CN115888711B - Sodium titanate nanowire supported copper catalyst and preparation method and application thereof - Google Patents
Sodium titanate nanowire supported copper catalyst and preparation method and application thereof Download PDFInfo
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a sodium titanate nanowire supported copper catalyst, which takes sodium titanate nanowires as carriers, copper nanoparticles are supported on the sodium titanate nanowires, and the size of the copper nanoparticles is 4nm-10nm; the nano-wires of the titanate are of a linear layered structure, and the average diameter is 70nm; the loading of the copper nano particles is 4% -20%. The invention also provides a preparation method of the sodium titanate supported copper catalyst and a method for preparing calcium lactate and hydrogen by using the sodium titanate supported copper catalyst. The sodium titanate nanowire supported copper catalyst is prepared by adopting a wet chemical reduction method, and has small size of the sodium titanate nanowire and the nano copper particle and good dispersibility and stability. When the catalyst is used for catalyzing the dehydrogenation of glycerin to prepare calcium lactate and hydrogen, high glycerin conversion rate, high selectivity of calcium lactate and high hydrogen yield can be obtained.
Description
Technical Field
The invention belongs to the field of calcium lactate preparation, and particularly relates to a sodium titanate nanowire supported copper catalyst, and a preparation method and application thereof.
Background
As an important organic acid calcium, the calcium lactate has the characteristics of high solubility, high dissolution speed, high bioavailability and good taste. Calcium lactate is widely applied to the fields of dairy products, beverages, food health products and the like. In the food industry, calcium lactate is a safe food additive that can be used as a solidifying agent, flavor enhancer, flavoring agent, ingredient, food softener, nutritional supplement, and stabilizer and thickener. The calcium lactate not only has the functions of reducing the permeability of capillary vessels and maintaining the normal excitability of nerves and muscles, but also can assist in preventing and treating various allergic diseases, thereby keeping the user to keep vigorous energy and physical strength. Calcium lactate has good water solubility, can be used as calcium supplement for human and animals, and can be widely applied in various calcium salts because of its absorption rate up to 32%.
The preparation method of the calcium lactate mainly comprises a neutralization method and a fermentation method. The neutralization method adopts lactic acid, calcium hydroxide, calcium carbonate and the like to neutralize and prepare calcium lactate. The fermentation method mainly uses glucose as a carbon source, lactic acid is obtained through microbial fermentation, and the lactic acid reacts with calcium carbonate in eggshell powder in fermentation liquor to generate calcium lactate. Zhang Pingzhi the calcium lactate is produced by a wheat starch wastewater double-enzyme saccharification and fermentation method, lactobacillus delbrueckii is adopted, and the total yield of twice crystallized calcium lactate can reach 78.9% at 50 ℃ when the initial sugar concentration is 7%, the corn steep liquor is 3% and the inoculation amount is 8%. The reaction process for preparing the calcium lactate by the fermentation method is relatively complicated, the impurity removal process is particularly complicated, the reaction period is long, the yield is low, and the impurity content in the product is high.
The glycerol is used as a downstream product of biodiesel, is mainly used for the production of cosmetics and the like, and reduces the application value of the biodiesel. Glycerol molecules having three hydroxyl groups can be used in the synthesis of a variety of chemicals, for example, 1, 2-propanediol, 1, 3-propanediol, acrolein, acrylic acid, lactic acid, and the like. The Kishida team reported for the first time the technique of hydrothermal synthesis of lactic acid in aqueous alkaline sodium hydroxide solution at 300 ℃.
However, under the condition of lower temperature (200 ℃ to 230 ℃), the alkaline sodium titanate carrier and the nano copper synergistically catalyze the glycerin to react with calcium hydroxide to synthesize calcium lactate in one step, and the calcium lactate product is prepared through crystallization separation, and the research of byproduct hydrogen is not reported.
Disclosure of Invention
The invention aims at the problems and overcomes the defects of the prior art, and provides a preparation method of a sodium titanate nanowire supported copper catalyst, which comprises the following specific steps:
(1) adding sodium hydroxide solution with the concentration of 2mol/L into the meta-titanic acid suspension according to the mol ratio of the meta-titanic acid to the sodium hydroxide of 1:3.5, and stirring for 2 hours to obtain a reaction solution; transferring the reaction solution into a reaction kettle, reacting for 12 hours at 80 ℃, and obtaining sodium titanate nanowires after the processes of cooling, washing, filtering and drying;
(2) 1.25mol/L copper nitrate trihydrate solution, sodium titanate nanowires and 30mL deionized water are mixed according to the mass ratio of the copper nitrate trihydrate to the sodium titanate nanowires of 6.04:8.4, heating to 60 ℃ and stirring for reaction for 1h to obtain suspension;
(3) dropwise adding 1.0mol/L NaOH solution into the suspension to ensure that the pH of the suspension is 11, and stirring for 0.5h; adding a hydrazine hydrate solution with the mass percentage of 85% at the speed of 1mL/min, wherein the molar ratio of hydrazine hydrate in the hydrazine hydrate solution to copper in copper nitrate trihydrate is 5-10:1, and continuously stirring and reducing for 4 hours to obtain a catalyst suspension; and washing and filtering to obtain the sodium titanate nanowire supported copper catalyst.
The purpose of the washing and filtering is to remove impurities such as nitrate.
The washing process is to wash the filtrate with deionized water until the conductivity of the filtrate is less than 2 mS.m -1 And then washing with absolute ethanol for 3 times.
And (3) storing the sodium titanate nanowire supported copper catalyst in absolute ethyl alcohol to prevent oxidation.
Micropump is used in the present invention to ensure a 1mL/min drip rate.
Preferably, the specific operation of the cooling, washing, filtering and drying process is that after the reaction liquid in the reaction kettle is cooled to room temperature, deionized water is used for washing until the conductivity of the filtrate is less than 2 mS.m -1 Filtering to obtain a filter cake, and then drying the filter cake in a drying oven at 120 ℃ for 12 hours to obtain the sodium titanate nanowire.
Preferably, the copper nitrate trihydrate solution is a solution obtained by dissolving 6.04g of copper nitrate trihydrate into 20mL of deionized water.
Preferably, the reaction kettle is a polytetrafluoroethylene reaction kettle.
Preferably, the meta-titanic acid suspension is a suspension obtained by adding meta-titanic acid into deionized water and stirring to uniformly disperse the meta-titanic acid in the deionized water.
The invention further aims to provide a sodium titanate nanowire supported copper catalyst, wherein the catalyst takes sodium titanate nanowires as carriers, and copper nanoparticles are supported on the sodium titanate nanowires; the size of the copper nano particles is 4nm-10nm; the nano-wires of the titanate are of a linear layered structure, and the average diameter is 70nm; the loading of the copper nano particles is 4% -20%.
The loading capacity of the copper nano particles is the percentage of the mass of the copper nano particles to the mass of the sodium titanate nanowire loaded copper catalyst.
The sodium titanate nanowire supported copper catalyst in the invention can be abbreviated as Cu/Na 2 TiO 3 The loading of the copper nano particles accounts for Cu/Na by the mass of the copper nano particles 2 TiO 3 The mass percent of the catalyst is expressed as 4%, 16% and 20% of copper nano particle load in the catalyst, which can be abbreviated as Cu (4)/Na 2 TiO 3 、Cu(16)/Na 2 TiO 3 、Cu(20)/Na 2 TiO 3 。
It is still another object of the present invention to provide an application of a sodium titanate nanowire-supported copper catalyst applied to the "one-step" reaction of glycerin with calcium hydroxide to produce calcium lactate and byproduct hydrogen.
Preferably, the specific method of application comprises the following steps: adding 200mL of glycerin aqueous solution with the concentration of 0.5-2mol/L, calcium hydroxide and sodium titanate nanowire supported copper catalyst into a reaction kettle according to the molar ratio of 0.4:1-0.8:1 of calcium hydroxide to glycerin and the mass ratio of 1:10-1:20 of sodium titanate nanowire supported copper catalyst to glycerin, evacuating air, slowly heating to 200-230 ℃, stirring at constant temperature for reacting for 0.5-6h, obtaining calcium lactate reaction liquid and hydrogen, and evaporating and crystallizing the calcium lactate reaction liquid to obtain a calcium lactate product.
Preferably, the stirring is at a rate of 500rpm.
The reaction mechanism of the invention is as follows: alkaline sodium titanate nanowire and nano copper double active site synergistic catalysis glycerol dehydrogenation and conversion to generate C-containing nano-copper 3 H 6 O 3 And the reaction intermediate reacts with calcium hydroxide in the reaction liquid to generate a calcium lactate product. The invention forms a technical route for synthesizing the calcium lactate in situ by one step from glycerin and calcium hydroxide, and overcomes the fermentation method in the process of preparing the calcium lactate by the traditional reaction of lactic acid and calcium hydroxideThe prepared lactic acid has the defect of high cost of raw materials, thereby realizing high glycerol conversion rate, high selectivity of target product calcium lactate and high hydrogen yield.
The invention has the beneficial effects that:
the sodium titanate nanowire supported copper catalyst is prepared by adopting a wet chemical reduction method, and has small size of the sodium titanate nanowire and the nano copper particle and good dispersibility and stability. When the catalyst is used for catalyzing the dehydrogenation of glycerin and reacting with calcium hydroxide to prepare calcium lactate and hydrogen, high glycerin conversion rate, high selectivity of target product calcium lactate and high hydrogen yield can be obtained.
Drawings
FIG. 1 is a Cu (16)/Na composition prepared according to the present invention 2 TiO 3 Transmission electron microscopy of the catalyst.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to specific embodiments. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
Example 1
(1) Catalyst preparation
9.8g of the meta-titanic acid-containing material was added to 100mL of deionized water, wherein the meta-titanic acid-containing material was prepared as TiO 2 The weight percentage is 46.6%, and the mixture is stirred for 0.5h under the action of a magnetic stirrer, so that the mixture is uniformly dispersed in water to obtain the metatitanic acid suspension. To the meta-titanic acid suspension was added 100mL of sodium hydroxide solution having a concentration of 2mol/L, in which meta-titanic acid (as TiO 2 Calculated by the mole ratio of the sodium hydroxide to the sodium hydroxide is 1:3.5, and stirring and reacting for 2 hours to obtain a reaction solution. The reaction solution was transferred to a polytetrafluoroethylene reaction vessel and reacted at 80℃for 12 hours. Cooling the reaction liquid in the reaction kettle to room temperature to obtain a sodium titanate nanowire sample, and washing the sodium titanate nanowire sample with deionized water until the conductivity of the filtrate is less than 2 mS.m -1 Filtering to obtain filter cake, oven drying at 120deg.C for 12 hr to obtain nanometer wire with average diameter of 70nm, as can be seen from figure 1The wire is in the form of a linear layer.
6.04g of copper nitrate trihydrate is weighed and dissolved in 20mL of deionized water, 8.4g of carrier sodium titanate nanowire and 30mL of deionized water are weighed, and the three materials are mixed and added into a 250mL round bottom flask to obtain a mixed solution. The mass of copper in the copper nitrate trihydrate accounts for 16% of the mass of the catalyst. The temperature of the mixture was kept at 60℃and stirred for 1 hour to obtain a suspension, which was added dropwise with a 1mol/L NaOH solution to adjust the pH of the suspension to 11. The reaction was continued at 60℃for 0.5h. The hydrazine hydrate solution was added dropwise at a flow rate of 1mL/min by a flow pump, wherein the mass percentage of hydrazine hydrate in the hydrazine hydrate solution was 85%, and the mass of the hydrazine hydrate solution was 7.54g. The number of moles of hydrazine hydrate is 5 times the number of moles of copper in nitric acid trihydrate. Adding hydrazine hydrate solution, and continuing stirring reduction reaction for 4 hours to obtain Cu (16)/Na 2 TiO 3 A catalyst suspension. Then washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and storing in absolute ethyl alcohol.
(2) Preparation of calcium lactate and hydrogen by glycerin catalytic dehydrogenation reaction
200mL of aqueous glycerin solution (0.5 mol/L) and 2mol/L, respectively, were charged into a reaction vessel equipped with a thermometer, a pressure gauge and a stirrer, according to Ca (OH) 2 Ca (OH) was added in a molar ratio of 0.6:1 to glycerol 2 1.84g of Cu (16)/Na was further added thereto 2 TiO 3 Catalyst, reuse of N 2 And (3) evacuating the air in the reaction kettle, starting stirring when the temperature of the reaction liquid reaches 230 ℃, adjusting the rotating speed to 500rpm, reacting for 4 hours to obtain calcium lactate reaction liquid and hydrogen, evaporating and crystallizing to obtain a calcium lactate product, and then analyzing the content of calcium lactate, wherein the experimental result is shown in table 1.
TABLE 1 application of Cu (16)/Na 2 TiO 3 Glycerol conversion rate, calcium lactate selectivity and hydrogen yield of calcium lactate and hydrogen prepared by catalyst
Example 2
(1) Catalyst preparation
As in example 1, the amount of copper nitrate trihydrate in step (1) was only varied such that the mass of copper in the catalyst was 4% and 20% of the mass of the catalyst, the molar ratio of hydrazine hydrate to copper being 5:1 and 10:1, respectively. Cu (4)/Na was prepared under different conditions 2 TiO 3 、Cu(20)/Na 2 TiO 3 A catalyst.
(2) Preparation of calcium lactate and hydrogen by glycerin catalytic dehydrogenation reaction
200mL of a 2mol/L aqueous glycerol solution was charged into a reaction vessel equipped with a thermometer, a pressure gauge and a stirrer, and the reaction vessel was charged with a catalyst according to Ca (OH) 2 Ca (OH) was added in a molar ratio of 0.6:1 to glycerol 2 1.84g of Cu (4)/Na was further added thereto 2 TiO 3 Or Cu (20)/Na 2 TiO 3 Catalyst, reuse of N 2 And (3) evacuating air in the reaction kettle, wherein the temperature of the reaction liquid reaches 230 ℃, the rotating speed is adjusted to 500rpm, and the calcium lactate reaction liquid and the hydrogen are obtained after 4 hours of reaction. Evaporating and crystallizing to obtain calcium lactate product, and analyzing calcium lactate content. The experimental results are shown in Table 2.
TABLE 2 Cu/Na application 2 TiO 3 Glycerol conversion rate, calcium lactate selectivity and hydrogen yield of calcium lactate and hydrogen prepared by the catalyst
Example 3
(1) Catalyst preparation
Catalyst Cu (16)/Na 2 TiO 3 The preparation conditions were the same as in example 1.
(2) Preparation of calcium lactate and hydrogen by glycerin catalytic dehydrogenation reaction
200mL of 2mol/L aqueous glycerin solution was added to a reaction vessel equipped with a thermometer, a pressure gauge and a stirrer, respectively, in accordance with Ca (OH) 2 Ca (OH) was added in a molar ratio to glycerol of 0.4:1, 0.6:1, 0.8:1 2 1.84g of Cu (16)/Na was further added thereto 2 TiO 3 Catalyst, using N 2 Evacuating air in the reaction kettle, regulating the rotation speed of the reaction liquid to 500rpm when the temperature of the reaction liquid reaches 230 ℃, and reacting for 4 hours to obtain milkCalcium acid reaction solution and hydrogen. Evaporating and crystallizing to obtain calcium lactate product, and analyzing calcium lactate content. The experimental results are shown in Table 3.
TABLE 3 application of Cu (16)/Na 2 TiO 3 Glycerol conversion rate, calcium lactate selectivity and hydrogen yield of calcium lactate and hydrogen prepared by the catalyst
Example 4
(1) Catalyst preparation
Catalyst Cu (16)/Na 2 TiO 3 The preparation conditions were the same as in example 1.
(2) Preparation of calcium lactate and hydrogen by glycerin catalytic dehydrogenation reaction
200mL of a 2mol/L aqueous glycerol solution was charged into a high-pressure reaction vessel equipped with a thermometer, a pressure gauge and a stirrer, and the mixture was stirred according to Ca (OH) 2 Ca (OH) was added in a molar ratio of 0.6:1 to glycerol 2 Then 1.84g or 3.68g of Cu (16)/Na was added thereto 2 TiO 3 Catalyst, reuse of N 2 And (3) evacuating air in the reaction kettle, regulating the rotating speed to 500rpm when the temperature of the reaction liquid reaches 200 ℃ and 230 ℃, and reacting for 0.5h, 4h and 6h to obtain the calcium lactate reaction liquid and hydrogen. Evaporating and crystallizing the calcium lactate reaction liquid to obtain a calcium lactate product, and then analyzing the content of calcium lactate. The experimental results are shown in Table 4.
TABLE 4 application of Cu (16)/Na 2 TiO 3 Glycerin conversion rate, calcium lactate selectivity and hydrogen yield of preparing calcium lactate and hydrogen by catalyzing glycerin dehydrogenation through catalyst
It should be understood that the foregoing detailed description of the present invention is provided for illustration only and is not limited to the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention may be modified or substituted for the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (9)
1. A preparation method of a sodium titanate nanowire supported copper catalyst is characterized by comprising the following steps of: the preparation method comprises the following specific steps:
(1) adding sodium hydroxide solution with the concentration of 2mol/L into the meta-titanic acid suspension according to the mol ratio of the meta-titanic acid to the sodium hydroxide of 1:3.5, and stirring for 2 hours to obtain a reaction solution; transferring the reaction solution into a reaction kettle, reacting for 12 hours at 80 ℃, and obtaining sodium titanate nanowires after the processes of cooling, washing, filtering and drying;
(2) 1.25mol/L copper nitrate trihydrate solution, sodium titanate nanowires and 30mL deionized water are mixed according to the mass ratio of the copper nitrate trihydrate to the sodium titanate nanowires of 6.04:8.4, heating to 60 ℃ and stirring for reaction for 1h to obtain suspension;
(3) dropwise adding 1.0mol/L NaOH solution into the suspension to ensure that the pH of the suspension is 11, and stirring for 0.5h; adding a hydrazine hydrate solution with the mass percentage of 85% at the speed of 1mL/min, wherein the molar ratio of hydrazine hydrate in the hydrazine hydrate solution to copper in copper nitrate trihydrate is 5-10:1, and continuously stirring and reducing for 4 hours to obtain a catalyst suspension; and washing and filtering to obtain the sodium titanate nanowire supported copper catalyst.
2. The method for preparing the sodium titanate nanowire supported copper catalyst according to claim 1, which is characterized in that: the specific operation of the cooling, washing, filtering and drying process is that after the reaction liquid in the reaction kettle is cooled to room temperature, deionized water is used for washing until the conductivity of the filtrate is less than 2 mS.m -1 Filtering to obtain a filter cake, and drying the filter cake in a drying oven at 120 ℃ for 12 hours to obtain the sodium titanate nanowire.
3. The method for preparing the sodium titanate nanowire supported copper catalyst according to claim 1, which is characterized in that: the copper nitrate trihydrate solution is a solution obtained by dissolving 6.04g of copper nitrate trihydrate into 20mL of deionized water.
4. The method for preparing the sodium titanate nanowire supported copper catalyst according to claim 1, which is characterized in that: the reaction kettle is a polytetrafluoroethylene reaction kettle.
5. The method for preparing the sodium titanate nanowire supported copper catalyst according to claim 1, which is characterized in that: the meta-titanic acid suspension is obtained by adding meta-titanic acid into deionized water and stirring to uniformly disperse the meta-titanic acid in the deionized water.
6. The sodium titanate nanowire supported copper catalyst is characterized in that: the catalyst takes sodium titanate nanowires as carriers, and copper nanoparticles are loaded on the sodium titanate nanowires; the size of the copper nano particles is 4nm-10nm; the nano-wires of the titanate are of a linear layered structure, and the average diameter is 70nm; the loading of the copper nano particles is 4% -20%.
7. The application of the sodium titanate nanowire supported copper catalyst is characterized in that: the sodium titanate nanowire supported copper catalyst is applied to catalyzing glycerol dehydrogenation and conversion and reacts with calcium hydroxide to prepare calcium lactate and hydrogen.
8. The use of a sodium titanate nanowire supported copper catalyst of claim 7, wherein: the specific method for the application comprises the following steps: adding 200mL of glycerin aqueous solution with the concentration of 0.5-2mol/L, calcium hydroxide and sodium titanate nanowire supported copper catalyst into a reaction kettle, wherein the molar ratio of the calcium hydroxide to the glycerin is 0.4:1-0.8:1, the mass ratio of the sodium titanate nanowire supported copper catalyst to the glycerin is 1:10-1:20, slowly heating to 200-230 ℃ after air is exhausted, stirring at constant temperature for reacting for 0.5-6h, and obtaining a calcium lactate reaction solution and hydrogen, and refining the calcium lactate reaction solution to obtain a calcium lactate product.
9. The use of a sodium titanate nanowire supported copper catalyst according to claim 8, wherein: the stirring rate was 500rpm.
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