CN113398991A - Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst - Google Patents
Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst Download PDFInfo
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Abstract
The invention provides a preparation method and application of a hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst. Firstly, adding the polystyrene-divinylbenzene resin white balls after drying and dehydration into an organic solvent for swelling, and then adding a sulfonation reagent for sulfonic acid functionalization; adding the dehydrated and dried sulfonic acid functionalized resin white balls and zirconium oxychloride into ethanol, stirring and mixing uniformly, stirring and heating under constant temperature for refluxing, sequentially filtering, washing with an organic reagent, washing with deionized water and drying, adding the zirconium-loaded strong-acid cation exchange resin into a solvent-diluted hydrophobic agent silane, standing after ultrasonic treatment, filtering, washing and drying to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst. The catalyst is applied to the synthesis reaction of polymethoxy dimethyl ether, the preparation method of the catalyst is simple and convenient, the activity and stability of the resin catalyst after hydrophobic treatment are enhanced, and the conversion rate of reactants and the selectivity of products are improved.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst and application of the catalyst in synthesis of diesel additive polymethoxy dimethyl ether.
Background
In recent years, polyoxymethylene dimethyl ethers (PODE for short)nCH with simple structure3O(CH2O)nCH3And n is more than or equal to 1 and less than or equal to 8, and is used as a clean diesel additive, thereby attracting the wide attention of researchers. Studies have shown that PODE3-6The additive is added into diesel oil as a diesel oil additive, so that the cetane number and oxygen content of the diesel oil can be effectively increased, the combustion phase rate is improved, and the emission of pollutants such as nitrogen oxides, particulate matters, hydrocarbons and the like is greatly reduced. At the same time, since PODE3-6The physical and chemical properties of the diesel oil are similar to those of diesel oil, so that the diesel oil can be directly mixed into the diesel oil without changing the basic structure of a diesel engine. Polyoxymethylene dimethyl ethers are synthesized by providing methyl-terminated compounds (e.g., methanol, methylal and dimethyl ether) and providing intermediate-group compounds (e.g., formaldehyde, paraformaldehyde and trioxane) in the presence of homogeneous or heterogeneous acid catalysts. PODEnThe mass production route of (a) is based on methanol, which can be synthesized from biomass-derived syngas, natural gas and carbon dioxide. Thus, PODE is synthesized from methanolnIs a more potential sustainable production path.
At present, sulfuric acid, hydrochloric acid, trifluorosulfonic acid, etc. are common conventional liquid acids for catalyzing the synthesis of PODEn, but these inorganic liquid acids are corrosive, environmentally harmful, and difficult to separate from the product. Compared with the traditional inorganic liquid catalyst, the ionic liquid catalyst has the advantages of environmental protection, convenient recovery and the like. The heterogeneous acid catalyst is widely applied to catalytic synthesis of PODEN, and has the advantages of low corrosivity, high catalytic activity, convenience in catalyst recovery, simplicity in product separation and the like. Strong acid cation resin catalysts are widely used in acid-catalyzed reactions due to their large pore and surface area, high catalytic activity, low corrosivity, and ease of recovery. Catalyst activity of traditional strong acid cation resinThe sexual position is single
The acid sites can be used for increasing the acid strength and the acid site number of the catalyst and improving the activity of the catalyst by loading Lewis acid on the strong acid cation resin catalyst, and simultaneously, the stability of the catalyst and the selectivity of a product can be improved by endowing the catalyst with hydrophobicity.
The patent CN106944135A discloses that the polystyrene-divinylbenzene sulfonic acid resin catalyst is used for the etherification catalytic reaction production process of polymethoxy dimethyl ether, and the catalyst has high reaction activity and long service life. The patent CN105749991A uses an organic sulfone solvent to load a sulfonic acid resin catalyst and is used for polymerization of polyoxymethylene dimethyl ethers, and the catalyst reaction activity and the selectivity of a product PODE3-8 are improved. In patent CN111841635A, Lewis acid AlCl3 loaded strong acid cation exchange resin catalyst is applied to the reaction of methylal and trioxymethylene to synthesize polymethoxy dimethyl ether, so that the stability of the catalyst is improved.
At present, the catalytic activity of the strong-acid cation exchange resin catalyst is lower compared with the synthetic reaction with different reaction paths and reaction mechanisms because the catalytic activity site of the strong-acid cation exchange resin catalyst is single. Therefore, it is necessary to develop a composition which is highly efficient, highly stable and contains
And a hydrophobic strong-acid cation exchange resin catalyst with Lewis acid site, which is used for the synthesis reaction of polymethoxy dimethyl ether.
Disclosure of Invention
The invention aims to solve the technical problems, provides a novel preparation method of a hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst aiming at the problems of single catalytic activity site and low catalytic activity of the existing strong-acid cation exchange resin catalyst, and applies the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst to the synthesis of catalytic diesel additive polymethoxy dimethyl ether.
The improvement idea of the invention is as follows: sequentially carrying out sulfonic acid functionalization, zirconium loading and silane thinning on cation exchange resinHydration, improving the acid strength and the acid site of the catalyst, enhancing the reaction stability of the catalyst, and further improving the methanol conversion rate and the PDE in the synthesis process of the polyoxymethylene dimethyl ethers3-6Mass selectivity of (2).
In a first aspect of the present invention, a preparation method of a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst is provided, which comprises the following steps:
A. sulfonic acid functionalization
Adding the dried and dehydrated polystyrene-divinylbenzene resin white balls into an organic solvent for swelling, then adding a sulfonation reagent for sulfonic acid functionalization, and filtering, washing and drying to obtain sulfonic acid functionalized resin white balls;
B. zirconium loading
Adding the sulfonic acid functional resin white balls and zirconium salt obtained in the step A into an alcohol solvent, stirring and mixing uniformly, stirring and heating under a constant temperature condition for refluxing, and then sequentially filtering, washing with an organic reagent, washing with deionized water and drying to obtain a zirconium-loaded strong-acid cation exchange resin;
C. hydrophobization
And D, adding the zirconium-loaded strong-acid cation exchange resin obtained in the step B into a hydrophobic agent silane diluted by a solvent, carrying out constant-temperature ultrasonic treatment, standing, filtering, washing and drying to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst.
The preferred reaction conditions in the above steps are as follows:
in the step A:
the degree of crosslinking of the polystyrene-divinylbenzene resin white balls is 5-20%, the drying and dehydrating temperature of the resin white balls is 80-110 ℃, and the drying time is 6-24 hours;
the organic solvent comprises at least one of dichloroethane, chloroform, acetone, tetrahydrofuran and toluene, and the swelling time of the polystyrene-divinylbenzene resin white ball is 1-6 h;
the sulfonation reagent comprises at least one of concentrated sulfuric acid and chlorosulfonic acid with the mass concentration of 98%, the sulfonation reaction temperature is 80-120 ℃, and the sulfonation time is 2-6 h;
the drying temperature of the sulfonic acid functionalized resin white ball is 80-110 ℃, and the drying time is 6-24 h.
In the step B:
the zirconium salt comprises at least one of zirconyl chloride and zirconyl nitrate, and the mass ratio of the zirconium salt to the sulfonic acid functionalized resin white ball is (0.5-2.5): 1;
the alcohol solvent is ethanol, the mass ratio of the sulfonic acid functionalized resin white balls to the ethanol is 1 (5-20), and the solid-liquid mass ratio in an ethanol aqueous solution is 10-20: 100.
In the loading process, stirring, heating and refluxing for 6-24 hours at the constant temperature of 20-80 ℃;
in the washing process, the organic reagent for washing is at least one of methanol, ethanol, acetone and tetrahydrofuran;
in the drying process, the drying temperature is 80-110 ℃, and the drying time is 6-24 h.
In the step C:
the silane comprises at least one of hexadecyl trimethoxy silane, gamma-methacryloxy silane, phenyl triethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane;
the solvent for diluting the silane comprises at least one of water, methanol, ethanol and isopropanol, and the concentration of the diluted silane is 1-20 wt%;
the mass ratio of the zirconium-loaded strong-acid cation exchange resin to the diluted silane is 1: 10-50.
In the hydrophobization process, carrying out ultrasonic treatment for 1-5 h at a constant temperature of 20-60 ℃, and standing for 6-24 h;
the washing reagent comprises at least one of water, methanol and ethanol;
in the drying process, the drying temperature is 90-130 ℃, and the drying time is 6-24 h.
In the second aspect of the invention, the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst obtained by the preparation method is provided, and the mass content of zirconium in the catalyst is 1.50-5.00%
In a third aspect of the invention, the application of the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst is provided, namely the application of the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst in the synthesis of diesel additive polymethoxy dimethyl ether.
The fourth aspect of the invention provides a synthesis method of a diesel additive polymethoxy dimethyl ether, wherein the reaction raw material comprises water, methanol and formaldehyde, the mass content of the water is 10%, and the molar ratio of the formaldehyde to the methanol is 1.0-3.0; the poly (methoxy-dimethyl ether) is synthesized by catalyzing the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst according to claim 7, wherein the addition amount of the catalyst is 1.0-5.0% of the mass of the reaction raw materials, 1.0MPa nitrogen is introduced, the reaction temperature is set to be 70-100 ℃, and the reaction time is 0.5-5.0 h.
The effect of the synthesis reaction is influenced by a number of factors:
according to the embodiments 1-5, the addition amount of the hydrophobizing agent silane influences the zirconium loading amount in the catalyst, and the zirconium loading amount gradually decreases with the increase of the addition amount of the silane; conversion of methanol, PODE3-6And PODE1-6The mass selectivity of (A) shows a trend of increasing first and then decreasing according to the increase of the zirconium loading, the effect is best when the zirconium loading is 3.14%, and the methanol conversion rate and the PODE (solid-to-liquid) are increased continuously along with the continuous increase of the zirconium loading3-6The mass selectivity all gradually declines.
The reaction temperature is also critical in the synthesis process of the polymethoxy dimethyl ether, and the transformation rate of the methanol is increased along with the increase of the reaction temperature (60-100 ℃), and the PODE3-6And PODE1-6The mass selectivity of (2) is also increased correspondingly, but the rate of increase is gradually reduced (examples 1, 6 to 9).
In the aspect of the addition amount of the catalyst, the catalytic effect tends to increase and decrease along with the increase of the addition amount, when the addition amount of the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst in the reaction kettle is 4.0 percent of the mass of the reaction raw materials, the effect is optimal, the conversion rate of methanol is 65.78 percent, and PODE (potassium iodide-doped ethylene) is3-6Mass selectivity 24.47%, PODE1-6The mass selectivity was 98.68%. The catalyst content was still high, and the catalyst poisoning phenomenon was likely to occur (examples 1, 10 to 13).
In summary, the reaction conditions described in example 13 are the optimal process conditions for the present invention.
The invention has the following beneficial effects:
firstly, in the synthesis method of the hydrophobic zirconium-loaded strong acid cation exchange resin catalyst, due to the addition of the hydrophobic reaction step, the acid strength and the acid position of the strong acid cation exchange resin catalyst are improved, the reaction stability of the catalyst is enhanced, and the reactant conversion rate and the product selectivity are improved.
Secondly, the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst can directionally control the morphology and acid property of the catalyst by regulating the silane content in the catalyst synthesis step, and the reaction condition is easy to control and the quantitative reaction is easy to realize.
Thirdly, it was confirmed through experiments that the hydrophobic zirconium-supported strong acid cation exchange resin catalyst prepared according to the method of the present invention significantly improves the conversion rate of methanol and PODE as compared with zirconium-supported strong acid cation exchange resin catalysts that have not been hydrophobized and commercial strong acid cation exchange resins3-6The optimal catalytic performance can reach 65.78 percent of methanol conversion rate and 24.47 percent of PODE3-6Selectivity and 98.68% PODE1-6And (4) selectivity.
Drawings
FIG. 1 shows the results of stability examination of the hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst (1.5Zr-SR @10PTS) prepared in example 1, wherein the abscissa shows the number of times of reaction (i.e., the number of times of catalyst use), the ordinate (left) shows the conversion of the reactant, and the ordinate (right) shows the Product (PODE)1～6And PODE3～6) Selectivity of (2).
Description of terms: xZr-SR @ yA represents different zirconium-supported hydrophobic strongly acidic cation exchange resin catalysts. Wherein x is the mass ratio of zirconium oxychloride to sulfonic acid functionalized resin white spheres, SR represents a strong acid cation exchange resin catalyst, y is the mass ratio of the hydrophobizing agent silane diluted by the solvent to the zirconium-loaded strong acid cation exchange resin, and A is the kind of the hydrophobizing agent silane.
Detailed Description
The following embodiments are implemented on the premise of the technical scheme of the present invention, and give detailed implementation modes and specific operation procedures, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconyl chloride into 120g of ethanol, stirring and mixing uniformly, stirring and heating at 40 ℃, refluxing for 12h, filtering, washing with ethanol, washing with deionized water, and drying at 100 ℃ for 12h to obtain the zirconium-loaded strong-acid cation exchange resin.
Adding 10g of zirconium-loaded strong-acid cation exchange resin into 100g of phenyltriethoxysilane ethanol solution with the concentration of 10 wt%, carrying out constant-temperature ultrasonic treatment at 50 ℃ for 3h, standing for 12h, filtering, washing with ethanol, and drying at 100 ℃ for 12h to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst 1.5Zr-SR @10 PTS.
The 1.5Zr-SR @10PTS catalyst obtained in this example had a zirconium content of 3.14% by mass.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 2
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconyl chloride into 120g of ethanol, stirring and mixing uniformly, stirring and heating at 40 ℃, refluxing for 12h, filtering, washing with ethanol, washing with deionized water, and drying at 100 ℃ for 12h to obtain the zirconium-loaded strong-acid cation exchange resin.
Adding 10g of zirconium-loaded strong-acid cation exchange resin into 50g of phenyltriethoxysilane ethanol solution with the concentration of 10 wt%, carrying out constant-temperature ultrasonic treatment at 50 ℃ for 3h, standing for 12h, filtering, washing with ethanol, and drying at 100 ℃ for 12h to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst 1.5Zr-SR @5 PTS.
The 1.5Zr-SR @5PTS catalyst obtained in this example had a zirconium content of 4.15% by mass.
This example 1.5 application of Zr-SR @5PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @5PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 3
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconyl chloride into 120g of ethanol, stirring and mixing uniformly, stirring and heating at 40 ℃, refluxing for 12h, filtering, washing with ethanol, washing with deionized water, and drying at 100 ℃ for 12h to obtain the zirconium-loaded strong-acid cation exchange resin.
Adding 10g of zirconium-loaded strong-acid cation exchange resin into 75g of phenyltriethoxysilane ethanol solution with the concentration of 10 wt%, carrying out constant-temperature ultrasonic treatment at 50 ℃ for 3h, standing for 12h, filtering, washing with ethanol, and drying at 100 ℃ for 12h to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst 1.5Zr-SR @7.5 PTS.
The 1.5Zr-SR @7.5PTS catalyst obtained in this example had a zirconium content of 3.76% by weight.
This example 1.5Zr-SR @7.5PTS catalyst for the synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @7.5PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature at 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 4
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconyl chloride into 120g of ethanol, stirring and mixing uniformly, stirring and heating at 40 ℃, refluxing for 12h, filtering, washing with ethanol, washing with deionized water, and drying at 100 ℃ for 12h to obtain the zirconium-loaded strong-acid cation exchange resin.
Adding 10g of zirconium-loaded strong-acid cation exchange resin into 125g of phenyltriethoxysilane ethanol solution with the concentration of 10 wt%, carrying out constant-temperature ultrasonic treatment at 50 ℃ for 3h, standing for 12h, filtering, washing with ethanol, and drying at 100 ℃ for 12h to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst 1.5Zr-SR @12.5 PTS.
The 1.5Zr-SR @12.5PTS catalyst obtained in this example had a zirconium content of 2.78% by weight.
This example 1.5Zr-SR @12.5PTS catalyst for the synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @12.5PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature at 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 5
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconyl chloride into 120g of ethanol, stirring and mixing uniformly, stirring and heating at 40 ℃, refluxing for 12h, filtering, washing with ethanol, washing with deionized water, and drying at 100 ℃ for 12h to obtain the zirconium-loaded strong-acid cation exchange resin.
Adding 10g of zirconium-loaded strong-acid cation exchange resin into 150g of phenyltriethoxysilane ethanol solution with the concentration of 10 wt%, carrying out constant-temperature ultrasonic treatment at 50 ℃ for 3h, standing for 12h, filtering, washing with ethanol, and drying at 100 ℃ for 12h to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst 1.5Zr-SR @15 PTS.
The 1.5Zr-SR @15PTS catalyst obtained in this example had a zirconium content of 2.06%.
The application of the zirconium-loaded strong-acid cation exchange resin catalyst in synthesizing polymethoxy dimethyl ether by using methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @15PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 6
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to be 60 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 7
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to be 70 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 8
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to be 90 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 9
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 3g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to be 100 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 10
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, then adding 1g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 11
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, then adding 2g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 12
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, adding 4g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Example 13
A hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst 1.5Zr-SR @10PTS having a zirconium content of 3.14% by mass was prepared according to the method of example 1.
This example 1.5 application of Zr-SR @10PTS catalyst in synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. Adding 100g of reaction raw materials into a 250mL high-pressure reaction kettle, then adding 5g of 1.5Zr-SR @10PTS catalyst into the reaction kettle, introducing nitrogen to 1.0MPa, setting the reaction temperature to 80 ℃, collecting reaction products after reacting for 2h, and carrying out quantitative analysis, wherein the reaction results are summarized in Table 1.
Comparative example 1
Drying a polystyrene-divinylbenzene resin white ball with the crosslinking degree of 9% at 100 ℃ for 12h, adding 10g of the polystyrene-divinylbenzene resin white ball into 50g of dichloroethane for swelling for 3h, then adding 60g of concentrated sulfuric acid with the mass concentration of 98%, stirring at 100 ℃ for 3h, cooling to room temperature, filtering, washing with water, and drying at 100 ℃ for 12h to obtain the sulfonic acid functionalized resin white ball.
Adding 10g of sulfonic acid functionalized resin white balls and 15g of zirconium oxychloride into 120g of ethanol, stirring and mixing uniformly, stirring, heating and refluxing for 12h at 40 ℃, sequentially filtering, washing with ethanol, washing with deionized water, and drying for 12h at 100 ℃ to obtain the zirconium-loaded strong-acid cation exchange resin 1.5 Zr-SR.
The application of the zirconium-loaded strong-acid cation exchange resin 1.5Zr-SR in synthesizing polymethoxy dimethyl ether by using methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. 100g of reaction raw materials are added into a 250mL high-pressure reaction kettle, then 3g of zirconium-loaded strong-acid cation exchange resin 1.5Zr-SR is added into the reaction kettle, nitrogen is introduced to the reaction kettle to reach 1.0MPa, the reaction temperature is set to 80 ℃, reaction products are collected after 2 hours of reaction and are subjected to quantitative analysis, and the reaction results are summarized in Table 1.
Comparative example 2
The application of this comparative example commercial strong acid cation exchange resin catalyst (Amberlyst 36) to the synthesis of polymethoxy dimethyl ether from methanol and formaldehyde solution comprises the following steps:
the reaction raw material composition is that the mass content of water is 10 percent, and the molar ratio of formaldehyde to methanol is 2.0. 100g of the reaction materials were charged into a 250mL autoclave, then 3g of a commercial strong acid cation exchange resin catalyst (Amberlyst 36) was added to the autoclave, nitrogen was introduced to 1.0MPa, the reaction temperature was set at 80 ℃ and the reaction products were collected and quantitatively analyzed after 2 hours of reaction, and the reaction results are summarized in Table 1.
Table 1 examples and comparative PODE synthesis results
As can be seen from the results in Table 1, the method improves the acid strength and the number of acid sites of the catalyst, enhances the activity and the stability of the resin catalyst, and improves the conversion rate of reactant methanol and the target product PODE (peroxidase) by carrying out hydrophobic modification on the zirconium-loaded strong-acid cation exchange resin catalyst3-6And (4) selectivity. Compared with comparative example 2, the hydrophobic zirconium supported strong acid cation exchange resin catalyst prepared in inventive example 1 performed better than the commercial strong acid cation exchange resin catalyst (Amberlyst 36).
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (10)
1. A preparation method of a hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst is characterized by comprising the following steps:
A. sulfonic acid functionalization
Adding the dried and dehydrated polystyrene-divinylbenzene resin white balls into an organic solvent for swelling, then adding a sulfonation reagent for sulfonic acid functionalization, and filtering, washing and drying to obtain sulfonic acid functionalized resin white balls;
B. zirconium loading
Adding the sulfonic acid functional resin white balls and zirconium salt obtained in the step A into an alcohol solvent, stirring and mixing uniformly, stirring and heating under a constant temperature condition for refluxing, and then sequentially filtering, washing with an organic reagent, washing with deionized water and drying to obtain a zirconium-loaded strong-acid cation exchange resin;
C. hydrophobization
And D, adding the zirconium-loaded strong-acid cation exchange resin obtained in the step B into a hydrophobic agent silane diluted by a solvent, carrying out constant-temperature ultrasonic treatment, standing, filtering, washing and drying to obtain the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst.
2. The method for preparing a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst according to claim 1, characterized in that:
in the step A, the degree of crosslinking of the polystyrene-divinylbenzene resin white balls is 5-20%, the drying and dehydrating temperature of the resin white balls is 80-110 ℃, and the drying time is 6-24 hours;
the organic solvent comprises at least one of dichloroethane, chloroform, acetone, tetrahydrofuran and toluene, and the swelling time of the polystyrene-divinylbenzene resin white ball is 1-6 h;
the sulfonation reagent comprises at least one of concentrated sulfuric acid and chlorosulfonic acid with the mass concentration of 98%, the sulfonation reaction temperature is 80-120 ℃, and the sulfonation time is 2-6 h;
the drying temperature of the sulfonic acid functionalized resin white ball is 80-110 ℃, and the drying time is 6-24 h.
3. The method for preparing a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst according to claim 1, characterized in that:
in the step B, the zirconium salt comprises at least one of zirconyl chloride and zirconyl nitrate, and the mass ratio of the zirconium salt to the sulfonic acid functionalized resin white balls is (0.5-2.5): 1;
the alcohol solvent is ethanol, the mass ratio of the sulfonic acid functionalized resin white balls to the ethanol is 1 (5-20), and the mass ratio of solid to liquid in an ethanol aqueous solution is 10-20: 100.
4. The method for preparing a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst according to claim 1, characterized in that:
in the step B, stirring, heating and refluxing for 6-24 hours at a constant temperature of 20-80 ℃ in the loading process;
in the washing process, the organic reagent for washing is at least one of methanol, ethanol, acetone and tetrahydrofuran;
in the drying process, the drying temperature is 80-110 ℃, and the drying time is 6-24 h.
5. The method for preparing a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst according to claim 1, characterized in that:
in the step C, the silane comprises at least one of hexadecyl trimethoxy silane, gamma-methacryloxy silane, phenyl triethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane;
the solvent for diluting the silane comprises at least one of water, methanol, ethanol and isopropanol, and the concentration of the diluted silane is 1-20 wt%;
the mass ratio of the zirconium-loaded strong-acid cation exchange resin to the diluted silane is 1: 10-50.
6. The method for preparing a hydrophobic zirconium-supported strongly acidic cation exchange resin catalyst according to claim 1, characterized in that:
wherein in the hydrophobization process, ultrasonic treatment is carried out for 1-5 hours at a constant temperature of 20-60 ℃, and the standing time is 6-24 hours;
the washing reagent comprises at least one of water, methanol and ethanol;
in the drying process, the drying temperature is 90-130 ℃, and the drying time is 6-24 h.
7. The hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst obtained by the preparation method according to any one of claims 1 to 6.
8. The hydrophobic zirconium-supported strong acid cation exchange resin catalyst of claim 7, characterized in that:
wherein, the mass content of zirconium in the catalyst is 1.50-5.00%.
9. The use of the hydrophobic zirconium-loaded strong acid cation exchange resin catalyst of claim 7 in the synthesis of diesel additive polymethoxy dimethyl ether.
10. The synthesis method of the diesel additive polymethoxy dimethyl ether is characterized in that reaction raw materials comprise water, methanol and formaldehyde, the mass content of the water is 10%, and the molar ratio of the formaldehyde to the methanol is 1.0-3.0; the poly (methoxy-dimethyl ether) is synthesized by catalyzing the hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst according to claim 7, wherein the addition amount of the catalyst is 1.0-5.0% of the mass of the reaction raw materials, 1.0MPa nitrogen is introduced, the reaction temperature is set to be 70-100 ℃, and the reaction time is 0.5-5.0 h.
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