method and a fermentation method. The main processes of the catalytic hydrogenation method include kettle type intermittent hydrogenation, external circulation intermittent hydrogenation, tubular continuous hydrogenation and the like. The kettle type intermittent hydrogenation production process is a traditional process for producing sorbitol in China, and is also a production process which adopts more processes at present, glucose is generally adopted as a raw material in the process, sorbitol is prepared through hydrogenation reaction under the action of a catalyst, and the used catalyst mainly comprises various modified Raney Ni catalysts or supported ruthenium catalysts. Ruthenium is the mainstream of sorbitol hydrogenation catalysts in the world at present, and the ruthenium is a relatively high-efficiency catalyst, but the ruthenium is relatively expensive, so that the use of the ruthenium is limited. The Raney Ni catalyst has the problems of poor stability, flammability in the processes of storage, transportation and use, great environmental pollution in the preparation process and the like. Therefore, the development of a novel glucose hydrogenation catalyst which is low in cost, environment-friendly and stable in performance has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and develop a nickel-based glucose hydrogenation catalyst which is low in cost, environment-friendly and high in activity.
The nickel-based glucose hydrogenation catalyst provided by the invention is composed of main active components of nickel and nickel oxide, an auxiliary agent, silicon oxide and zirconium oxide; the content of the main active component nickel is 3-40 wt%, and the content of nickel oxide is 35-72%; the content of the auxiliary agent is 0.1 to 10 weight percent; the content of silicon oxide is 10-39 wt%, and the balance is zirconium oxide; wherein the auxiliary agent is one or two of cobalt and iron.
In the nickel-based glucose hydrogenation catalyst, the molar ratio of the main active component nickel to the nickel oxide is preferably 0.2:1-1: 1.
The auxiliary agent is preferably cobalt and iron, and the atomic ratio of the cobalt to the iron is 1: 1-4:1.
The atomic ratio of silicon to zirconium in the catalyst is preferably from 2:1 to 8: 1.
The nickel-based glucose hydrogenation catalyst of the invention is preferably prepared by the following preparation method:
1) preparing a catalyst precursor filter cake: adding a zirconium salt solution and a mixed solution dissolved with sodium metasilicate and an alkaline precipitator into a base solution of a deionized water solution dissolved with nickel salt, an auxiliary agent salt and a small amount of polyethylene glycol in a parallel flow manner, and carrying out coprecipitation under the microwave radiation condition, wherein the pH value is kept at 7.0-9.0 in the precipitation process, the precipitation time is within 1 hour, and the microwave radiation power is 120-550W; after the precipitation is finished, stirring and aging for 0.5-6.0h, filtering and washing to obtain a catalyst precursor filter cake;
2) crystallizing a catalyst precursor filter cake: adding deionized water into the catalyst precursor filter cake, stirring uniformly, transferring into a high-pressure kettle, heating to 100 ℃ and 160 ℃, and crystallizing for 2.0-48.0h under the stirring condition; filtering and washing after crystallization, drying at 70-120 ℃, and roasting in air atmosphere at 300-650 ℃ to obtain a catalyst precursor;
3) reduction and passivation of a catalyst precursor: introducing N into the catalyst precursor2、H2Reducing the mixed gas at 350-800 ℃ for 2-5h, and cooling to 30-70 ℃; then introducing mixed gas of nitrogen and oxygen, or passivating the mixed gas with air for 2 to 10 hours to prepare the nickel-based glucose hydrogenation catalyst.
The invention also provides a preparation method of the nickel-based glucose hydrogenation catalyst, which comprises the following steps:
1) preparing a catalyst precursor filter cake:
dissolving zirconium salt into deionized water to obtain a solution I; dissolving sodium metasilicate and an alkaline precipitator into deionized water to obtain a solution II; preparing a base solution, wherein the base solution is a deionized water solution dissolved with nickel salt and auxiliary agent salts, and a small amount of polyethylene glycol is dissolved as a dispersing agent; the addition amount of the polyethylene glycol is preferably 0.1-2% of the total mass of the base solution;
when a catalyst precursor filter cake is prepared by coprecipitation, adding the solution I and the solution-II into a base solution in a parallel flow manner, carrying out coprecipitation under the microwave radiation condition, keeping the pH value at 7.0-9.0 in the precipitation process, controlling the precipitation time within 1 hour, and controlling the microwave power at 120-550W; stirring and aging for 0.5-6.0h after precipitation is finished, and performing suction filtration and washing to obtain a catalyst precursor filter cake;
2) crystallizing a catalyst precursor filter cake:
adding a proper amount of deionized water into the catalyst precursor filter cake, uniformly stirring, transferring into a high-pressure kettle, heating to 100 ℃ and 160 ℃, and crystallizing for 2.0-48.0h under the stirring condition; after crystallization, carrying out suction filtration and washing, drying at 70-120 ℃, and roasting in an air atmosphere at 300-650 ℃ to obtain a catalyst precursor;
3) reduction and passivation of a catalyst precursor:
introducing N into the catalyst precursor2、H2Mixed gas (N)2/H21.5-3.0 volume ratio), reducing for 2-5 hours at 350-800 ℃, and cooling to 30-70 ℃; then introducing mixed gas of nitrogen and oxygen, or passivating the mixed gas with air for 2 to 10 hours to prepare the nickel-based glucose hydrogenation catalyst.
In the above preparation method, the zirconium salt, the nickel salt and the auxiliary salt are preferably nitrate, sulfate, acetate, formate or chloride of the corresponding metal element.
The alkaline precipitant preferably comprises one or a mixture of two or more of sodium carbonate, sodium hydroxide, hexamethylenetetramine, urea and triethanolamine.
The nickel-based glucose hydrogenation catalyst has the characteristics of low price, environmental protection and stable performance. The preparation method of the catalyst adopts a microwave-assisted precipitation method to prepare the catalyst, shortens the reaction time, reduces the preparation energy consumption of the catalyst compared with the traditional heating method, and saves the production cost; in addition, the microwave-assisted precipitation reaction can enhance the stability of acid and alkali of the catalyst, improve the activity of the catalyst in the hydrogenation reaction and prolong the service life of the catalyst. The specified auxiliary agent is added in the preparation process of the catalyst, so that the selectivity of the catalyst in the reaction process can be improved while the higher hydrogenation activity of the catalyst is ensured; in the preparation process, the active component and the auxiliary agent salt are dissolved and then used as a base solution for precipitation preparation, and a proper amount of dispersing agent is added into the base solution, so that the particle size of catalyst particles can be effectively reduced, the particle size distribution of the catalyst is more concentrated and uniform (the average particle size is 7-15 mu m), and the activity of the catalyst is improved; the preparation process of the catalyst can realize zero emission and no pollution, and the catalyst is filtered and collected after being used and can be regenerated, thereby avoiding the pollution to the environment. The preparation method is simple to operate, good in repeatability of batch preparation and low in cost.
The catalyst has another advantage that the catalyst can be directly fed into a hydrogenation reaction kettle for reaction in the using process, and the problem that the reaction raw material liquid needs to be adjusted to be alkaline before the skeletal nickel catalyst is used is solved. Since the aqueous glucose solution is weakly acidic, its ionization constant increases and acidity increases as the temperature increases. The acidity has a corrosive effect on Raney Ni catalyst, and the activity of the Raney Ni catalyst is reduced along with the loss of active components. Therefore, the reaction solution generally needs to be adjusted to be alkaline, but under alkaline conditions, glucose is easy to generate polycondensation reaction to generate carbonization and coking phenomena, and the quality of the product is seriously influenced. The catalyst prepared by the invention overcomes the defects through the synergistic effect of silicon oxide, amphoteric oxide zirconium oxide and active component elements, has good stability in a weak acidic environment of a glucose aqueous solution, and has longer service life than a skeletal nickel catalyst.
Drawings
FIG. 1 is a graph of the particle size distribution of the catalysts prepared in examples 1-4 and comparative example 4;
FIG. 2 is a graph of temperature programmed reduced H for the catalysts prepared in examples 1-42-a TPR graph;
figure 3 is the XRD spectrum of the catalyst prepared in example 4.
Detailed Description
The technical solutions and technical effects of the present invention are further described below with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1 25.30g of zirconium nitrate pentahydrate was weighed and dissolved in deionized water to obtain 500mL of solution I, 80.85g of sodium metasilicate nonahydrate, 44.28g of sodium carbonate and 50.14g of sodium hydroxide were weighed and added to deionized water to obtain 500mL of solution II, 121.0g of nickel nitrate hexahydrate, 24.3g of cobalt nitrate hexahydrate and 2.0g of polyethylene glycol were weighed and dissolved in deionized water to obtain 1000mL of a base solution. Starting stirring, keeping the rotation speed at 650rpm, and dripping the solution I and the solution II into the base solution while maintaining a certain feeding speed under the microwave power of 300W, controlling the pH value of the reaction to be 8.0-9.0, and finishing the coprecipitation reaction within about 30 minutes. The reaction slurry was aged for 45 minutes. And after the aging is finished, carrying out suction filtration and washing on the slurry until the slurry is neutral, thus obtaining a catalyst precursor filter cake.
Adding the filter cake into 2L of deionized water for pulping, transferring the mixture into a high-pressure reaction kettle, starting a stirring and heating system, and heating the mixture to 120 ℃ for crystallization. After crystallization for 3.0h, the material is pumped, washed with water, dried for 3.0h at 110 ℃, and roasted for 4.0h at 400 ℃ by programmed heating to obtain a catalyst precursor. Crushing the catalyst precursor, sieving with a 200-mesh sieve, and passing N at 400 DEG C2、H2Mixed gas (N)2/H23: 1 volume ratio) for 2.0 hours, and the temperature is reduced to 70 ℃. And introducing mixed gas of nitrogen and oxygen for passivation for 3.0 hours to obtain the nickel-based glucose hydrogenation catalyst after passivation. The catalyst is marked a.
The hydrogenation performance of the catalyst is investigated by the reaction for preparing sorbitol by hydrogenating glucose. The reaction was carried out in a 2L autoclave. 1kg of glucose aqueous solution (glucose mass fraction is 50%), 10g of catalyst, 4.0MPa of hydrogen pressure, 100 ℃ of reaction temperature and 120 ℃ of reaction time is 2.0 h. The conversion of glucose was determined by conventional Felling reagent chemical titration. The product was analyzed by gas chromatography to investigate the selectivity of the reaction. The results of the catalyst activity evaluation are shown in Table 1.
The prepared catalyst was subjected to particle size distribution measurement using a Mastersizer 2000 laser particle sizer, and the measurement results are shown in fig. 1. The particle size distribution is a normal distribution curve, the abscissa represents the particle size of the particles, and the ordinate represents the percentage of particles of the corresponding particle size. The higher the peak value of the curve, the narrower the peak width, indicating that the particle size distribution is more concentrated and the uniformity is better. The catalyst particle size distribution is shown in FIG. 1.
The stability of the catalyst was determined by subjecting the catalyst precursor to a hydrogen temperature programmed reduction (H)2TPR), a higher reduction temperature indicates a higher catalyst stability. Catalyst H2The results of the TPR measurement are shown in FIG. 2.
Example 2 Nickel oxide and Nickel was roughly calculated to be nickel
Weighing 25.30g of zirconium nitrate pentahydrate, dissolving into deionized water to prepare 500mL of solution I, weighing 80.85g of sodium metasilicate nonahydrate, 37.75g of sodium carbonate, 71.23g of sodium hydroxide and 34.0g of hexamethylenetetramine, adding into deionized water to prepare 1000mL of solution II, weighing 241.0g of nickel nitrate hexahydrate, 18.33g of cobalt nitrate hexahydrate, 5.08g of ferric nitrate nonahydrate and 4.0g of polyethylene glycol, and dissolving into deionized water to prepare 1000mL of base solution. Starting stirring, keeping the rotation speed at 650rpm, and dripping the solution I and the solution II into the base solution while maintaining a certain feeding speed under the microwave power of 420W, controlling the reaction pH value to be 8.0-8.5, finishing the coprecipitation reaction within about 45 minutes, and aging the reaction slurry for 1 hour. And after the aging is finished, carrying out suction filtration and washing on the slurry until the slurry is neutral to obtain a catalyst precursor filter cake.
Adding the filter cake into 2L of deionized water for pulping, transferring the mixture into a high-pressure reaction kettle, starting a stirring and heating system, and heating the mixture to 120 ℃ for crystallization. After crystallization for 6.0h, the material is pumped, washed with water, dried at 110 ℃ for 3.0h, and roasted at 400 ℃ for 4.0h by programmed heating to obtain a catalyst precursor. The precursor is crushed and sieved by a 200-mesh sieve, and N is introduced at 400 DEG C2、H2Mixed gas (N)2/H22:1 volume ratio) was reduced for 2.0 hours, and the temperature was decreased to 30 ℃. And introducing mixed gas of nitrogen and oxygen for passivation for 3.0 hours to obtain the nickel-based glucose hydrogenation catalyst after passivation. The catalyst is marked b.
The method for evaluating the hydrogenation performance of the catalyst was the same as in example 1.
The prepared catalyst was subjected to particle size distribution measurement using a Mastersizer 2000 laser particle sizer, and the measurement results are shown in fig. 1. Catalyst H2The results of the TPR measurement are shown in FIG. 2.
Example 3
Weighing 25.30g of zirconium nitrate pentahydrate, dissolving into deionized water to prepare 500mL of solution I, weighing 50.21g of sodium metasilicate nonahydrate, 71.23g of sodium hydroxide and 249.6g of hexamethylenetetramine, adding into deionized water to prepare 1000mL of solution II, weighing 241.0g of nickel nitrate hexahydrate, 18.33g of cobalt nitrate hexahydrate, 7.62g of ferric nitrate nonahydrate and 4.0g of polyethylene glycol, and dissolving into deionized water to prepare 1000mL of base solution. Starting stirring, keeping the rotation speed at 650rpm, and dripping the solution I and the solution II into the base solution while maintaining a certain feeding speed under the microwave power of 420W, controlling the reaction pH value to be 8.0-8.5, and finishing the coprecipitation reaction within about 45 minutes. The reaction slurry was aged for 1 hour. And after the aging is finished, carrying out suction filtration and washing on the slurry until the slurry is neutral to obtain a catalyst precursor filter cake.
Adding the filter cake into 2L of deionized water for pulping, transferring the mixture into a high-pressure reaction kettle, starting a stirring and heating system, and heating the mixture to 120 ℃ for crystallization. After crystallization for 6.0h, the materials are pumped, washed with water, dried for 3.0h at 110 ℃, and roasted for 4.0h at 400 ℃. And obtaining the catalyst precursor. The precursor is crushed and sieved by a 200-mesh sieve, and N is introduced at 450 DEG C2、H2Mixed gas (N)2/H22:1 volume ratio) was reduced for 3.0 hours, and the temperature was decreased to 30 ℃. And introducing mixed gas of nitrogen and oxygen for passivation for 3.0 hours to obtain the nickel-based glucose hydrogenation catalyst after passivation. The catalyst is labeled c.
The method for evaluating the hydrogenation performance of the catalyst was the same as in example 1.
The prepared catalyst was subjected to particle size distribution measurement using a Mastersizer 2000 laser particle sizer, and the measurement results are shown in fig. 1. Catalyst H2The results of the TPR measurement are shown in FIG. 2.
Example 4
In the other preparation scheme, as in example 3, 25.30g of zirconium nitrate pentahydrate is weighed and dissolved in deionized water to prepare 500mL of solution I, 33.47g of sodium metasilicate nonahydrate, 71.23g of sodium hydroxide and 275g of hexamethylenetetramine are weighed and added in deionized water to prepare 1000mL of solution II, and coprecipitation reaction is carried out.
The crystallization temperature is raised to 150 ℃ after the precursor filter cake is beaten, and the crystallization time is prolonged to 12 hours. The catalyst is labeled d.
The method for evaluating the hydrogenation performance of the catalyst was the same as in example 1. The prepared catalyst was subjected to particle size distribution measurement using a Mastersizer 2000 laser particle sizer, and the measurement results are shown in fig. 1. Catalyst H2The results of the TPR measurement are shown in FIG. 2. The crystal phase structure of the catalyst was measured by using a Japanese Denko model D/MAX-2500X-ray diffractometer, and the measurement spectrum is shown in FIG. 3.
Example 5
The other preparation scheme is the same as that of example 4, the precursor is crushed and sieved by a 200-mesh sieve, and N is introduced at 500 DEG C2、H2Mixed gas (N)2/H22:1 vol) was reduced for 4.0 hours, and the temperature was decreased to 30 ℃. Then introducing mixed gas of nitrogen and oxygen for passivation for 3.0h,and preparing the nickel-based glucose hydrogenation catalyst after the passivation is finished. The method for evaluating the hydrogenation performance of the catalyst was the same as in example 1.
Comparative example 1
Other preparation scheme is the same as example 4, when solution I and solution II are fed at a certain speed and added dropwise into the base solution, the reaction system is heated to 75 ℃ by using an infrared heating plate without using microwave assistance. The catalyst was prepared under the same evaluation conditions as in example 1.
Comparative example 2
Other preparation scheme is the same as example 4, when solution I and solution II are fed at a certain speed and added dropwise into the base solution, the reaction system is heated to 85 ℃ by using an infrared heating plate without using microwave assistance. The catalyst was prepared under the same evaluation conditions as in example 1.
Comparative example 3
Other preparation scheme is the same as example 4, when solution I and solution II are fed at a certain speed and added dropwise into the base solution, the reaction system is heated to 95 ℃ by using an infrared heating plate without using microwave assistance. The catalyst was prepared under the same evaluation conditions as in example 1.
Comparative example 4
10g of a commercially available skeletal nickel catalyst (Raney-Ni, nickel content not less than 90 wt%) was weighed and added to a high-pressure reactor, and the catalyst activity evaluation conditions were the same as in example 1.
Comparative example 5
10g of a commercially available ruthenium/carbon catalyst (Ru/C, ruthenium content: 5 wt%) was weighed and charged into a high-pressure autoclave, and the catalyst activity evaluation conditions were the same as in example 1.
Comparative example 6
In the industrial production process of the glucose hydrogenation reaction, a small amount of fresh catalyst is properly added after the catalyst is used for one time, and the catalyst is reused for many times, and the fresh catalyst can not be completely replaced until the activity of the catalyst does not meet the requirement. Therefore, the longer the service life of the catalyst, the more times of application, and the lower the production cost.
A lifetime test of the catalyst was carried out using the catalysts of example 4, comparative example 2 and commercially available Ru/C (ruthenium content 5 wt%). The glucose hydrogenation reaction was carried out in a 2L autoclave. 1Kg of glucose aqueous solution (glucose mass fraction 50%), 13g of the first catalyst, 4.0MPa of hydrogen pressure, 100 ℃ of reaction temperature and 120 ℃ of reaction time of 2.0 h. After the reaction is finished, the original 1/3 catalyst is added in the second hydrogenation reaction to meet the reaction requirement, namely, the added fresh catalyst is 1/3 of the original dosage each time, and the service life of the catalyst is inspected by carrying out recovery and application experiments on the three catalysts by the method. The conversion of glucose was determined by conventional Felling reagent chemical titration. The product was analyzed by gas chromatography to investigate the selectivity of the reaction. The results of the catalyst activity evaluation are shown in Table 2.
TABLE 1 results of activity evaluation of different catalysts
TABLE 2 investigation of catalyst Life test results
Claims (8)
1. A nickel-based glucose hydrogenation catalyst is characterized in that: the catalyst consists of main active components of nickel, nickel oxide, an auxiliary agent, silicon oxide and zirconium oxide; the content of the main active component nickel is 3-40 wt%, and the content of nickel oxide is 35-72%; the content of the auxiliary agent is 0.1-10 wt%; the content of silicon oxide is 10-39 wt%, and the balance is zirconium oxide; wherein the auxiliary agent is one or two of cobalt and iron;
the catalyst is prepared by the following method:
1) preparing a catalyst precursor filter cake: adding a zirconium salt solution, a mixed solution of sodium metasilicate and an alkaline precipitator into a base solution of a deionized water solution in which nickel salt, an auxiliary salt and a small amount of polyethylene glycol are dissolved in a concurrent flow manner, and carrying out coprecipitation under the condition of microwave radiation, wherein the pH value is kept at 7.0-9.0 in the precipitation process, the precipitation time is controlled within 1 hour, and the microwave power of the microwave radiation is 120-550W; after the precipitation is finished, stirring and aging for 0.5-6.0h, filtering and washing to obtain a catalyst precursor filter cake;
2) crystallizing a catalyst precursor filter cake: adding deionized water into the catalyst precursor filter cake, uniformly stirring, transferring into an autoclave, heating to 100-160 ℃, and crystallizing for 2.0-48.0 hours under the stirring condition; filtering and washing after crystallization, drying at 70-120 ℃, and roasting at 300-650 ℃ in air atmosphere to obtain a catalyst precursor;
3) reduction and passivation of a catalyst precursor: introducing N into the catalyst precursor2、H2Reducing the mixed gas at 350-800 ℃ for 2-5h, and cooling to 30-70 ℃; and then introducing mixed gas of nitrogen and oxygen, or passivating the mixed gas with air for 2-10h to prepare the nickel-based glucose hydrogenation catalyst.
2. The nickel-based glucose hydrogenation catalyst according to claim 1, wherein the molar ratio of the main active component nickel to the nickel oxide is 0.2:1 to 1: 1.
3. The nickel-based glucose hydrogenation catalyst of claim 1, wherein the promoter is cobalt and iron, and the cobalt to iron atomic ratio is 1: 1-4: 1.
4. The nickel-based glucose hydrogenation catalyst of claim 1, wherein the atomic ratio of silicon to zirconium in the catalyst is 2:1 to 8: 1.
5. A method of preparing the nickel-based glucose hydrogenation catalyst of claim 1, wherein:
1) preparing a catalyst precursor filter cake:
dissolving zirconium salt into deionized water to obtain a solution I; dissolving sodium metasilicate and an alkaline precipitator into deionized water to obtain a solution II; preparing a base solution, wherein the base solution is a deionized water solution dissolved with nickel salt and auxiliary agent salts, and a small amount of polyethylene glycol is dissolved as a dispersing agent; adding the solution I and the solution II into the base solution in a parallel flow manner, and carrying out coprecipitation under the microwave radiation condition, wherein the pH value is kept at 7.0-9.0 in the precipitation process, the precipitation time is within 1 hour, and the microwave radiation power is 120-550W; after the precipitation is finished, stirring and aging for 0.5-6.0h, filtering and washing to obtain a catalyst precursor filter cake;
2) crystallizing a catalyst precursor filter cake:
adding a proper amount of deionized water into the precursor filter cake, uniformly stirring, transferring into an autoclave, heating to 100-160 ℃, and crystallizing for 2.0-48.0 hours under the stirring condition; filtering and washing after crystallization, drying at 70-120 ℃, and roasting at 300-650 ℃ in air atmosphere to obtain a catalyst precursor;
3) reduction and passivation of a catalyst precursor:
introducing N into the catalyst precursor2、H2Reducing the mixed gas at 350-800 ℃ for 2-5h, and cooling to 30-70 ℃; then introducing mixed gas of nitrogen and oxygen, or passivating the mixed gas with air for 2-10h to prepare the nickel-based glucose hydrogenation catalyst; wherein N is2、H2In the mixed gas, N2And H2The volume ratio of (A) to (B) is 1.5 to 3.0.
6. The preparation method according to claim 5, wherein the addition amount of the polyethylene glycol is 0.1-2% of the total mass of the base solution.
7. The method according to claim 5, wherein the zirconium salt, the nickel salt and the auxiliary salts are nitrates, sulfates, acetates, formates or chlorides of the corresponding metal elements.
8. The method of claim 5, wherein the alkaline precipitant comprises one or more of sodium carbonate, sodium hydroxide, hexamethylenetetramine, urea and triethanolamine.
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CN102746117B (en) * | 2012-06-27 | 2015-02-04 | 中国科学院大连化学物理研究所 | Method for catalytic conversion preparation of hexahydric alcohol from jerusalem artichoke as raw material |
CN104107691A (en) * | 2013-04-19 | 2014-10-22 | 厦门大学 | Novel Ru/CNTs catalyst used for preparing sorbitol through glucose hydrogenation, and preparation and application method thereof |
CN104370692B (en) * | 2013-08-13 | 2017-02-15 | 北京化工大学 | Polyol preparation method through glucose hydrogenolysis |
CN104190426B (en) * | 2014-09-02 | 2016-08-17 | 山东巨业精细化工有限公司 | A kind of preparation method of Ni-based consaturated oil hydrogenation catalyst |
CN106861704B (en) * | 2017-02-28 | 2019-09-10 | 山西大学 | A kind of preparation method and application of nickel-auxiliary agent-alumina-silica Zr catalyst |
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