CN113522344A - Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof - Google Patents

Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof Download PDF

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CN113522344A
CN113522344A CN202110830200.XA CN202110830200A CN113522344A CN 113522344 A CN113522344 A CN 113522344A CN 202110830200 A CN202110830200 A CN 202110830200A CN 113522344 A CN113522344 A CN 113522344A
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acid
zirconium
kit
aluminum
composite oxide
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CN113522344B (en
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于峰
张豆豆
潘大海
任所财
闫晓亮
刘同慧
陈树伟
褚格
闫贝贝
王恒燕
李瑞丰
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Taiyuan University of Technology
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Abstract

The invention discloses an ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material which is obtained by taking a KIT-6 material with a three-dimensional cubic ordered mesoporous pore structure as a carrier, uniformly coating a layer of zirconium-aluminum composite oxide on the surface of the carrier and stably immobilizing a large amount of sulfuric acid groups. The solid acid material prepared by the invention has a highly regular and ordered three-dimensional cubic mesoporous pore channel structure, a larger specific surface area and pore volume, and uniform mesoporous pore diameter, and the surface acid amount, acid center type, acid density and acid strength of the mesoporous pore wall are adjustable, so that the solid acid material can be used for catalyzing the transesterification reaction of soybean oil and methanol to synthesize biodiesel, and shows excellent biodiesel yield, catalytic stability and regeneration reusability.

Description

Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof
Technical Field
The invention belongs to the technical field of preparation of inorganic porous solid acid catalytic materials, and relates to a sulfated zirconia-based composite metal oxide solid acid material and a preparation method thereof. The composite metal oxide solid acid material has a three-dimensional cubic mesoporous channel structure with high regularity and order, higher specific surface area and pore volume, uniform mesoporous aperture, and adjustable pore wall surface acid amount, acid density, acid center type and acid strength, and can be used for catalyzing the transesterification reaction of soybean oil and methanol to synthesize biodiesel.
Background
In the field of acid catalysis, with conventional liquid acid catalysts (e.g. H)2SO4HF and H3PO4) Compared with the prior art, the solid acid catalyst has the advantages of no corrosion, no pollution, easy separation, reusability, simple operation process and the like, becomes a novel green catalyst, and has wide application prospect in catalytic cracking, alkylation, isomerization, acylation, esterification and ester exchange reactions(Prog. Chem., 2011,23, 860；J. Mol. Catal. A-Chem., 2005, 237, 93)。
The solid acid catalyst is a solid material with Br ӧ nsted (B) acid and/or Lewis (L) acid catalytic active center on the surface. Sulfated zirconia as a representative of solid acid catalysts, whose surface acid center is derived from the surface hydroxyl defect of zirconia and the induction of S = O bond: (Catal. Today, 1994, 20, 295；Catal. Rev., 1996, 38, 329). Coordination adsorption of SO on surface of zirconia4 2-Then, due to the strong electron withdrawing effect of S = O bond, the electron cloud on the Zr-O bond on the surface is strongly deviated, so that the Zr atom has the capability of accepting electron pair and generates an L acid center; at the same time, the strong electron-withdrawing induction effect of S = O bond can reduce the electron cloud density in the Zr-OH, weaken the H-O bond function and generate the B acid center (B acid center) capable of providing protonJ. Catal., 1994, 150, 143)。
The electronic property, coordination state and Zr-OH content of Zr species on the surface of the carrier are changed by increasing the specific surface area of the zirconia carrier and by virtue of selective doping of metal heteroatoms with larger electronegativity, SO that the method is beneficial to enhancing the zirconia carrier and SO4 2-Promote large amount of SO by the bonding effect between4 2-The stable immobilization can realize the effective regulation and control of the type, distribution and strength of the acid center on the surface of the obtained solid acid material, and the sulfated zirconia solid acid catalytic material (with more excellent catalytic performance) is expected to be obtainedJ. Phys. Chem. C, 2007, 111, 18731；Chem. Eng. J., 2019, 364, 111)。
However, the mesoporous zirconia carrier prepared by the traditional method not only shows poor porosity, low specific surface area and small pore diameter, but also is easy to generate crystal phase transformation in the heating process, SO that the mesoporous zirconia carrier is loaded with SO4 2-The obtained solid acid material generally has the defects of low acid content, poor structural thermal stability, difficult regulation and control of acid center type and distribution, easy loss and inactivation of active components in the catalytic process and the like, thereby seriously limiting the practical application of the solid acid material in a plurality of catalytic reactions.
Therefore, how to get throughThe zirconia-based carrier material which has high structural stability, large specific surface area, excellent mass transfer capacity and strong bonding effect with sulfuric acid groups is obtained through a simple and easily repeated preparation process, SO that SO is treated4 2-The method has important research value and practical significance for the development of high-performance sulfated zirconia-based solid acid catalytic materials with practical application values by regulating and controlling the type, distribution and strength of acid centers on the surface of the obtained solid acid material while stabilizing and immobilizing a large amount of solid acid materials.
Disclosure of Invention
The invention aims to provide an ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and a preparation method thereof, wherein a surface in-situ coating technology is used for coating zirconium-aluminum composite oxide on the surface of the pore wall of an ordered mesoporous KIT-6 material with a three-dimensional cubic mesoporous pore structure in a highly uniform manner, and the ordered mesoporous KIT-6 material is used as a carrier for SO4 2-A large amount of groups are stably immobilized, and the sulfated zirconia-based composite metal oxide solid acid catalytic material which has good pore canal connectivity, regular and ordered mesoporous structure, larger specific surface area and pore volume, high structure stability, adjustable surface acid amount, acid center type and acid strength is prepared.
The ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material is prepared by the following method:
1) dissolving inorganic acid, organic carboxylic acid and triblock copolymer nonionic surfactant P123 in deionized water according to the molar ratio of silicon source, organic carboxylic acid, inorganic acid, deionized water, n-butyl alcohol and triblock copolymer nonionic surfactant P123= (30-100) = (0-100): (0-800): (100-750): (8000-18000): 15-100): 1, slowly adding n-butyl alcohol, stirring uniformly, adding a silicon source, stirring uniformly, performing hydrothermal treatment in a sealed high-pressure reaction kettle at the temperature of 80-160 ℃, and preparing the ordered mesoporous KIT-6 material wrapping the surfactant micelle;
2) carrying out high-temperature treatment on the ordered mesoporous KIT-6 material at 350-750 ℃ in an inert atmosphere so as to partially carbonize surfactant micelles existing in mesoporous channels of the KIT-6 material;
3) placing the ordered mesoporous KIT-6 material subjected to high-temperature treatment in an aqueous solution in which a zirconium source and an aluminum source are dissolved for impregnation treatment, taking out the material and roasting the material in the air at 450-650 ℃ to remove partially carbonized surfactant micelles, thus preparing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide;
4) and placing the ordered mesoporous KIT-6 material with the surface of the pore wall coated with the zirconium-aluminum composite oxide in a sulfuric acid solution for dipping treatment, taking out the material and roasting the material in the air at the temperature of 300-650 ℃, thus preparing the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
In the preparation method of the invention, the silicon source is one of methyl orthosilicate, ethyl orthosilicate, water glass or white carbon black, or a mixture of several of them in any proportion.
In the preparation method, the aluminum source is one of aluminum isopropoxide, aluminum tert-butoxide, aluminum isobutanolate, aluminum nitrate or aluminum chloride, or a mixture of several of the aluminum sources in any proportion.
In the above preparation method of the present invention, the zirconium source is one of zirconium oxychloride, zirconium isopropoxide, zirconium acetate or zirconium nitrate, or a mixture of several of them in any proportion.
In the above preparation method of the present invention, the inorganic acid is hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
In the preparation method of the invention, the organic carboxylic acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
In the step 1), after the n-butanol and the silicon source are respectively added, the mixture is fully stirred. Particularly, after the silicon source is added, the mixture is stirred for not less than 24 hours and then is subjected to hydrothermal treatment.
More specifically, the above-mentioned stirring treatment is preferably performed at normal temperature or slightly higher than normal temperature.
The time of the hydrothermal treatment is preferably 12-36 h.
In the step 2), the ordered mesoporous KIT-6 material is subjected to high-temperature treatment for 0.5-5 hours in an inert atmosphere.
In the step 3), the ordered mesoporous KIT-6 material subjected to high-temperature treatment is placed in an aqueous solution in which a zirconium source and an aluminum source are dissolved for impregnation treatment according to the solid/liquid volume ratio of (0.02-1) to 1.
In the aqueous solution in which the zirconium source and the aluminum source are dissolved, the concentrations of the zirconium source and the aluminum source are respectively 0.01-1.0 mol/L.
Further, the ordered mesoporous KIT-6 material after high-temperature treatment is preferably soaked in an aqueous solution in which a zirconium source and an aluminum source are dissolved for 10-60 min under stirring.
Further, it is preferable that the product obtained by the immersion treatment in the aqueous solution in which the zirconium source and the aluminum source are dissolved is baked in air for 2 to 6 hours.
In the step 4), the ordered mesoporous KIT-6 material with the zirconium-aluminum composite oxide coated on the surface of the pore wall is placed in a sulfuric acid solution with the concentration of 0.1-2 mol/L for dipping treatment according to the solid/liquid volume ratio of (0.01-0.1) to 1.
Further, preferably, the ordered mesoporous KIT-6 material with the surface of the pore wall coated with the zirconium-aluminum composite oxide is subjected to dipping treatment for 10-60 min in a sulfuric acid solution under stirring.
Furthermore, the product after dipping treatment in the sulfuric acid solution is preferably roasted in the air for 2-6 h.
In the self-assembly process of KIT-6, the organic carboxylic acid is selectively and properly introduced to inhibit the hydrolysis-polymerization reaction rate of a silicon precursor, increase the content of silicon hydroxyl which is not completely polymerized in a synthetic solution, enhance the hydrogen bond interaction between the silicon hydroxyl and the hydrophilic block of the triblock copolymer nonionic surfactant P123, and promote the cooperative self-assembly between inorganic silicon hydroxyl species and P123 molecules, so that the ordered mesoporous KIT-6 material which has higher order and wraps organic surfactant micelles is obtained.
And then, carrying out partial carbonization treatment on the surfactant micelle in the KIT-6 mesoporous pore canal in an inert atmosphere, so that an obvious gap exists between the surfactant micelle after carbonization and shrinkage and the KIT-6 mesoporous pore wall, and the method is used for uniformly coating the zirconium-aluminum composite oxide on the surface of the KIT-6 mesoporous pore wall in the dipping treatment process.
Then, removing the partially carbonized surfactant micelle in the mesoporous pore channel by air roasting treatment to obtain a KIT-6 material with a layer of zirconium-aluminum composite oxide uniformly coated on the surface of the mesoporous pore wall, and using the KIT-6 material as a carrier for SO4 2-A large amount of stable immobilization.
In the preparation process, the stability, the specific surface area, the pore volume, the pore diameter and the coating amount and the electronic property of the zirconium-aluminum composite oxide on the surface of the KIT-6 pore structure can be regulated and controlled by regulating the introduction type and the introduction amount of the organic carboxylic acid, the hydrothermal treatment temperature, the micelle carbonization shrinkage heat treatment condition of the surfactant, the zirconium-aluminum composite oxide impregnation treatment condition and the air roasting condition, and finally the SO is introduced4 2-After the group is formed, the surface acid amount, the acid center type, the distribution and the acid strength of the obtained ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material are effectively regulated and controlled.
The preparation method of the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material is simple and easy to implement and has high reproducibility. The obtained solid acid material has a highly regular and ordered three-dimensional cubic mesoporous pore channel structure, high structural stability, large specific surface area and mesoporous pore diameter, and the zirconium-aluminum composite oxide coating degree on the surface of the pore wall is adjustable and the surface acidity is controllable.
Through determination, the specific surface area of the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is 250-600 m2Per g, pore volume of 0.3-1.0 cm3The pore diameter is 4.0-12.0 nm, the molar ratio of zirconium/aluminum atoms on the surface of the mesoporous pore wall can be adjusted within the range of 0.01-100, and the acid content, the acid density, the ratio of B acid center to L acid center and the content of super acid center on the surface of the pore wall can be respectively 1.0-4.5 mmol/g, 0.0001-0.02 mmol/m20.01 to 1.8, and 0.02 to 1.0 mmol/g.
The ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is used as a catalyst, and shows extremely high catalytic activity, stability and regenerability.
The ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material prepared by the method is used as a catalyst in the transesterification reaction of soybean oil and methanol to synthesize biodiesel, not only can the soybean oil be completely converted at 140 ℃, but also the yield of the biodiesel is not lower than 99.0%, and the yield of the biodiesel is still not lower than 80.0% after the biodiesel is repeatedly used for 5 times.
Meanwhile, the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material which is used for many times is calcined and regenerated, and the structure, the texture, the surface acidity and the catalytic performance of the material are not changed.
Drawings
FIG. 1 is an XRD spectrum of an ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material.
FIG. 2 is a TEM photograph of an ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material.
FIG. 3 is N of ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material2Adsorption-desorption isotherms (A) and corresponding pore size distribution curves (B).
FIG. 4 is NH of ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material3TPD desorption profile.
FIG. 5 is a pyridine-infrared spectrum of an ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material.
FIG. 6 is a graph showing the effect of the number of repeated use of the ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material on the yield of biodiesel.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and perform the operations according to the conventional conditions or conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
Example 1.
2.0g of n-butanol was slowly added dropwise to 80mL of a 0.5mol/L hydrochloric acid solution in which 3.26g of glacial acetic acid and 2.0g of 2.0g P123 were dissolved, and after strongly stirring at 35 ℃ for 6 hours, 4.3g of ethyl orthosilicate was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 140 ℃ for hydrothermal polymerization treatment for 24h, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 550 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 20mL of aqueous solution in which 0.02mol of zirconium oxychloride and 0.02mol of aluminum nitrate are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 550 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the hole wall surface coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 15mL of 1.0mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 550 ℃ in an air atmosphere, and roasting for 5h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
As can be seen from the small-angle XRD spectrum of fig. 1 (fig. 1A), the sample showed a sharp diffraction peak and a weak diffraction peak at 2 θ =1.26 and 1.42 °, corresponding to the (211) and (220) crystal plane diffraction peaks assigned to the cubic Ia3d space group, respectively, indicating that the obtained solid acid material has a highly ordered three-dimensional cubic mesoporous channel structure. In addition, in the large-angle XRD spectrogram of FIG. 1B, no crystal phase diffraction peak of zirconia or alumina is detected in the sample with the 2 theta of 10-80 degrees, which indicates that Zr and Al species on the surface of the mesoporous pore wall of the sample are highly uniformly dispersed.
The TEM characterization result of fig. 2 further confirms that the sample has a regular and ordered three-dimensional cubic mesoporous channel structure and highly uniform mesoporous pore diameter, and the mesoporous pore diameter is about 7.0 nm.
From N of FIG. 32As can be seen from the adsorption-desorption isotherm (a) and the corresponding pore size distribution curve (B), the sample exhibits a typical IV-type adsorption isotherm and an H1-type hysteresis loop, and shows a very steep capillary condensation curve within a relative pressure range of 0.5 to 0.7 (fig. 3A), indicating that the sample has a highly regular and ordered mesoporous channel structure and a large and uniformly distributed mesoporous pore size (e.g., 3B). The specific surface area and the pore volume of the sample were calculated to be 366m, respectively2G and 0.42cm3The mesoporous aperture is 6.6 nm.
From NH of the sample3As can be seen from the-TPD spectrogram (figure 4), the sample shows two obvious and wider ammonia desorption peaks within 170-500 ℃, which indicates that weak acid, medium acid and strong acid centers exist on the surface of the pore wall of the sample at the same time. In addition, the appearance of ammonia desorption peak at 550 ℃ indicates that the surface of the pore wall of the sample has super acid centers. Through peak fitting of an ammonia desorption curve and calculation of peak areas of desorption peaks, the total acid amount of the sample is 2.18mmol/g, wherein the acid amounts of the surface weak acid, the medium strong acid, the strong acid and the super strong acid are respectively 0.71, 0.54, 0.84 and 0.09 mmol/g.
The pyridine adsorption-desorption infrared spectrum of FIG. 5 shows that the samples were 1543, 1490 and 1454cm when pyridine was desorbed at 150, 250 and 350 deg.C-1All shows three obvious absorption peaks, which indicates that B acid and L acid centers exist on the surface of the pore wall of the sample. By passing1543 and 1454cm in infrared curve for pyridine desorption at different temperatures-1The acid amount ratio of the total B acid center and the total L acid center of the sample was found to be 1.22 by calculation from the adsorption peak area, wherein the acid amount ratio of the B acid to the L acid in the strong acid center to the strong acid center was 0.45 and 0.77, respectively.
The prepared sample is used as a solid acid catalyst for preparing biodiesel through transesterification of soybean oil and methanol, and the catalytic performance of the catalyst is examined.
According to the molar ratio of soybean oil to methanol of 1: 20, 40g of reactants and 1.2g of catalyst are put into a closed reaction kettle with a stirrer, and the reaction is started at 140 ℃ under the condition of stirring speed of 600rpm, and the reaction time is 5 h.
After the reaction, solid-liquid separation was carried out by a centrifuge. The liquid reaction mixture was first distilled under reduced pressure to remove unreacted methanol, then left to stand until the mixed solution was layered up and down, and a quantitative upper layer solution was taken, diluted with pyridine, and subjected to product composition analysis on a gas chromatograph equipped with a hydrogen Flame Ionization Detector (FID).
The separated solid acid catalyst was washed with methanol and hexane, dried, and then put into use again to examine the catalytic stability of the catalyst.
The catalytic evaluation result (figure 6) shows that the catalytic material can realize the complete conversion of the soybean oil after the reaction is carried out at the low temperature of 140 ℃ for 5 hours, and the yield of the biodiesel in the product can reach 99.2 percent, which indicates that the catalyst has excellent transesterification reaction activity of the biodiesel synthesized from the soybean oil and methanol.
In addition, as can be seen from the trend that the yield of the biodiesel varies with the repeated use times of the catalyst, the yield of the biodiesel of the catalyst is kept above 82.0 percent in 5 repeated use processes.
More importantly, after the catalyst after being reused is calcined and regenerated for 2 hours at 550 ℃, the structure, texture and surface acidity of the catalyst are not obviously changed compared with those of a fresh catalyst, the complete conversion of soybean oil at 140 ℃ can be realized again, and the yield of the biodiesel reaches 97.4%.
Therefore, the catalyst shows excellent catalytic activity, stability and regeneration performance in the process of biodiesel transesterification reaction synthesized from soybean oil and methanol.
Example 2.
2.5g of n-butanol was slowly added dropwise to 65mL of a 1.0mol/L hydrochloric acid solution in which 3.0g of glacial acetic acid and 2.5g P123 were dissolved, and after vigorously stirring at 35 ℃ for 10 hours, 3.02g of methyl orthosilicate was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 120 ℃ for hydrothermal polymerization treatment for 24h, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 450 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 15mL of aqueous solution in which 0.3mol of zirconium nitrate and 0.1mol of aluminum nitrate are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 600 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the hole wall surface coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 15mL of 1.5mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 450 ℃ in an air atmosphere, and roasting for 5h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM and N2The adsorption-desorption and other characteristic results prove that the prepared sample has a highly regular and ordered three-dimensional cubic mesoporous channel structure and uniform mesoporous aperture. The specific surface area and the pore volume of the sample were calculated to be 465m, respectively2G and 0.58cm3G, the mesoporous aperture is 7.5 nm.
NH3The results of-TPD and pyridine adsorption-desorption infrared characterization prove that weak acid, medium strong acid, strong acid and superstrong acid exist on the surface of the sample simultaneouslyAcid centers in amounts of 0.75, 0.52, 1.16 and 0.10mmol/g, respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.02, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.58 and 0.68, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst. When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the product biodiesel can reach 99.5%. In addition, the yield of the biodiesel of the sample is kept above 82.0 percent in the process of 5 times of repeated use.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, the complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.0%.
Example 3.
2.0g of n-butanol was slowly added dropwise to 80mL of a 2.0mol/L hydrochloric acid solution in which 0.84g of citric acid and 2.2g P123 were dissolved, and after vigorously stirring at 35 ℃ for 8 hours, 0.96g of white carbon black was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 120 ℃ for hydrothermal polymerization treatment for 24h, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 550 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 15mL of aqueous solution in which 0.02mol of zirconium nitrate and 0.02mol of aluminum nitrate are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 550 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the hole wall surface coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 20mL of 1.5mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 550 ℃ in an air atmosphere, and roasting for 5h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM and N2The adsorption-desorption and other characteristic results prove that the prepared sample has a highly regular and ordered three-dimensional cubic mesoporous channel structure and uniform mesoporous aperture. By calculation, the specific surface area and the pore volume of the sample were 428m, respectively2G and 0.56cm3The mesoporous aperture is 7.8 nm.
NH3The infrared characterization results of TPD and pyridine adsorption-desorption prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.78, 0.60, 1.15 and 0.09mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.15, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.78 and 0.85, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst. When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the product biodiesel can reach 99.3%. In addition, the yield of the biodiesel of the sample is kept above 80.0 percent in the process of 5 times of repeated use.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, the complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.0%.
Example 4.
2.0g of n-butanol was slowly added dropwise to 75mL of a 2.5mol/L hydrochloric acid solution in which 1.25g of oxalic acid and 2.6g P123 were dissolved, and after strongly stirring at 45 ℃ for 8 hours, 3.66g of ethyl orthosilicate was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 100 ℃ for hydrothermal polymerization treatment for 24 hours, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 550 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 15mL of aqueous solution in which 0.10mol of zirconium oxychloride and 0.10mol of aluminum isopropoxide are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 450 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the surface of the pore wall coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 15mL of 1.2mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 550 ℃ in an air atmosphere, and roasting for 4h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM and N2The adsorption-desorption and other characteristic results prove that the prepared sample has a highly regular and ordered three-dimensional cubic mesoporous channel structure and uniform mesoporous aperture. The specific surface area and pore volume of the sample were calculated to be 455m, respectively2G and 0.63cm3The aperture of the mesoporous is 8.1 nm.
NH3TPD and pyridine adsorption-desorption infrared characterization results prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.68, 0.62, 1.11 and 0.12mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.08, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.83 and 0.76, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst. When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the product biodiesel can reach 99.7%. In addition, the yield of the biodiesel of the sample is kept above 83.2 percent in the process of 5 times of repeated use.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, the complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches up to 99.4%.
Example 5.
2.5g of n-butanol were slowly added dropwise to 60mL of a 1.6mol/L hydrochloric acid solution in which 2.2g P123 was dissolved, and after strongly stirring at 45 ℃ for 8 hours, 3.0g of methyl orthosilicate was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 150 ℃ for hydrothermal polymerization treatment for 24h, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 550 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 15mL of aqueous solution in which 0.35mol of zirconium acetate and 0.16mol of aluminum isopropoxide are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 550 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the hole wall surface coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 18mL of 1.6mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 500 ℃ in an air atmosphere, and roasting for 5h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM and N2The adsorption-desorption and other characteristic results prove that the prepared sample has a highly regular and ordered three-dimensional cubic mesoporous channel structure and uniform mesoporous aperture. The specific surface area and the pore volume of the sample were calculated to be 408m, respectively2G and 0.52cm3The aperture of the mesoporous is 8.9 nm.
NH3-TPD and pyridine adsorption-desorption infrared characterization resultsIt was confirmed that weak acid, medium acid, strong acid and super acid centers were present simultaneously on the surface of the sample at 0.76, 0.60, 1.08 and 0.11mmol/g, respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.16, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.87 and 0.79, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst. When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the product biodiesel can reach 99.5%. In addition, the yield of the biodiesel of the sample is kept above 82.6 percent in the process of 5 times of repeated use.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, the complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.2%.
Example 6.
2.2g of n-butanol were slowly added dropwise to 85mL of a 1.0mol/L hydrochloric acid solution in which 1.18g of citric acid and 2.8g P123 were dissolved, and after vigorously stirring at 45 ℃ for 8 hours, 3.86g of ethyl orthosilicate was added to the reaction solution, and stirring was continued for 24 hours while maintaining the temperature.
And (3) placing the white solid suspension obtained by self-assembly in a closed high-pressure reaction kettle, heating to 130 ℃ for hydrothermal polymerization treatment for 24h, taking out a reaction product, and performing suction filtration, washing and drying to prepare the ordered mesoporous KIT-6 material white solid wrapping the surfactant micelle.
In N2And heating the obtained white solid to 650 ℃ under the atmosphere, and carrying out high-temperature heat treatment for 2h to promote partial carbonization and shrinkage of the surfactant micelle in the KIT-6 mesoporous pore canal.
And then, placing the carbonized material into 15mL of aqueous solution in which 0.15mol of zirconium isopropoxide and 0.45mol of aluminum isopropoxide are dissolved, stirring for 30min at room temperature, carrying out suction filtration, drying for 12h at 80 ℃, heating to 650 ℃ under an air atmosphere, and carrying out roasting treatment for 5h to prepare the ordered mesoporous KIT-6 material with the hole wall surface coated with the zirconium-aluminum composite oxide.
And (2) placing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide in 20mL of 1.2mol/L sulfuric acid solution, stirring at room temperature for 30min, then carrying out suction filtration, drying at 100 ℃ for 12h, heating to 650 ℃ in an air atmosphere, and roasting for 5h to prepare the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
XRD, TEM and N2The adsorption-desorption and other characteristic results prove that the prepared sample has a highly regular and ordered three-dimensional cubic mesoporous channel structure and uniform mesoporous aperture. The specific surface area and the pore volume of the sample were calculated to be 385m, respectively2G and 0.58cm3G, the mesoporous aperture is 7.6 nm.
NH3TPD and pyridine adsorption-desorption infrared characterization results prove that weak acid, medium acid, strong acid and super acid centers exist on the surface of the sample at the same time, and the contents are 0.81, 0.72, 1.12 and 0.08mmol/g respectively. The acid amount ratio of the total B acid center and L acid center on the surface of the sample was 1.21, wherein the acid amount ratio of B acid to L acid in the strong acid center to the strong acid center was 0.92 and 0.83, respectively.
The transesterification reaction of soybean oil and methanol was carried out under the reaction conditions of example 1, and the sample of this example was examined for its catalytic performance as a catalyst. When the sample is used for the first time, the complete conversion of soybean oil can be realized, and the yield of the product biodiesel can reach 99.6%. In addition, the yield of the biodiesel of the sample is kept above 81.8 percent in the process of 5 times of repeated use.
After the used sample is roasted at 550 ℃ for regeneration for 2 hours, the structure, texture and surface acidity of the sample are not obviously changed compared with those before reaction, the complete conversion of soybean oil can be realized again, and the yield of the biodiesel reaches 99.1%.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.

Claims (10)

1. A preparation method of an ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material comprises the following steps:
1) dissolving inorganic acid, organic carboxylic acid and triblock copolymer nonionic surfactant P123 in deionized water according to the molar ratio of silicon source, organic carboxylic acid, inorganic acid, deionized water, n-butyl alcohol and triblock copolymer nonionic surfactant P123= (30-100) = (0-100): (0-800): (100-750): (8000-18000): 15-100): 1, slowly adding n-butyl alcohol, stirring uniformly, adding a silicon source, stirring uniformly, performing hydrothermal treatment in a sealed high-pressure reaction kettle at the temperature of 80-160 ℃, and preparing the ordered mesoporous KIT-6 material wrapping the surfactant micelle;
2) carrying out high-temperature treatment on the ordered mesoporous KIT-6 material at 350-750 ℃ in an inert atmosphere so as to partially carbonize surfactant micelles existing in mesoporous channels of the KIT-6 material;
3) placing the ordered mesoporous KIT-6 material subjected to high-temperature treatment in an aqueous solution in which a zirconium source and an aluminum source are dissolved for impregnation treatment, taking out the material and roasting the material in the air at 450-650 ℃ to remove partially carbonized surfactant micelles, thus preparing the ordered mesoporous KIT-6 material with the pore wall surface coated with the zirconium-aluminum composite oxide;
4) and placing the ordered mesoporous KIT-6 material with the surface of the pore wall coated with the zirconium-aluminum composite oxide in a sulfuric acid solution for dipping treatment, taking out the material and roasting the material in the air at the temperature of 300-650 ℃, thus preparing the ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material.
2. The preparation method according to claim 1, wherein the silicon source is one of or a mixture of methyl orthosilicate, ethyl orthosilicate, water glass and white carbon black in any proportion; the aluminum source is one of aluminum isopropoxide, tert-butyl alcohol aluminum, isobutyl alcohol aluminum, aluminum nitrate or aluminum chloride, or a mixture of several of the aluminum source and the tert-butyl alcohol aluminum; the zirconium source is one of zirconium oxychloride, zirconium isopropoxide, zirconium acetate or zirconium nitrate, or a mixture of several of the zirconium oxychloride, the zirconium isopropoxide and the zirconium acetate in any proportion.
3. The method according to claim 1, wherein the inorganic acid is hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid; the organic carboxylic acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
4. The method according to claim 1, wherein the mixture is stirred for not less than 24 hours after the addition of the silicon source, and then subjected to hydrothermal treatment.
5. The method according to claim 1, wherein the hydrothermal treatment time is 12 to 36 hours.
6. The preparation method of claim 1, wherein the high-temperature treated ordered mesoporous KIT-6 material is immersed in an aqueous solution containing a zirconium source and an aluminum source at concentrations of 0.01 to 1mol/L, respectively, at a solid/liquid volume ratio of (0.02 to 1) to 1.
7. The preparation method according to claim 1, wherein the ordered mesoporous KIT-6 material with the zirconium-aluminum composite oxide coated on the surface of the pore wall is immersed in a sulfuric acid solution with a concentration of 0.1-2 mol/L according to a solid/liquid volume ratio of (0.01-0.1) to 1.
8. The method according to claim 1, wherein the high-temperature treatment time in the inert atmosphere is 0.5 to 5 hours, and the calcination treatment time in air is 2 to 6 hours.
9. The ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material prepared by the preparation method of claim 1 has a highly regular and ordered three-dimensional cubic connected mesoporous pore structure and a specific surface area of 250-600 m2Per g, pore volume of 0.3-1.0 cm3The pore diameter is 4.0-12.0 nm, the molar ratio of zirconium/aluminum atoms on the surface of the mesoporous pore wall is adjusted within the range of 0.01-100, and the acid content, the acid density, the ratio of B acid center to L acid center and the acidity of the surface of the pore wall are in super-strong acidThe core content is 1.0-4.5 mmol/g, 0.0001-0.02 mmol/m20.01 to 1.8, and 0.02 to 1.0 mmol/g.
10. The use of the ordered mesoporous KIT-6 supported sulfated zirconium-aluminum composite oxide solid acid material of claim 9 as a catalyst for transesterification of biodiesel synthesis from soybean oil and methanol.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115121237A (en) * 2022-05-31 2022-09-30 西安凯立新材料股份有限公司 Modified molecular sieve catalyst for catalytic synthesis of triacetonamine and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102380362A (en) * 2011-08-25 2012-03-21 太原理工大学 Ordered zirconia-alumina mesoporous material and its preparation method
CN102417437A (en) * 2011-08-18 2012-04-18 内蒙古大学 Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof
CN102614900A (en) * 2012-03-08 2012-08-01 天津大学 Mesoporous carbon-loaded catalyst for synthesizing diethyl carbonate by gas phase oxidation carbonyl of ethanol and preparation method thereof
CN103285938A (en) * 2012-12-13 2013-09-11 华东理工大学 Mesoporous material loaded with metallic oxide and preparation method and application thereof
CN103691454A (en) * 2013-12-24 2014-04-02 天津大学 Preparation method for mesoporous carbon-based solid acid catalyst and application of mesoporous carbon-based solid acid catalyst
CN105327709A (en) * 2014-08-15 2016-02-17 陕西延长石油（集团）有限责任公司 Preparation method of catalyst used for synthesizing diphenyl carbonate by ester exchange method
CN110357114A (en) * 2019-08-14 2019-10-22 太原理工大学 A kind of hole wall is rich in ordered meso-porous silicon oxide material and its preparation of microcellular structure
CN110465278A (en) * 2019-09-05 2019-11-19 太原理工大学 A kind of order mesoporous titanium-aluminium composite oxide and its preparation method and application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417437A (en) * 2011-08-18 2012-04-18 内蒙古大学 Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof
CN102380362A (en) * 2011-08-25 2012-03-21 太原理工大学 Ordered zirconia-alumina mesoporous material and its preparation method
CN102614900A (en) * 2012-03-08 2012-08-01 天津大学 Mesoporous carbon-loaded catalyst for synthesizing diethyl carbonate by gas phase oxidation carbonyl of ethanol and preparation method thereof
CN103285938A (en) * 2012-12-13 2013-09-11 华东理工大学 Mesoporous material loaded with metallic oxide and preparation method and application thereof
CN103691454A (en) * 2013-12-24 2014-04-02 天津大学 Preparation method for mesoporous carbon-based solid acid catalyst and application of mesoporous carbon-based solid acid catalyst
CN105327709A (en) * 2014-08-15 2016-02-17 陕西延长石油（集团）有限责任公司 Preparation method of catalyst used for synthesizing diphenyl carbonate by ester exchange method
CN110357114A (en) * 2019-08-14 2019-10-22 太原理工大学 A kind of hole wall is rich in ordered meso-porous silicon oxide material and its preparation of microcellular structure
CN110465278A (en) * 2019-09-05 2019-11-19 太原理工大学 A kind of order mesoporous titanium-aluminium composite oxide and its preparation method and application

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
JONGJIN KIM ET AL.: "Synthesis of high-energy-density fuel over mesoporous aluminosilicate catalysts", 《CATALYSIS TODAY》 *
S. GOPINATH ET AL.: "Efficient mesoporous SO4 2 /Zr-KIT-6 solid acid catalyst for green diesel production from esterification of oleic acid", 《FUEL》 *
SATOSHI FURUTA ET AL.: "Biodiesel fuel production with solid amorphous-zirconia catalysis in fixed bed reactor", 《BIOMASS AND BIOENERGY》 *
SHIH-YUAN CHEN ET AL.: "Carbonaceous Ti-incorporated SBA-15 with enhanced activity and durability for high-quality biodiesel production: Synthesis and utilization of the P123 template as carbon source", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *
刘同慧: "介孔KIT-6的改性合成及其表酯交换反应中的催化性能", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 *
张文博: "不同模板剂导向制备具有晶体结构的介孔氧化锆的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 *
徐玉然: "高分散 Mn-KIT-6 催化剂的制备及催化性能研究", 《化学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115121237A (en) * 2022-05-31 2022-09-30 西安凯立新材料股份有限公司 Modified molecular sieve catalyst for catalytic synthesis of triacetonamine and preparation method and application thereof

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