CN110560073A - Nickel-based catalyst for preparing formic acid by hydrogenating bicarbonate and preparation method thereof - Google Patents
Nickel-based catalyst for preparing formic acid by hydrogenating bicarbonate and preparation method thereof Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
A nickel-based catalyst for preparing formic acid by hydrogenating bicarbonate and a preparation method thereof belong to the cross field of nano catalysis and energy environment. The method comprises the steps of adding a cationic surfactant, a cosurfactant and an oil phase into ammonia water, adding a nickel nitrate aqueous solution and a zinc nitrate aqueous solution, and dripping tetraethyl orthosilicate and isopropanol into the mixture to obtain a reaction solution. Then, the reaction solution was subjected to ultrasonic treatment and centrifugation, and the obtained solid phase was washed and dried. And then placing the dried sample in a tubular furnace for calcining to obtain the nickel-zinc metal oxide/silicon dioxide. Finally, H is introduced2And N2the mixed gas reduces the high-valence nickel in the sample to finally obtain the product Ni-ZnO/SiO2A catalyst. The preparation process is simple, and the prepared composite material is used as a heterogeneous catalystThe catalyst has high activity and high stability for catalyzing hydrogen carbonate hydrogenation reduction to prepare formic acid.
Description
Technical Field
The invention belongs to the cross field of nano catalysis and energy environment, and relates to Ni-ZnO/SiO2Composite material and preparation thereof for catalyzing hydrogen carbonate hydrogenation to prepare formic acid
Background
Since the use of large amounts of fossil fuels leads to an increase in the carbon dioxide content in the atmosphere, causing severe greenhouse effect, causing global temperature rise, glaciers melting, and sea level rise, the conversion and utilization of carbon dioxide is imminent. Due to the characteristic of low chemical activity of carbon dioxide, higher energy is required to be provided by direct utilization, and the economic benefit is lower. After the carbon dioxide reacts with alkali to be converted into bicarbonate, the chemical activity is obviously improved.
Gonz lez et al (Applied Catalysis B: Environmental,2018,224:368.) supported nickel on carbon as a catalyst, and hydrogenated with sodium bicarbonate water as a carbon source, and the yield of formic acid was only 1.2% at normal temperature and pressure, but no by-product was generated during the reaction. Wang et al (Green Chemistry,2017,19:716.) have shown good results in the hydrogenation reduction of bicarbonates by improving the preparation method of Raney nickel to increase the specific surface area of metallic nickel and thus the catalyst effect. The yield of formic acid can reach 86.6% at most under the conditions of 200 ℃ and 6MPa by using sodium bicarbonate as a carbon source; when the carbon source was replaced with potassium bicarbonate, the yield of formic acid reached 92.1% and substantially no by-products were formed. However, raney nickel has the disadvantages of being easily oxidized and difficult to store.
based on the above, the invention aims to synthesize a nickel-based catalyst with silicon dioxide as a carrier and zinc oxide as a modifier. Because of the electron transmission function between the nickel and the zinc oxide, the two components have a synergistic effect, and the activity and the stability of the catalyst can be obviously improved.
Disclosure of Invention
The invention provides a composite material Ni-ZnO/SiO2Wherein the silicon dioxide carrier is spherical and has a particle size of 20-100 nm(ii) a The active component nickel-zinc oxide is highly dispersed in the silicon dioxide spheres, and the particle size is 1.0-3.0 nm. The content of the active component is 1 wt% -10 wt%. The material is used as a heterogeneous catalyst and has higher activity and stability for catalyzing the preparation of formic acid by the hydrogenation of bicarbonate.
In order to prepare the catalyst, the technical scheme adopted by the invention is as follows:
A process for preparing the Ni-base catalyst used for preparing formic acid by hydrogenating hydrocarbonate is disclosed, which is Ni-ZnO/SiO2The preparation method of the composite material comprises the following steps:
(1) Adding a cationic surfactant, a cosurfactant and cyclohexane into analytically pure ammonia water, stirring at 25-35 ℃ until the mixture is clear, adding a nickel nitrate aqueous solution with the concentration of 0.1-1 mol/L and a zinc nitrate aqueous solution with the concentration of 0.1-1 mol/L, heating to 35-45 ℃, stirring for 30-50 min, dropwise adding tetraethyl orthosilicate, and continuing to react for 2-4 h; and finally adding isopropanol to react for 10-30 min to obtain reaction liquid.
The molar ratio of the cationic surfactant to the cosurfactant to the cyclohexane is 1: 4-7: 13-18. The ammonia water is analytically pure, the concentration of the ammonia water is 25% -28%, and the molar ratio of the cationic surfactant to the ammonia water to the nickel nitrate to the zinc nitrate to the tetraethyl orthosilicate is 10: 15-30: 0.080-0.80: 3-6: 130-260.
The cationic surfactant is cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride; the cosurfactant comprises n-propanol, n-butanol, n-pentanol, n-hexanol and cyclohexanol (C3-C6 short carbon chain alcohol).
The stirring speed is 500-600 rpm.
(2) And (2) at room temperature, transferring the reaction liquid obtained in the step (1) into an ultrasonic instrument, performing ultrasonic treatment for 10-30 min, transferring the reaction liquid into a centrifugal tube, performing centrifugal separation for 10-20 min at the rotating speed of 8000-10000 rpm, pouring to remove a liquid phase after the centrifugal separation, washing an obtained solid phase with isopropanol, and drying at 70-150 ℃ for 6-15 h.
(3) after the dried sample obtained in the step (2) is cooled to room temperature, the sample is cooledGrinding into powder. Calcining in a tubular furnace at 500-600 ℃, and keeping for 4-6 h to obtain NiO-ZnO/SiO2。
(4) Cooling the sample obtained in the step (3) to room temperature, and introducing 5% H into the tube furnace2And 95% N2The mixed gas of (2) reduces the high-valence nickel in the sample. Heating to 500-600 ℃, and keeping for 2-5 h. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2a catalyst.
The heating rate in the step (3) and the step (4) is 2-6 ℃/min; and (4) introducing the mixed gas in the step (4) at a rate of 20-60 mL/min.
The invention has the beneficial effects that:
(1) The Ni-ZnO/SiO of the invention2The catalyst has high activity in the process of catalyzing the reduction of bicarbonate, and can obtain higher yield of formic acid of 97 percent; the selectivity of the catalyst to formic acid is 100%, and no by-product is generated in the reaction process.
(2) The Ni-ZnO/SiO of the invention2As the catalyst for preparing formic acid by hydrogenating bicarbonate, the preparation process is simple and the conditions are mild. The synthesized catalyst has high stability and can be stored in the environment for a long time.
Drawings
FIG. 1 shows 1.2 wt% Ni-ZnO/SiO of the catalyst prepared in example 12A TEM image of the material;
FIG. 2 shows 5.4 wt% Ni-ZnO/SiO of the catalyst prepared in example 22A TEM image of the material;
FIG. 3 shows 9.0 wt% Ni-ZnO/SiO of the catalyst prepared in example 52A TEM image of the material;
FIG. 4 shows 5.4 wt% Ni-ZnO/SiO of the catalyst prepared in example 22HRTEM image of (A);
FIG. 5 shows 5.4 wt% Ni-ZnO/SiO of the catalyst prepared in example 22The active component under the HRTEM of (1);
FIG. 6 shows 5.4 wt% Ni-ZnO/SiO of the catalyst prepared in example 22The histogram of the catalyst particle diameter (a) and the size distribution of the active component (b) of (a).
Detailed Description
The present invention will be described in further detail with reference to embodiments, but it should be understood that the present invention is not limited to the embodiments.
Example 1
(1)0.01mol of cationic surfactant cetyl trimethyl ammonium bromide is added into a flask as a template agent, and then 5mL of cosurfactant n-butanol, 17mL of oil phase cyclohexane and 0.8mL of ammonia water are added, and the mixture is stirred at the rotation speed of 500rpm at 25 ℃ until the mixture is clear. 0.16mL of a 0.5mol/L aqueous nickel nitrate solution and 0.16mL of a 0.5mol/L aqueous zinc nitrate solution were added in this order with stirring. After warming to 35 ℃ and continuing stirring for 50min, 1.8mL of tetraethyl orthosilicate was added. After reacting for 4h, 10mL of isopropanol is added, and the reaction is continued for 10min to obtain a reaction solution.
(2) The reaction solution was transferred to an ultrasonic instrument for 30min, then transferred to a 10mL centrifuge tube and centrifuged at 8000rpm for 20 min. The centrifuged liquid phase was then removed by decantation and the remaining solid was washed by adding isopropanol. The washed solid-liquid mixture was further centrifuged at 8000rpm for 20 min. After removal of the ethanol wash by pouring, the remaining solid was dried in an oven at 70 ℃ for 15 h.
(3) After drying, the sample was cooled to room temperature, ground to a powder and placed in a tube furnace. The temperature rise rate of the tubular furnace is 2 ℃/min, the temperature is kept for 6h after being raised to 500 ℃, air is introduced in the process, and the air rate is kept to be 20 mL/min.
(4) After the sample was cooled to room temperature, 5% H was introduced at a gas rate of 20mL/min2And 95% N2The mixed gas of (2) reduces the high-valence nickel in the sample. The heating rate is 2 ℃/min, and the temperature is kept for 5h after being heated to 500 ℃. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2The loading amount of the catalyst, measured by ICP-MS, is 1.2 wt% (wherein the amount of Ni and ZnO is 1:1), the particle size of the catalyst is 28nm, and the particle size of the active component is 1.8nm, as observed by a transmission electron microscope.
The catalyst prepared in example 1 was used in the reaction for producing formic acid as a catalyst for hydrogenation reduction.
Adding the Ni-ZnO/SiO prepared in example 1 to a reaction kettle2458mg (calculated based on 5.5mg of Ni-ZnO), sodium bicarbonate was used as a carbon source for producing formic acid by hydrogenation, and 10mL of a 0.1mol/L aqueous solution of sodium bicarbonate was placed in an autoclave. Using 99.99% hydrogen as reducing agent, firstly replacing air in the reaction kettle with 1MPa hydrogen, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material to hydrogen in the reaction system to be 30(P (H)2)/C(NaHCO3)). The reaction was carried out at 200 ℃ for 2h, and the yield of formic acid by HPLC was 42.1%.
FIG. 1 shows 1.2 wt% Ni-ZnO/SiO of the catalyst prepared in example 12TEM images of the material.
Example 2
(1)0.01mol of cetyltrimethylammonium bromide, a cationic surfactant, was added as a template to the flask, followed by 5mL of n-butanol, 17mL of oil-phase cyclohexane, 0.8mL of aqueous ammonia, and stirred at 550rpm at 30 ℃ until clear. 0.80mL of a 0.5mol/L aqueous nickel nitrate solution and 0.80mL of a 0.5mol/L aqueous zinc nitrate solution were added in this order with stirring. After warming to 40 ℃ and stirring for 40min, 1.8mL tetraethyl orthosilicate was added. After reacting for 3h, 15mL of isopropanol is added, and the reaction is continued for 20min to obtain a reaction solution.
(2) The reaction solution was transferred to an ultrasonic instrument for 20min, then transferred to a 10mL centrifuge tube, and centrifuged at 9000rpm for 15 min. The centrifuged liquid phase was then removed by decantation and the remaining solid was washed by adding isopropanol. The solid-liquid mixture after washing was further centrifuged, and similarly centrifuged at 9000rpm for 15 min. After removing the ethanol wash by pouring, the remaining solid was dried in an oven at 100 ℃ for 12 h.
(3) After drying, the sample was cooled to room temperature, ground to a powder and placed in a tube furnace. The temperature rise rate of the tubular furnace is 4 ℃/min, the temperature is kept for 5h after being raised to 550 ℃, air is introduced in the process, and the air rate is kept to be 40 mL/min.
(4) After the sample was cooled to room temperature, 5% H was introduced at a gas rate of 40mL/min2And 95% N2The mixed gas of (2) is used for feeding high-valence nickel in the sampleAnd (5) performing row reduction. The heating rate is 4 ℃/min, and the temperature is kept for 3.5h after being heated to 550 ℃. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2The loading amount of the catalyst, measured by ICP-MS, of Ni-ZnO is 5.4 wt% (wherein the amount of Ni and ZnO is 1:1), the particle size of the catalyst is 61nm, and the particle size of the active component is 2.0nm, as observed by a transmission electron microscope.
FIG. 2 shows 5.4 wt% Ni-ZnO/SiO of the catalyst prepared in example 22TEM images of the material.
The catalysts prepared in the above cases were used in cases 3 and 4 as catalysts for the reduction of sodium bicarbonate to formic acid.
Embodiment 3
Adding the Ni-ZnO/SiO prepared in example 2 to a reaction kettle2110mg (calculated using 5.5mg Ni-ZnO) of sodium bicarbonate as the carbon source for the production of formic acid by hydrogenation, 10mL of aqueous sodium bicarbonate solution was placed in the autoclave. Using 99.99% hydrogen as reducing agent, firstly replacing air in the reaction kettle with 1MPa hydrogen, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material concentration in the reaction system to hydrogen pressure to be 30(P (H)2)/C(NaHCO3)). The reaction was carried out at 200 ℃ for 2h, and the yield of formic acid by HPLC was 66.7%.
The remaining procedures were identical to those in example 3, except that the ratio of the raw material to hydrogen in the reaction was 60(P (H)2)/C(NaHCO3) In this case), the conversion reached 81.3%. The ratio of feedstock to hydrogen was 80(P (H)2)/C(NaHCO3) In a reaction vessel, the conversion reached 83.0%.
Example 4
Adding the Ni-ZnO/SiO prepared in example 2 to a reaction kettle2110mg (calculated based on 5.5mg of Ni-ZnO), sodium bicarbonate is used as a carbon source for preparing formic acid by hydrogenation, and 10mL of 0.05mol/L aqueous solution of sodium bicarbonate is placed in an autoclave. Using 99.99% hydrogen as reducing agent, firstly using 1MPa hydrogen to replace air in the reaction kettle, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material to hydrogen in the reaction system to be 60(P (H)2)/C(NaHCO3)). The yield of formic acid by HPLC at 140 ℃ for 2h was 53.7%.
The rest of the process was identical to example 4, except that the reaction was carried out at 200 ℃ for 2h, and the conversion reached 81.3%. The reaction is carried out for 2h at 260 ℃, and the conversion rate reaches 97.0 percent.
Example 5
(1)0.01mol of cetyltrimethylammonium bromide, a cationic surfactant, was added as a template to the flask, followed by 5mL of n-butanol, 17mL of cyclohexane, 0.8mL of ammonia, and stirred at 600rpm at 35 ℃ until clear. 1.5mL of a 0.5mol/L aqueous nickel nitrate solution and 1.5mL of a 0.5mol/L aqueous zinc nitrate solution were added in this order with stirring. After warming to 45 ℃ and continuing stirring for 30min, 1.8mL of tetraethyl orthosilicate was added. After reacting for 2h, 20mL of isopropanol is added, and the reaction is continued for 30min to obtain a reaction solution.
(2) The reaction solution was transferred to an ultrasonic instrument for 10min, then transferred to a 10mL centrifuge tube and centrifuged at 10000rpm for 10 min. The centrifuged liquid phase was then removed by decantation and the remaining solid was washed by adding isopropanol. The washed solid-liquid mixture was further centrifuged, and similarly centrifuged at 10000rpm for 10 min. After removal of the ethanol wash by pouring, the remaining solid was dried in an oven at 150 ℃ for 6 h.
(3) After drying, the sample was cooled to room temperature, ground to a powder and placed in a tube furnace. The temperature rise rate of the tubular furnace is 6 ℃/min, the temperature is kept for 4h after being raised to 600 ℃, air is introduced in the process, and the air rate is kept to be 60 mL/min.
(4) After the sample was cooled to room temperature, 5% H was introduced at a gas rate of 60mL/min2And 95% N2The mixed gas of (2) reduces the high-valence nickel in the sample. The heating rate is 6 ℃/min, and the temperature is kept for 2h after being heated to 600 ℃. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2The loading amount of the catalyst, measured by ICP-MS, of Ni-ZnO is 9.0 wt% (wherein the amount of Ni and ZnO is 1:1), the particle size of the catalyst is 95nm, and the particle size of the active component is 3.0nm, as observed by a transmission electron microscope.
FIG. 3 shows 9.0 wt% Ni-ZnO/SiO of the catalyst prepared in example 52TEM images of the material.
The catalyst prepared in the above case was used in the reaction of reducing sodium bicarbonate to formic acid.
Addition of Ni-ZnO/SiO prepared in example 5 to the reaction vessel266mg (calculated based on 5.5mg of Ni-ZnO) of sodium bicarbonate was used as a carbon source for producing formic acid by hydrogenation, and 10mL of a 0.05mol/L aqueous solution of sodium bicarbonate was placed in an autoclave. Using 99.99% hydrogen as reducing agent, firstly replacing air in the reaction kettle with 1MPa hydrogen, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material to hydrogen in the reaction system to be 30(P (H)2)/C(NaHCO3)). The yield of formic acid by HPLC was 46.3% at 200 ℃ for 2 h.
Example 6
(1)0.01mol of cetyltrimethylammonium chloride, a cationic surfactant, was added as a template to the flask, followed by 4.1mL of n-propanol, 12.4mL of cyclohexane in the oil phase, 0.6mL of aqueous ammonia, and stirred at 550rpm at 30 ℃ until clear. 0.80mL of a 0.1mol/L aqueous nickel nitrate solution and 0.80mL of a 0.1mol/L aqueous zinc nitrate solution were added in this order with stirring. After the temperature is raised to 35 ℃ and stirring is continued for 40min, 0.36mL of tetraethyl orthosilicate is added. After reacting for 2.5h, adding 15mL of isopropanol, and continuing to react for 15min to obtain a reaction solution.
(2) The reaction solution was transferred to an ultrasonic instrument for 15min, then transferred to a 10mL centrifuge tube and centrifuged at 10000rpm for 10 min. The centrifuged liquid phase was then removed by decantation and the remaining solid was washed by adding isopropanol. The washed solid-liquid mixture was further centrifuged, and similarly centrifuged at 10000rpm for 10 min. After removal of the ethanol wash by pouring, the remaining solid was dried in an oven at 100 ℃ for 15 h.
(3) After drying, the sample was cooled to room temperature, ground to a powder and placed in a tube furnace. The temperature rise rate of the tubular furnace is 2 ℃/min, the temperature is kept for 4h after being raised to 550 ℃, air is introduced in the process, and the air rate is kept to be 40 mL/min.
(4) After the sample was cooled to room temperature, 5% H was introduced at a gas rate of 40mL/min2and 95% N2The mixed gas of (2) reduces the high-valence nickel in the sample. The rate of temperature rise is 2Heating to 600 deg.C/min, and maintaining at 2.5 hr. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2The catalyst had a Ni-ZnO loading of 5.4 wt% as determined by ICP-MS.
The catalyst prepared in the above case was used in the reaction of reducing sodium bicarbonate to formic acid.
Addition of Ni-ZnO/SiO prepared in example 7 to the reaction vessel2110mg (calculated using 5.5mg Ni-ZnO) of sodium bicarbonate as the carbon source for the production of formic acid by hydrogenation, 10mL of aqueous sodium bicarbonate solution was placed in the autoclave. Using 99.99% hydrogen as reducing agent, firstly replacing air in the reaction kettle with 1MPa hydrogen, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material concentration in the reaction system to hydrogen pressure to be 30(P (H)2)/C(NaHCO3)). The reaction was carried out at 200 ℃ for 2h, and the yield of formic acid by HPLC was 61.0%.
Example 7
(1)0.01mol of cetyltrimethylammonium bromide as a cationic surfactant was added to the flask as a template, followed by 5.7mL of n-hexanol, 21.6mL of oil-phase cyclohexane, 1.0mL of aqueous ammonia, and stirred at 550rpm at 30 ℃ until clear. 0.80mL of a 1mol/L aqueous nickel nitrate solution and 0.80mL of a 1mol/L aqueous zinc nitrate solution were added in this order with stirring. After the temperature was raised to 35 ℃ and stirring was continued for 40min, 3.6mL of tetraethyl orthosilicate was added. After reacting for 2.5h, adding 15mL of isopropanol, and continuing to react for 15min to obtain a reaction solution.
(2) The reaction solution was transferred to an ultrasonic instrument for 15min, then transferred to a 10mL centrifuge tube and centrifuged at 10000rpm for 10 min. The centrifuged liquid phase was then removed by decantation and the remaining solid was washed by adding isopropanol. The washed solid-liquid mixture was further centrifuged, and similarly centrifuged at 10000rpm for 10 min. After removing the ethanol wash by pouring, the remaining solid was dried in an oven at 100 ℃ for 12 h.
(3) After drying, the sample was cooled to room temperature, ground to a powder and placed in a tube furnace. The temperature rise rate of the tubular furnace is 2 ℃/min, the temperature is kept for 4h after being raised to 550 ℃, air is introduced in the process, and the air rate is kept to be 40 mL/min.
(4) After the sample was cooled to room temperature, 5% H was introduced at a gas rate of 40mL/min2And 95% N2the mixed gas of (2) reduces the high-valence nickel in the sample. The heating rate is 2 ℃/min, and the temperature is kept for 2.5h after being heated to 600 ℃. The sample obtained after reduction is the corresponding Ni-ZnO/SiO2The catalyst had a Ni-ZnO loading of 5.4 wt% as determined by ICP-MS.
The catalyst prepared in the above case was used in the reaction of reducing sodium bicarbonate to formic acid.
Addition of Ni-ZnO/SiO prepared in example 7 to the reaction vessel2110mg (calculated using 5.5mg Ni-ZnO) of sodium bicarbonate as the carbon source for the production of formic acid by hydrogenation, 10mL of aqueous sodium bicarbonate solution was placed in the autoclave. Using 99.99% hydrogen as reducing agent, firstly replacing air in the reaction kettle with 1MPa hydrogen, then charging hydrogen into the reaction kettle to 3MPa, and controlling the ratio of raw material concentration in the reaction system to hydrogen pressure to be 30(P (H)2)/C(NaHCO3)). The reaction was carried out at 200 ℃ for 2h, and the yield of formic acid by HPLC was 63.2%.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (7)
1. A preparation method of a nickel-based catalyst for preparing formic acid by hydrogenating bicarbonate is characterized by comprising the following steps:
(1) Adding a cationic surfactant, a cosurfactant and cyclohexane into analytically pure ammonia water, stirring at 25-35 ℃ until the mixture is clear, adding a nickel nitrate aqueous solution with the concentration of 0.1-1 mol/L and a zinc nitrate aqueous solution with the concentration of 0.1-1 mol/L, heating to 35-45 ℃, stirring for 30-50 min, dropwise adding tetraethyl orthosilicate, and continuing to react for 2-4 h; finally, adding isopropanol to react for 10-30 min to obtain reaction liquid;
The molar ratio of the cationic surfactant to the cosurfactant to the cyclohexane is 1: 4-7: 13-18; the molar ratio of the cationic surfactant to ammonia water to nickel nitrate to zinc nitrate to tetraethyl orthosilicate is 10: 15-30: 0.080-0.80: 3-6: 130-260.
(2) Transferring the reaction liquid obtained in the step (1) to an ultrasonic instrument for ultrasonic treatment at room temperature, centrifuging, then pouring off the liquid phase after centrifugal separation, washing the obtained solid phase with isopropanol, and drying at 70-150 ℃ for 6-15 h;
(3) After the dried sample obtained in the step (2) is cooled to room temperature, grinding the sample into powder; calcining in a tubular furnace at 500-600 ℃, and keeping for 4-6 h to obtain NiO-ZnO/SiO2；
(4) Cooling the sample obtained in the step (3) to room temperature, and introducing H into the tube furnace2And N2The mixed gas of (2) reduces the high-valence nickel in the sample; heating to 500-600 ℃, and keeping for 2-5 h; the sample obtained after reduction is the corresponding Ni-ZnO/SiO2A catalyst.
2. the method for preparing the nickel-based catalyst for preparing the formic acid by hydrogenating the bicarbonate according to the claim 1, wherein the cationic surfactant in the step (1) is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride; the cosurfactant comprises n-propanol, n-butanol, n-pentanol, n-hexanol and cyclohexanol.
3. The preparation method of the nickel-based catalyst for preparing formic acid through bicarbonate hydrogenation according to claim 1, wherein the ultrasonic treatment time in the step (2) is 10-30 min.
4. The method for preparing the nickel-based catalyst used for preparing the formic acid by hydrogenating the bicarbonate according to claim 1, wherein the centrifugal rotation speed in the step (2) is 8000-10000 rpm, and the centrifugal time is 10-20 min.
5. The method for preparing the nickel-based catalyst used for preparing the formic acid by hydrogenating the bicarbonate according to claim 1, wherein the temperature rise rate in the step (3) and the temperature rise rate in the step (4) are both 2-6 ℃/min.
6. The preparation method of the nickel-based catalyst for preparing formic acid through hydrogen carbonate hydrogenation according to claim 1, wherein the velocity of the mixed gas introduced in the step (4) is 20-60 mL/min.
7. The method according to claim 1, wherein the mixed gas introduced in step (4) comprises 5% H2And 95% N2。
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| CN113278995A (en) * | 2021-05-14 | 2021-08-20 | 中国科学院山西煤炭化学研究所 | Method for preparing oxalic acid from carbon dioxide or bicarbonate or carbonate |
| CN113578326A (en) * | 2021-08-18 | 2021-11-02 | 哈尔滨工业大学（深圳） | SiO2Ni-loaded double-layer core-shell catalyst and preparation method and application thereof |
| CN114618504A (en) * | 2022-04-14 | 2022-06-14 | 大连理工大学 | Nickel-oxide composite catalyst for preparing iodoarylamine from iodoaromatic nitro compound at high selectivity and application of nickel-oxide composite catalyst |
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