CN114939430A - Boron-nitrogen-phosphorus co-doped metal-free catalyst and preparation method and application thereof - Google Patents
Boron-nitrogen-phosphorus co-doped metal-free catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a boron-nitrogen-phosphorus co-doped metal-free catalyst and a preparation method and application thereof, belonging to the technical field of catalytic materials, wherein sucrose, boric acid, deionized water, aluminum nitrate nonahydrate, phosphoric acid and melamine are sequentially added into a container and then uniformly stirred, acetic acid is added until the solution is completely clarified, the obtained solution is dried to remove moisture to obtain dry gel, the obtained dry gel is roasted and ground in a muffle furnace, sieved by a 40-60-mesh sieve and crystallized at 700-900 ℃, and then is washed by nitric acid to obtain the boron-nitrogen-phosphorus co-doped metal-free catalyst; the obtained catalyst is used for catalytically synthesizing the carbonic acid glyceride. The catalyst of the invention has simple synthesis process, cheap and easily obtained raw materials, and can be recycled for many times.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method and application of a boron-nitrogen-phosphorus co-doped metal-free catalyst, and further relates to a boron-nitrogen-phosphorus co-doped metal-free catalyst for glycerol carbonate synthesis reaction, and a preparation method and application thereof.
Background
With the development of science and technology, the country advocates 'green environmental protection', and the life is dominated by green energy. In the development of new energy, carbon materials play an increasingly important role by virtue of excellent characteristics such as high temperature resistance, high strength, conductivity, recoverability and recyclability. The carbon materials are various, including graphite materials, carbon composite materials, carbon fibers, graphene and the like, and have a wide application range, such as carbon nanotubes, graphene, fullerene, activated carbon and the like, and have been widely noticed by researchers at home and abroad due to their own unique physical properties and unique structures. In the field of catalysis, carbon materials are mainly used as catalysts, and can also be used as catalyst carriers to load specific metals so as to improve the catalytic activity of the catalysts. At present, scientific technology is continuously developed, researchers have prepared carbon materials with various structural properties, and the carbon materials have potential application values in the fields of catalysis, photovoltaics, wind power, lithium batteries and the like.
Glycerol Carbonate (GC) is an important glycerol derivative that is widely used as a protic solvent, additive and chemical intermediate. GC is used as a humectant for cosmetics and a carrier solvent for pharmaceutical preparations due to its low toxicity, low evaporation rate, low flammability and moisture retention. In the chemical industry, glycerol carbonate is a relatively new material that has great potential as a new component of gas separation membranes, as a solvent for several materials, and as a bio-lubricant, due to its ability to adhere to metal surfaces, resist oxidation, hydrolysis, and stress. Currently, several methods for preparing glycerol carbonate are reported: phosgene process, CO oxidative carbonylation process, ester exchange process, carbonylation process of glycerol and urea and CO 2 And (3) a conversion method. Among them, the alcoholysis of urea with glycerol and urea as raw materials is considered to be an efficient molecular reaction process, because ammonia gas is a by-product generated in the alcoholysis of urea and can also be used as a raw material for synthesizing urea. The method has the advantages of mild reaction conditions, safe operation, high product yield and the like. The catalysts for synthesizing GC are mainly divided into two categories, namely homogeneous catalysts and heterogeneous catalysts. The homogeneous catalysts being mainly inorganic salts, e.g. ZnSO 4 And MgSO 4 . Heterogeneous catalysts mainly comprise: hydrotalcite-based catalyst (HT (Mg/Zn/Al), zeolite-based catalyst (Zn-FAU), boiler waste ash-based catalyst (K) 2 SiO 3 ) Tungsten based catalysts (WO) 3 -TiO 2 ) Imidazolyl catalyst (PS- (Im) 2 ZnBr 2 ) Mesoporous crystalline materials (Zn/MCM-41), functionalized reticulated metal organic frameworks (F-IRMOF-3(BuI)), and the like. Homogeneous catalysis reported in the patent and literature at presentThe agent, urea and glycerol are mixed at a molecular level, and the catalytic activity can be regulated and controlled through a catalyst structure, but the stability of the catalyst structure and the recovery of the catalyst are important problems in the scientific and industrial fields. In contrast, although the structure of the heterogeneous catalyst cannot be accurately characterized, the active points of the heterogeneous catalyst are relatively stable, and the service life of the heterogeneous catalyst is relatively long, so that the heterogeneous catalyst is beneficial to recovery. However, the existing catalysts contain metal ions, which are not in accordance with the concept of green environmental protection, and have high cost, and the catalytic activity is continuously reduced in the circulating process, which is not beneficial to industrial production.
In summary, the above-mentioned catalysts for catalyzing urea and glycerol to glycerol carbonate have some problems. Mainly solves the problems that the metal catalyst has high cost and complicated recovery in the preparation process, does not accord with the green environmental protection idea, and the catalytic performance is reduced after circulation, so that the development of the non-metallic carbon material catalyst is very important for the alcoholysis reaction of the urea.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the background technology and provides a preparation method and application of a boron-nitrogen-phosphorus co-doped metal-free catalyst. The method utilizes a sol-gel method to prepare the boron-nitrogen-phosphorus co-doped metal-free catalyst. The preparation method of the boron-nitrogen-phosphorus co-doped catalyst is green and environment-friendly, and the preparation process is simple. The prepared boron-nitrogen-phosphorus co-doped metal-free catalyst is applied to the reaction of synthesizing the glycerol carbonate from urea and glycerol, and has good catalytic activity and stability.
The specific technical scheme of the invention is as follows:
in order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a boron-nitrogen-phosphorus co-doped metal-free catalyst comprises the steps of sequentially adding cane sugar, boric acid, deionized water, aluminum nitrate nonahydrate, phosphoric acid and melamine into a container, uniformly stirring, adding acetic acid until the solution is completely clear, drying the obtained solution to remove water to obtain dry gel, roasting the dry gel in a muffle furnace to obtain black solid, grinding the black solid, sieving the black solid with a 40-60-mesh sieve to obtain black particles with uniform particles, crystallizing the black particles at 700-900 ℃ in a vapor deposition furnace, and washing the black particles with 3-5 mol/L nitric acid to obtain the boron-nitrogen-phosphorus co-doped metal-free catalyst; wherein, according to molar ratio, the content of sucrose: boric acid: aluminum nitrate: phosphoric acid: melamine-7.5: 10:6.75:24: 1.
The preferred crystallization temperature is 800 ℃.
The preferred concentration of nitric acid is 4 mol/L.
A boron nitrogen phosphorus codoped metal-free catalyst is prepared according to the method.
The application of the boron-nitrogen-phosphorus co-doped metal-free catalyst is used for catalytically synthesizing glycerol carbonate, and specifically comprises the steps of mixing glycerol and urea according to a molar ratio of 1: 1-2 under the condition of a vacuum degree of 7.0KPa, adding a catalyst accounting for 5% of the mass of the glycerol, reacting at 120-140 ℃ to obtain glycerol carbonate, and filtering the catalyst after the reaction is finished. The reaction products were quantitatively analyzed by gas chromatography (Shimadzu, GC-2010Plus) equipped with a Wondacap WAX capillary column (30m) and a FID detector. And calculating the content of the glycerol carbonate by using an internal standard method, and judging the conversion rate of the glycerol and the selectivity of the glycerol carbonate.
The preferred molar ratio of glycerol to urea is 1:1.5 and the reaction temperature is 140 ℃.
Has the advantages that:
1. the carbon material catalyst disclosed by the invention is simple in synthesis process, cheap and easily available in raw materials, and the cost of the catalyst is greatly reduced;
2. the carbon material catalyst shows higher selectivity in a system for catalyzing urea and glycerol to generate glycerol carbonate, and generates fewer byproducts;
3. compared with other catalysts for catalyzing and synthesizing the glycerol carbonate, the carbon material catalyst disclosed by the invention is free of metal and more accords with the green development concept;
4. the carbon material catalyst is easy to separate after the reaction is finished, can be recycled for a plurality of times through simple washing and drying, prolongs the service life of the catalyst, and further reduces the cost.
Drawings
FIG. 1 is an SEM image of the catalyst BNP @ C-800 prepared in example 2.
FIG. 2 is an infrared image of the catalyst BNP @ C-800 prepared in example 2.
FIG. 3 is a drawing showing the nitrogen adsorption stripping of the catalyst BNP @ C-800 prepared in example 2.
FIG. 4 is an XPS survey of the catalyst BNP @ C-800 prepared in example 2.
FIG. 5 is a graph of the cycling performance of the catalyst BNP @ C-800 prepared in example 2.
FIG. 6 is an XRD pattern before and after reaction of the catalyst BNP @ C-800 prepared in example 2.
Detailed Description
Example 1
1) Preparation of boron nitrogen phosphorus codoped metal-free catalyst
10.3g of sucrose and 2.5g of boric acid are dissolved in 140mL of distilled water, stirred until the mixture is completely dissolved, 10g of aluminum nitrate is added, after the aluminum nitrate is dissolved, 5.5mL of phosphoric acid is added, 0.5g of melamine is added, the mixture is transferred to a water bath at 40 ℃, an appropriate amount of acetic acid is added until the solution is completely clarified, the mixture is placed on a water bath kettle at 80 ℃ for drying, after the solution is completely dried, the mixture is roasted for 10min in a muffle furnace at 300 ℃, then the mixture is ground and sieved by a sieve of 40-60 meshes to obtain black particles with uniform particles, the black particles are crystallized by a vapor deposition furnace and a program temperature rise to 700 ℃ under the condition of argon to obtain a carbon material, then 1.0g of the crystallized carbon material is washed by 10mL of 3mol/L of nitric acid at 60 ℃ for 5h, and dried in vacuum to obtain the boron-nitrogen-phosphorus co-doped metal-free catalyst which is marked as BNP @ C-700.
2) Experiment for synthesizing glycerol carbonate by catalyzing glycerol and urea
4.6g (0.05mol) of glycerin and 3.0g (0.05mol) of urea were added to a 100mL two-necked flask. When the urea was completely dissolved, the catalyst BNP @ C-700 (5% of the glycerol mass) was added to the flask. The reaction was carried out under a vacuum of 7.0KPa at 140 deg.C for 4h, and the conversion of glycerol was found to be 91% and the selectivity of glycerol carbonate was found to be 77%.
Example 2
1) Preparation of boron nitrogen phosphorus codoped metal-free catalyst
10.3g of sucrose and 2.5g of boric acid are dissolved in 140mL of distilled water, stirred until the mixture is completely dissolved, 10g of aluminum nitrate is added, after the aluminum nitrate is dissolved, 5.5mL of phosphoric acid is added, 0.5g of melamine is added, the mixture is transferred to a water bath at 40 ℃, an appropriate amount of acetic acid is added until the solution is completely clarified, the mixture is placed on a water bath kettle at 80 ℃ for drying, after the solution is completely dried, the mixture is roasted for 10min in a muffle furnace at 300 ℃, then the mixture is ground and sieved by a 40-60-mesh sieve to obtain black particles with uniform particles, the black particles are subjected to temperature programming to 800 ℃ under the condition of argon through a vapor deposition furnace for crystallization, then 1.0g of crystallized carbon material is taken, washed for 5 hours under the condition of 60 ℃ by using 4mol/L of nitric acid, and dried in vacuum to obtain the boron-nitrogen-phosphorus-free metal catalyst which is marked as @ BNP C-800. The SEM of this sample is shown in FIG. 1, the IR is shown in FIG. 2, the adsorption and desorption of nitrogen is shown in FIG. 3, and the XPS is shown in FIG. 4.
2) Experiment for synthesizing glycerol carbonate by catalyzing glycerol and urea
4.6g (0.05mol) of glycerol and 4.5g (0.075mol) of urea were added to a 100mL two-necked flask. When the urea was completely dissolved, the catalyst BNP @ C-800 (5% of the mass of glycerol) was added to the flask. The reaction is carried out under the condition of vacuum degree of 7.0KPa, the temperature is 140 ℃, the reaction time is 4h, the conversion rate of the glycerol is 93 percent, and the selectivity of the glycerol carbonate is 93 percent.
Example 3
1) Preparation of boron nitrogen phosphorus codoped metal-free catalyst
10.3g of sucrose and 2.5g of boric acid are dissolved in 140mL of distilled water, the mixture is stirred until the mixture is completely dissolved, 10g of aluminum nitrate is added, after the aluminum nitrate is dissolved, 5.5mL of phosphoric acid is added, 0.5g of melamine is added, the mixture is transferred to a water bath at 40 ℃, a proper amount of acetic acid is added until the solution is completely clarified, the mixture is placed on a water bath kettle at 80 ℃ for drying, after the solution is completely dried, the mixture is roasted for 10min in a muffle furnace at 300 ℃, then the mixture is ground and sieved by a sieve of 40-60 meshes to obtain black particles with uniform particles, the black particles are subjected to temperature programming in a vapor deposition furnace under the condition of argon to 900 ℃ for crystallization, then 1.0g of crystallized carbon material is washed for 5 hours under the condition of 60 ℃ by 5mol/L of nitric acid, and dried in vacuum to obtain the codoped boron-nitrogen-phosphorus metal-free catalyst which is marked as @ BNP C-900.
2) Experiment for synthesizing glycerol carbonate by catalyzing glycerol and urea
4.6g (0.05mol) of glycerin and 6.0g (0.10mol) of urea were added to a 100mL two-necked flask. When the urea was completely dissolved, the catalyst BNP @ C-900 was added to the flask. The reaction is carried out under the condition of vacuum degree of 7.0KPa, the temperature is 140 ℃, the reaction time is 4h, the conversion rate of the glycerol is 89%, and the selectivity of the glycerol carbonate is 60%.
Example 4
1) Preparation of boron nitrogen phosphorus codoped metal-free catalyst
The procedure was the same as in example 2.
2) Experiment for synthesizing glycerol carbonate by catalyzing glycerol and urea
When the reaction temperature was 130 ℃, the conversion of glycerol was 75% and the selectivity of glycerol carbonate was 77%.
Example 5
1) Preparation of boron nitrogen phosphorus codoped metal-free catalyst
The procedure was the same as in example 2.
2) Experiment for synthesizing glycerol carbonate by catalyzing glycerol and urea
When the reaction temperature is 120 ℃, the conversion rate of the glycerol is 60 percent, and the selectivity of the glycerol carbonate is 71 percent.
The experimental data of the above examples 1-5 for the catalytic synthesis of glycerol carbonate with different catalysts under different conditions are shown in table 1.
TABLE 1 conversion of glycerol and selectivity of glycerol carbonate in the synthesis of glycerol carbonate under different conditions
Example 6
1) Recovery treatment of catalyst
The solution obtained after the reaction of catalyzing the glycerol and the urea to synthesize the glycerol carbonate in the example 2 is filtered by a G5 sand core funnel, and the catalyst is obtained by filtration. And (3) cleaning the catalyst with absolute ethyl alcohol, placing the cleaned catalyst in a vacuum oven, and drying for 24 hours at 80 ℃ to obtain the recovered catalyst.
2) Cycle performance testing of the recovered catalyst
And (3) repeatedly carrying out 5 times of experiments for catalyzing glycerol and urea to synthesize the glycerol carbonate by using the recovered catalyst, wherein the experimental conditions are that the ratio of the glycerol to the urea is 1:1.5, the reaction temperature is 140 ℃, and the using amount of the catalyst is 5% of the mass of the glycerol. The performance of the catalyst in 5-cycle experiments is shown in fig. 5, and as can be seen from fig. 5, the catalytic efficiency of the BNP @ C-800 prepared by the invention is not obviously lost after being recycled for a plurality of times. In addition, the stability of the BNP @ C-800 after 5 times of circulation is researched by XRD, and as shown in figure 6, an XRD spectrum is consistent with a spectrum before reaction, which indicates that the BNP @ C-800 can be used as a stable catalyst for the reaction.
Claims (6)
1. Adding cane sugar, boric acid, deionized water, aluminum nitrate nonahydrate, phosphoric acid and melamine into a container in sequence, uniformly stirring, adding acetic acid until the solution is completely clear, drying the obtained solution to remove water to obtain dry gel, roasting the dry gel in a muffle furnace to obtain black solid, grinding the black solid, sieving the black solid with a 40-60-mesh sieve to obtain black particles with uniform particles, crystallizing the black particles at 700-900 ℃ in a vapor deposition furnace, and washing the black particles with 3-5 mol/L of nitric acid to obtain the boron-nitrogen-phosphorus co-doped metal-free catalyst; wherein, the molar ratio of sucrose, boric acid, aluminum nitrate, phosphoric acid and melamine is 7.5:10:6.75:24: 1.
2. The method for preparing the boron-nitrogen-phosphorus co-doped metal-free catalyst according to claim 1, wherein the crystallization temperature is 800 ℃.
3. The preparation method of the boron-nitrogen-phosphorus co-doped metal-free catalyst according to claim 1, wherein the concentration of the nitric acid is 4 mol/L.
4. A boron nitrogen phosphorus co-doped metal-free catalyst, which is prepared according to the method of claim 1.
5. The application of the boron-nitrogen-phosphorus co-doped metal-free catalyst prepared according to claim 1 in catalyzing and synthesizing glycerol carbonate comprises the specific steps of mixing glycerol and urea according to a molar ratio of 1: 1-2 under the condition that the vacuum degree is 7.0KPa, adding a catalyst accounting for 5% of the mass of the glycerol, reacting at 120-140 ℃ to obtain glycerol carbonate, and filtering the catalyst after the reaction is finished.
6. The application of the boron, nitrogen and phosphorus co-doped metal-free catalyst according to claim 5, wherein the molar ratio of glycerol to urea is 1:1.5, and the reaction temperature is 140 ℃.
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