CN113828330A - Mesoporous solid acid S2O82-/ZrO2-TiO2-La2O3Preparation method and application of - Google Patents

Mesoporous solid acid S2O82-/ZrO2-TiO2-La2O3Preparation method and application of Download PDF

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CN113828330A
CN113828330A CN202111120349.5A CN202111120349A CN113828330A CN 113828330 A CN113828330 A CN 113828330A CN 202111120349 A CN202111120349 A CN 202111120349A CN 113828330 A CN113828330 A CN 113828330A
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tio
solid acid
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顾正桂
叶申
葛盛才
张佩祥
曹晓艳
沙玉英
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Gpro New Materials Co ltd
Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention discloses a mesoporous solid acid S2O8 2‑/ZrO2‑TiO2‑La2O3The preparation method comprises the following steps: mixing zirconium oxychloride, titanium salt, lanthanum salt and template agent, adding precipitant to make coprecipitation, filtering, washing and drying so as to obtain the carrier ZrO2‑TiO2‑La2O3(ii) a Immersing the carrier in ammonium persulfate solution, and filteringDrying and calcining. The application of the solid acid in polyethylene glycol oleate is provided. The mesoporous material is prepared by modifying the carrier with the template agent, so that the aperture and the specific surface area of the catalyst are improved; interaction force among the rare earth element, the metal element, the O element and the S element is enhanced, and the S element is not easy to fall off in the reaction process, so that better catalytic activity and stability are shown; the catalyst is used for synthesizing polyethylene glycol oleate, has high catalytic efficiency and good stability, does not need an acid neutralization post-treatment process, and is convenient to recycle and reuse.

Description

Mesoporous solid acid S2O82-/ZrO2-TiO2-La2O3Preparation method and application of
Technical Field
The invention relates to a preparation method and application of solid acid, in particular to mesoporous solid acid S2O8 2-/ZrO2-TiO2-La2O3The preparation method and the application thereof.
Background
Polyethylene glycol fatty acid esters are the most important class of products among modern nonionic surfactants. Polyethylene glycol oleate is one of polyethylene glycol fatty acid esters, and can be used as emulsifier of pesticide, and also can be used for pickling water-soluble paint and printed circuit board, etc.
The current methods for preparing polyethylene glycol oleate mainly comprise an ethoxylation method, an ester exchange method and an esterification method. The ethoxylation method is mature in process and is commonly used for synthesizing the monoester, but the raw material ethylene oxide is flammable and explosive, and the reaction condition is harsher. The ester exchange method is to use the ester exchange of polyethylene glycol and methyl oleate under the catalysis of alkali, the conditions are easy to control, but the content of single and double esters is not easy to control, and the price of methyl oleate is high; the esterification method has mild conditions and easily controlled mono-diester and diester proportion. At present, the polyethylene glycol oleate is synthesized by adopting homogeneous acid, however, the homogeneous acid has certain corrosivity to equipment, and alkali is still required to be added for neutralization after the reaction is finished, so that salt-containing wastewater is generated.
Patent CN101747192 mentions that organic acid dodecylbenzene sulfonic acid is used as catalyst to synthesize polyethylene glycol fatty acid ester by vacuum pumping, and after the reaction is finished, triethylamine is used for neutralization. Patent CN 107814924 mentions that p-toluenesulfonic acid is used as a catalyst, sodium sulfite is used as an antioxidant to synthesize polyethylene glycol oleate, and sodium bicarbonate is used for neutralization after the reaction is finished.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a mesoporous solid acid S with high catalytic efficiency and easy recycling2O8 2-/ZrO2-TiO2-La2O3The preparation method of (1);
the second purpose of the invention is to provide a mesoporous solid acid S2O8 2-/ZrO2-TiO2-La2O3Application in preparing polyethylene glycol oleate.
The technical scheme is as follows: the mesoporous solid acid S of the invention2O8 2-/ZrO2-TiO2-La2O3The preparation method comprises the following steps:
(1) mixing zirconium oxychloride, titanium salt, lanthanum salt and template agent by coprecipitation method, adding precipitant to make coprecipitation, filtering, washing and drying so as to obtain the carrier ZrO2-TiO2-La2O3；
(2) ZrO of the support2-TiO2-La2O3Soaking in ammonium persulfate solution, filtering, drying, and calcining.
Wherein in the step (1), the mass ratio of the zirconium oxychloride to the titanium salt is 1.61-8.05: 1.22.
In the step (1), the mass ratio of the lanthanum salt to the zirconium oxychloride is 0.06-0.54: 4.84.
In the step (1), the mass ratio of the zirconium oxychloride to the template is 1.61-8.05: 0.61.
Wherein, in the step (1), before adding the precipitator, the zirconium oxychloride, the titanium salt, the lanthanum salt and the template agent are mixedAnd (3) carrying out constant-temperature oil bath treatment on the mixed solution, wherein the temperature of the constant-temperature oil bath is 30-80 ℃, adding a precipitator to adjust the pH value to 9-11, and aging at 80-100 ℃ for 18-24 h. After cooling, the filter cake is washed to neutrality without Cl-After the detection, drying the mixture at 90-120 ℃ for 8-14 h.
In the step (2), the concentration of the ammonium persulfate solution is 0.5-1.5 mol/L, and the dipping time is 8-14 h. And then filtering, and drying the filter cake at 90-120 ℃ for 8-16 h. Then grinding the solid particles and sieving the solid particles with a 100-mesh sieve, calcining the catalyst for 4 to 8 hours at 500 to 700 ℃, removing the template agent, and finally preparing the solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3。
The mesoporous solid acid S2O8 2-/ZrO2-TiO2-La2O3The mesoporous solid acid S prepared by the preparation method2O8 2-/ZrO2-TiO2-La2O3Application in preparing polyethylene glycol oleate.
The method comprises the following specific application: polyethylene glycol, oleic acid and solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3Mixing, adding dimethylbenzene as a water-carrying agent, filtering and separating the catalyst after reaction, and removing the water-carrying agent by atmospheric distillation to obtain the polyethylene glycol oleate.
Wherein the molecular weight of the polyethylene glycol is 600, the mass ratio of the polyethylene glycol to the oleic acid is 30.00: 25.42-33.89, the dosage of the catalyst is 0.5-3.5% of the total mass of the raw materials, the reaction temperature is 160-220 ℃, and the reaction time is 3-8 h.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: 1. the template agent modifies the carrier to prepare the mesoporous material in the synthesis process, so that the aperture and the specific surface area of the catalyst are effectively improved, and the raw material can enter a catalyst pore passage to fully contact with an active site; the interaction force among the rare earth element, the metal element, the O element and the S element is enhanced, and the S element is not easy to fall off in the reaction process, thereby showing better catalytic activity and stabilityAnd (5) performing qualitative determination. 2. TiO 22The introduction of the metal ions enhances the average electronegativity of the metal ions, and improves the effective acid sites on the surface of the catalyst; the ZrO can be stabilized by introducing a small amount of rare earth element La2The tetragonal phase of the catalyst improves the catalytic activity of the catalyst. 3. With solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3The synthesized polyethylene glycol oleate has high catalytic efficiency and good stability, does not need an acid neutralization post-treatment process, and is convenient for recovering and reusing the catalyst.
Drawings
FIG. 1 is a graph comparing the catalytic performance of three catalysts for synthesizing PEG600 DO;
FIG. 2 is a comparative scanning electron micrograph of three catalysts;
FIG. 3 is a comparison of infrared spectra for three catalysts;
FIG. 4 is a comparative XRD pattern for three catalysts;
FIG. 5 shows NH of three catalysts3-TPD contrast map;
FIG. 6 is a graph showing the comparison of nitrogen adsorption and desorption and pore size distribution of three catalysts;
FIG. 7 shows catalyst S2O8 2-/ZrO2-TiO2-La2O3And (5) reusing the performance test chart.
Detailed Description
The present invention is described in further detail below.
Example 1
Mesoporous solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3The preparation method comprises the following steps:
(1) weighing 4.84g of ZrOCl2·8H2O, 1.20g of Ti (SO)4)20.18g of La (NO)3)3·6H2Dissolving O and 0.61g CTAB in 150ml of deionized water, uniformly mixing, stirring in a constant-temperature oil bath kettle at 60 ℃, adjusting the pH value of the precipitate to 10 by dropwise adding ammonia water, stopping dropwise adding, continuously stirring for 2 hours, and standing and aging for 12 hours. Cooling, taking out, washing with deionized water until no Cl is formed-Detecting with 0.1mol/LAgNO3Detecting the solution, and then drying at 110 ℃ for 12h to obtain ZrO2-TiO2-La2O3A carrier precursor.
(2) ZrO 2 is mixed with2-TiO2-La2O3The carrier precursor is added at a concentration of 15ml/g to 1mol/L (NH)4)2S2O8The solution was immersed for 12h, filtered and dried at 110 ℃ for 12 h. Finally calcining the catalyst in a muffle furnace at 550 ℃ for 6h to obtain the composite mesoporous solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3。
Example 2
The composite mesoporous solid acid catalyst S is adopted2O8 2-/ZrO2-TiO2-La2O3The method for synthesizing the polyethylene glycol oleate comprises the following steps:
(1) 30.00g of polyethylene glycol 600, 29.65g of oleic acid and 0.89g of solid acid catalyst S were weighed2O8 2-/ZrO2-TiO2-La2O3Placed in a round bottom flask and 15ml of water-carrying agent xylene was added. And connecting the upper end of the water separator with a spherical condensing pipe for condensation and reflux, heating to 200 ℃ by adopting an electric heating jacket, stirring for reacting for 6 hours, stopping the experiment, cooling, filtering and recovering the catalyst, and distilling to remove xylene as a water-carrying agent under normal pressure to obtain the product polyethylene glycol oleate. The method of GB/T1668-2008 is adopted to titrate the acid value to determine the conversion rate of the oleic acid, and the method of GB/T7383-2020 is adopted to determine the content of the diester.
At the same time, to S2O8 2-/ZrO2、S2O8 2-/ZrO2-TiO2、S2O8 2-/ZrO2-TiO2-La2O3The catalytic performances were compared and the results are shown in figure 1. Wherein S2O8 2-/ZrO2Preparation basic procedure the method of example 1 was followed, in the course of which only ZrO was used2As a precursor; s2O8 2-/ZrO2-TiO2In the preparation ofWith only ZrO2-TiO2As a precursor. As can be seen from the other figures, TiO2The introduction of the catalyst can improve the average electronegativity of the carrier, and the template hexadecyl trimethyl is added to modify the pore diameter and the specific surface area of the catalyst which are effectively improved; ZrO stabilized by doping with small amounts of La2The tetragonal phase improves the catalytic activity of the catalyst. With S2O8 2-/ZrO2-TiO2-La2O3The catalyst has the best catalytic effect, the conversion rate of oleic acid is 96.81%, and the content of diester is 94.08%.
The following characterization analyses were carried out simultaneously on the different catalysts:
the results of the SEM analysis are shown in FIG. 2, where (a), (b), and (c) in FIG. 2 are S2O8 2-/ZrO2、S2O8 2-/ZrO2-TiO2And S2O8 2-/ZrO2-TiO2-La2O3In the scanning electron microscope image of (a), (b) and (c) in fig. 2, all the particles are in a random spherical structure, most of the particles in (a) are tightly clustered and have larger particle size, and the particles in (b) and (c) are dispersed more uniformly and have smaller particle size. Shows that the modified catalyst has better dispersity, especially La2O3Further improves ZrO2-TiO2Degree of dispersion of the carrier.
The infrared spectrum analysis result is shown in figure 3, and the infrared absorption peak positions of the three catalysts in the spectrogram are consistent. Wherein 3436cm-1And 1633cm-1The corresponding absorption peak is the stretching vibration absorption peak of the hydroxyl in the water absorbed by the surface of the catalyst. 1135cm-1And 1058cm-1The absorption peaks of (a) correspond to symmetrical stretching vibration absorption peaks of O ═ S ═ O and S-O-S, 1207cm respectively-1The absorption peak at corresponds to S2O8 2-And a bidentate chelate absorption peak formed between the metal oxide is a characteristic absorption peak of the super acid. Furthermore, S2O8 2-The characteristic absorption peak of (A) is located at 1620-1630cm-1No absorption peak is observed in the spectrum, which indicates that the sulfur-oxygen bond on the surface of the catalyst is not separatedThe sub-form exists, but is bonded to the oxide surface in a bonding form. The simultaneous introduction of titanium and lanthanum does not change S2O8 2-Bonding with metal oxide.
The results of X-ray diffraction analysis are shown in FIG. 4, which is an XRD pattern of the three catalysts at 550 ℃ calcination, in which trace ZrO appears at 28 ℃, (c)2The monoclinic characteristic peak, 30 degrees, 35 degrees, 50 degrees and 60 degrees, is tetragonal phase (T) ZrO2Characteristic diffraction peak of (1). With the doping modification of the catalyst, monoclinic crystal disappears, which shows that TiO2Or La2O3Introduction of (2) stabilizes ZrO2And in S2O8 2-/ZrO2-TiO2-La2O3No TiO is observed in the XRD pattern of2And La2O3The characteristic diffraction peak of (2) and the phenomenon of diffraction peak shift are generated, which illustrate that TiO2And La2O3The composite material is highly dispersed in the crystal and has good composite effect.
NH3The TPD analysis results are shown in FIG. 5, in which the desorption peak corresponds to a weak acid center at about 250 ℃, a medium acid center at about 400 ℃ and a strong acid center at about 500 ℃, and the peak area represents the acid amount. Thus, the modified S2O8 2-/ZrO2-TiO2-La2O3The acid strength is significantly enhanced at the strong acid center at 500 ℃ and the acid amount is also increased. From this, it was found that the composite solid acid catalyst S2O8 2-/ZrO2-TiO2-La2O3Has higher acid strength and acid quantity, which is beneficial to the synthesis of polyethylene glycol oleate, thereby improving the catalytic activity of esterification reaction and improving the conversion rate of oleic acid and the content of diester.
N2The results of the adsorption and desorption analysis are shown in fig. 6, the nitrogen adsorption and desorption and pore size distribution diagram of the three catalysts are shown, the specific surface area and the pore size of the catalyst are determined by the BJH equation, and the results show that S is2O8 2-/ZrO2-TiO2-La2O3The pore diameter is 20.3152nm, and the specific surface area is 156.3596m2(g), composite support ZrO modified with template cetyl trimethylammonium bromide2-TiO2Has larger specific surface area and pore diameter and proper La2O3The doping further enlarges the aperture, is beneficial to the full contact of oleic acid macromolecules and active sites inside the pore channels in the esterification reaction process, thereby improving the catalytic efficiency of the catalyst.
Example 3
The basic procedure was the same as in example 1 except that the amounts of Zr and Ti in the carrier were changed to examine the effect of the catalyst on the synthesis of polyethylene glycol oleate, and the results are shown in Table 1.
TABLE 1 results of oleic acid conversion and polyglycol oleic acid diester content of example 3
Serial number Zr:Ti Oleic acid conversion (%) Diester content (%)
1 1.61:1.22 88.36 76.32
2 3.22:1.22 95.28 90.55
3 4.82:1.22 96.81 94.08
4 6.45:1.22 93.31 89.94
5 8.05:1.22 92.05 87.23
As can be seen from Table 1, when Zr and Ti are used as the composite carrier, the average electronegativity of the whole catalyst is improved, the acid strength of the catalyst is increased, and the catalytic efficiency is improved; and when the ratio of Zr to Ti is larger, the ratio of Ti is smaller, the intermetallic chelation degree is reduced, and the oleic acid conversion rate is reduced. So m (ZrOCl) is selected2·8H2O):m(Ti(SO4)2) The effect is best when the ratio of the oleic acid to the oleic acid is 4.82:1.20, the conversion rate of the oleic acid reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 4
The basic procedure was the same as in example 1 except that the amounts of Zr and La in the carrier were changed and polyethylene glycol oleate was synthesized using the catalyst, and the results are shown in Table 1.
TABLE 2 results of oleic acid conversion and polyglycol oleic acid diester content of example 4
Serial number La:Zr Oleic acid conversion (%) Diester content (%)
1 0.06:4.84 95.28 92.17
2 0.18:4.84 96.81 94.08
3 0.30:4.84 94.33 90.23
4 0.42:4.84 91.12 84.76
5 0.54:4.84 87.69 80.36
As is clear from Table 2, when the addition ratio of La to Zr was increased, lanthanum, which is a rare earth element, stabilized ZrO2The tetragonal phase of (a) enhances the interaction force between elements, and as the lanthanum content is further increased, the acidity of the catalyst is reduced, thereby reducing the catalytic activity. Therefore, m (La (NO) is selected3)3·6H2O):m(ZrOCl2·8H2The best effect is achieved when O) is 0.18:4.84, and the oleic acid is converted into the fatty acidThe chemical rate reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 5
The basic procedure was the same as in example 1, except that polyethylene glycol 600 and oleic acid were varied in molar ratio to synthesize polyethylene glycol oleate at different ratios of raw materials, and the results are shown in Table 3.
TABLE 3 results of oleic acid conversion and polyglycol oleic acid diester content of example 5
Serial number Alcohol to acid ratio Oleic acid conversion (%) Diester content (%)
1 30.00:25.42 98.41 81.69
2 30.00:26.83 97.64 85.97
3 30.00:28.24 97.12 89.84
4 30.00:29.65 96.81 94.08
5 30.00:31.07 93.26 88.25
6 30.00:32.48 88.87 82.99
7 30.00:33.89 83.68 75.90
As can be seen from table 3, the molar ratio of the alkyd has a greater influence on the content of the diester, and the increase in the alkyd specific energy can increase the oleic acid conversion rate and the diester content to some extent, whereas when the alkyd specific energy is increased, the oleic acid concentration in the reaction system is decreased, and the viscosity of the system is increased, resulting in a decrease in the oleic acid conversion rate. Considering the conversion rate and diester content in the reaction process, the best effect is achieved by selecting the reaction alcohol-acid ratio of m (polyethylene glycol 600) to m (oleic acid) of 30.01:29.65, the conversion rate of oleic acid reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 6
The basic procedure was the same as in example 1 except that the reaction temperature was changed and polyethylene glycol oleate was synthesized at different temperatures, and the results are shown in Table 4.
TABLE 4 results of oleic acid conversion and polyethyleneglycol diester oleate content of example 6
Serial number Reaction temperature (. degree.C.) Oleic acid conversion (%) Diester content (%)
1 160.0 59.06 27.77
2 170.0 73.57 51.25
3 180.0 80.21 65.33
4 190.0 88.33 76.59
5 200.0 96.81 94.08
6 210.0 96.83 94.18
7 220.0 96.95 94.55
It can be seen from table 4 that the reaction temperature has a large influence on the conversion rate, the high temperature accelerates the reaction rate, promotes the full contact between the reactants and the active sites of the catalyst, when the temperature is higher than 200 ℃, the conversion rate has not changed significantly, and when the temperature is too high, oleic acid is easily oxidized, so that the color of the product is deepened, and the comprehensive consideration shows that the optimal effect is achieved when the reaction temperature is 200 ℃, the conversion rate of oleic acid reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 7
The basic procedure was the same as in example 1 except that the amount of the catalyst was changed to synthesize polyethylene glycol oleate at different catalyst amounts, and the results are shown in Table 5.
TABLE 5 results of oleic acid conversion and polyethyleneglycol diester oleate content of example 7
Serial number Amount of catalyst used (wt%) Oleic acid conversion (%) Diester content (%)
1 0.5 78.33 69.75
2 1.0 91.54 86.77
3 1.5 96.81 94.08
4 2.0 96.51 94.25
5 2.5 96.60 93.71
6 3.0 95.74 92.88
7 3.5 95.13 91.73
As can be seen from table 5, the oleic acid conversion increased with increasing catalyst usage. When the catalyst dosage is increased to 1.5 percent, the conversion rate and the selectivity are higher, which indicates that the active sites of the catalyst reach sufficient levels; when the amount of catalyst is further increased, the conversion and selectivity are reduced because the hydrolysis of the reverse reaction polyethylene glycol oleic acid diester is accelerated by the excessive amount of catalyst. Therefore, the catalyst dosage is selected to be 1.5%, the effect is optimal, the oleic acid conversion rate reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 8
The basic procedure was the same as in example 1 except that the reaction time was changed and polyethylene glycol oleate was synthesized at different times, and the results are shown in Table 5.
TABLE 6 results of oleic acid conversion and polyethyleneglycol diester oleate content of example 8
Serial number Reaction time (h) Oleic acid conversion (%) Diester content (%)
1 2 40.21 10.21
2 3 55.34 32.11
3 4 73.68 58.66
4 5 81.25 76.89
5 6 96.81 94.08
6 7 97.01 93.85
7 8 97.68 94.11
As can be seen from Table 4, the conversion and selectivity of the reaction increased with the increase of the reaction time, and when the reaction time reached more than 6 hours, the conversion and selectivity did not change significantly, and it is likely that the reaction equilibrium was limited, and increasing the reaction time only increased the reaction rate, but not the percent conversion. It can be seen that the reaction has substantially reached equilibrium when the reaction time is 6 h. The reaction time is selected to be 6h, the effect is optimal, the conversion rate of oleic acid reaches 96.81%, and the content of polyethylene glycol oleic acid diester reaches 94.08%.
Example 9
The catalyst of example 1 was recovered by filtration, washed with 50ml of cyclohexane, magnetically stirred for 3 times to remove adhered organic substances, filtered, dried at 110 ℃ for 12 hours, and then calcined at high temperature in a muffle furnace to remove carbon deposits on the surface of the catalyst, and the results were repeated as shown in FIG. 7.
It can be seen from fig. 7 that after the catalyst is repeatedly used for 4 times, the catalytic performance is slightly reduced, which may be caused by leaching of part of active components in the reaction process, but the catalyst has good stability and long service life when used for synthesizing polyethylene glycol oleate.
Example 10
The basic procedure is the same as in example 1, except that:
in the step (1), adding a precipitator to adjust the pH value of the solution to 9, controlling the precipitation temperature to be 50 ℃, controlling the temperature of the standing process to be 80 ℃ and the time to be 24 hours, and controlling the drying temperature to be 90 ℃ and the time to be 14 hours;
in the step (2), (NH)4)2S2O8The solution concentration is 0.5mol/L, and the dipping time is 14 h; the drying temperature is 90 ℃, and the drying time is 14 h; the catalyst calcination temperature is 500 ℃ and the time is 8 h.
Example 11
The basic procedure is the same as in example 1, except that:
in the step (1), adding a precipitator to adjust the pH value of the solution to 11, controlling the precipitation temperature to be 70 ℃, controlling the temperature of the standing process to be 100 ℃ and the time to be 18 hours, and controlling the drying temperature to be 120 ℃ and the time to be 8 hours;
in the step (2), (NH)4)2S2O8The solution concentration is 1.5mol/L, and the dipping time is 8 h; the drying temperature is 120 ℃, and the drying time is 8 hours; the catalyst calcination temperature is 700 ℃ and the time is 4 h.

Claims (10)

1. Mesoporous solid acid S2O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized by comprising the following steps:
(1) mixing zirconium oxychloride, titanium salt, lanthanum salt and template agent by using coprecipitation method, then adding precipitant to make coprecipitation, filtering, washing and drying so as to obtain carrier ZrO2-TiO2-La2O3；
(2) ZrO of the support2-TiO2-La2O3Soaking in ammonium persulfate solution, filtering, drying, and calcining.
2. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (1), the mass ratio of the zirconium oxychloride to the titanium salt is 1.61-8.05: 1.22.
3. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (1), the mass ratio of the lanthanum salt to the zirconium oxychloride is 0.06-0.54: 4.84.
4. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (1), the mass ratio of the zirconium oxychloride to the template is 1.61-8.05: 0.61.
5. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (1), a precipitator is added to adjust the pH value to 9-11.
6. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (1), a precipitator is added and then aged for 18-24 hours at the temperature of 80-100 ℃.
7. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (2), the concentration of the ammonium persulfate solution is 0.5-1.5 mol/L, and the dipping time is 8-14 h.
8. The mesoporous solid acid S according to claim 12O8 2-/ZrO2-TiO2-La2O3The preparation method is characterized in that in the step (2), the calcining temperature is 500-700 ℃ and the time is 4-8 h.
9. The mesoporous solid acid S of claim 12O8 2-/ZrO2-TiO2-La2O3The mesoporous solid acid S prepared by the preparation method2O8 2-/ZrO2-TiO2-La2O3Application in preparing polyethylene glycol oleate.
10. The mesoporous solid acid S according to claim 92O8 2-/ZrO2-TiO2-La2O3The application in the preparation of polyethylene glycol oleate is characterized in that a water-carrying agent used in the preparation process is xylene.
CN202111120349.5A 2021-09-24 2021-09-24 Mesoporous solid acid S2O82-/ZrO2-TiO2-La2O3Preparation method and application of Pending CN113828330A (en)

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