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CN110841665A - High-activity sulfuric acid-promoted solid super-strong composite acid and preparation method thereof - Google Patents

High-activity sulfuric acid-promoted solid super-strong composite acid and preparation method thereof Download PDF

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CN110841665A
CN110841665A CN201911161998.2A CN201911161998A CN110841665A CN 110841665 A CN110841665 A CN 110841665A CN 201911161998 A CN201911161998 A CN 201911161998A CN 110841665 A CN110841665 A CN 110841665A
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acid
solid super
sulfuric acid
promoted
strong
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CN110841665B (en
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李力成
佘洁
赵学娟
吴臻煜
岳海芹
花泽林
李龙
魏童童
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Nanjing Forestry University
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Abstract

The invention discloses a high-activity sulfuric acid-promoted solid super-strong composite acid and a preparation method thereof, wherein the high-activity sulfuric acid-promoted solid super-strong composite acid is promoted by sulfuric acidType solid super acid (SO)4 2‑/MxOy) And the assistant acid. The mass percentage content of sulfate radicals in the sulfuric acid-promoted solid super acid is 0.1-10%; the auxiliary acid comprises at least one of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, chloric acid, perchloric acid, hypochloric acid and nitric acid, and the molar ratio of the auxiliary acid to sulfate radicals is 0.01-10. The invention provides a method for compounding an auxiliary acid onto a sulfuric acid-promoted solid super strong acid, which enables the catalytic performance of the sulfuric acid-promoted solid super strong composite acid to be remarkably improved in alkylation reaction and isomerization reaction compared with the sulfuric acid-promoted solid super strong acid, HZSM-5 solid acid, Amberlyst-15 solid acid and liquid sulfuric acid under the same condition. The novel high-activity solid super-strong composite acid disclosed by the invention is simple in preparation method and has important significance for high-efficiency acid catalysis.

Description

High-activity sulfuric acid-promoted solid super-strong composite acid and preparation method thereof
Technical Field
The invention relates to the technical field of material preparation, in particular to a novel high-activity sulfuric acid-promoted solid super acid and a preparation method thereof.
Background
Acid catalysis has played an important role in many applications, such as the production of various important chemicals by cracking, reforming, isomerization, and olefin hydration, aromatic alkylation, acylation, isomerization, alkyd esterification, and the like. At present, liquid inorganic acids represented by sulfuric acid and hydrofluoric acid and metal halide solid acid catalysts represented by aluminum trichloride are industrially used, but the traditional acid catalysts have the defects of difficult separation, easy corrosion, large pollution, low reaction efficiency, incapability of recycling and the like. In the case of sulfuric acid, the consumption of the sulfuric acid as an 'unrecoverable catalyst' is more than 1500 ten thousand tons every year, which wastes resources and energy and generates a large amount of waste products. With the shift of economic strategy to high-quality development in China, the development of high-efficiency solid acid to replace the traditional liquid acid for the reaction is urgently needed.
Among the current numerous solid acid materials, the sulfuric acid promoted solid Superacid (SO)4 2-/MxOy) The advantages of simple composition, easy obtaining of products and the like cause wide attention of all fields. SO (SO)4 2-And itAn electron induction effect exists between carriers, and the acid strength of the sulfuric acid-promoted solid superacid can reach more than 1 ten thousand times of 100% concentrated sulfuric acid; after the reaction with surface hydroxyl, L acid on the sulfuric acid promoted solid superacid can be converted into B acid, and excellent catalytic performance can be shown in most reaction systems.
However, the reaction efficiency of alkylation, isomerization and the like is obviously influenced by the acid type and the acid strength, and the conventional sulfuric acid promoted solid superacid is difficult to meet the production requirement under the new potential, such as SbF if adopted5、FSO3H-ASF5、FSO3H-SbF5(1∶1)、HF-SbF5(1∶1)、FSO3H-TaF5The special acid with stronger acidity, such as (5: 1), can obtain ideal reaction effect, but the production cost is greatly increased. Aiming at the problems existing at present, the project reports a novel solid super-strong composite acid based on a sulfuric acid promoted solid acid, and the material is more conventional sulfuric acid promoted solid super-strong acid (SO)4 2-/MxOy) Has higher acid strength and more B acid content, can show high activity in a plurality of reaction systems such as alkylation, isomerization and the like, and is obviously superior to liquid sulfuric acid under the same condition. The invention also aims to introduce a preparation method of the solid super-strong composite acid, which is simple and convenient to operate and suitable for industrial production.
Disclosure of Invention
The purpose of the invention is as follows:
the invention aims to solve the problems and report a novel sulfuric acid-promoted solid super-strong composite acid which is higher than the conventional sulfuric acid-promoted solid super-strong acid (SO)4 2-/MxOy) Has higher acid strength and more B acid content, can show high activity in a plurality of reaction systems such as alkylation, isomerization and the like, and is obviously superior to liquid sulfuric acid under the same condition.
The technical scheme is as follows:
the invention also aims to provide a preparation method of the sulfuric acid-promoted solid super-strong composite acid, which is simple and convenient to operate and suitable for industrial production.
The aim of the invention can be achieved by the following measures:
a high-activity sulfuric acid-promoted solid super-strong composite acid is prepared from sulfuric acid-promoted solid super-strong acid (SO)4 2-/MxOy) And assistant acid, wherein sulfate radical (SO) in the sulfuric acid-promoted solid super acid4 2-) The mass percentage content of the compound is 0.1-10 percent; the molar ratio of the auxiliary acid to the sulfate radical is 0.01-10.
The carrier of the sulfuric acid-promoted solid super acid contains one or more metal oxides of aluminum, zirconium, titanium, tin, iron and hafnium elements.
The "builder acid" includes, but is not limited to, exemplified inorganic acids which, in minor amounts, complex with solid acids to form solid super strong complex acids which possess stronger acid catalytic activity than ordinary solid super acids.
The auxiliary acid can be one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, chloric acid, perchloric acid, hypochloric acid and nitric acid.
In summary, the adjuvant acid is merely a general description and includes all inorganic acids that can greatly enhance the acid catalytic activity of the complex acid in a small amount.
The preparation method of the high-activity sulfuric acid-promoted solid super-strong composite acid comprises the following steps: adding auxiliary acid into a bubbler, introducing nitrogen, introducing gas at the outlet of the bubbler into a closed container filled with sulfuric acid-promoted solid super strong acid for compounding after passing through a drying tube, controlling the compounding temperature and the compounding time, performing heat treatment on the obtained sample, and finally preparing the sulfuric acid-promoted solid super strong composite acid
The preparation method of the high-activity sulfuric acid-promoted solid superstrong composite acid has the composite temperature of-20-260 ℃.
The preparation method of the high-activity sulfuric acid-promoted solid superstrong composite acid has the compounding time of 0.2-12 h.
The preparation method of the high-activity sulfuric acid-promoted solid superstrong composite acid has the heat treatment temperature of 30-500 ℃.
Compared with the prior art, the invention has the advantages that:
1) the high-activity sulfuric acid-promoted solid super-strong composite acid has higher acid strength and more B acid content than the conventional sulfuric acid-promoted solid super-strong acid.
2) The high-activity sulfuric acid-promoted solid superstrong composite acid can show high activity in reaction systems such as alkylation, isomerization and the like, and is obviously superior to liquid concentrated sulfuric acid under the same acid amount;
3) the preparation method of the high-activity sulfuric acid-promoted solid superstrong composite acid has the advantages of simple and convenient operation, industrial application and the like.
Drawings
FIG. 1 is a pyridine infrared absorption (Py-IR) spectrum of a solid super-strong complex acid and a solid super-strong acid in example 1 of the present invention, and FIG. 2 is a temperature programmed desorption (NH-absorption) spectrum of a solid super-strong complex acid and a solid super-strong acid in example 1 of the present invention3-TPD) map.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be described in more detail with reference to the embodiments of the present invention. The described embodiments are, of course, part of the embodiments of the invention and should not be taken as limiting the scope of the invention.
Example 1:
according to the literature[1]Preparation of 3% SO4 2-/TiO2The preparation method of the sulfuric acid-promoted solid superacid comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing the materials according to the mass ratio of 3: 100, and roasting the mixture at high temperature to prepare sulfuric acid-promoted solid superacid marked as 3 percent SO4 2-/TiO2。
0.5g of the above 3% SO was weighed4 2-/TiO2Adding solid super acid into a three-neck flask, and adjusting the temperatureAnd raising the temperature to 60 ℃, wherein an inlet of the three-neck flask is connected with a hydrochloric acid bubbler after being dried by a section of drying column, hydrochloric acid is entrained by bubbling of nitrogen and enters the three-neck flask, so that the gas is fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 0.6h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 60 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing with a sample labeled as HCl-3% SO4 2-/TiO2。
The reaction performance data of the solid acid is obtained by two reaction evaluations of benzyl alcohol, anisole alkylation and limonene isomerization, and the specific reaction evaluation steps are shown in the following method I and method II. The contents of the components of the solid acid are determined by X-ray fluorescence spectrum (XRF) analysis, and the acid type, acid strength and acid amount are respectively determined by pyridine absorption infrared (Py-IR) and ammonia gas adsorption temperature-programmed desorption (NH)3TPD), the specific experimental procedure is as follows.
The method comprises the following steps: namely, the alkylation reaction of benzyl alcohol and anisole (see formula 1). Weighing solid acid, weighing benzyl alcohol and anisole in a three-neck flask, adding naphthalene as an internal standard substance, wherein the mass of naphthalene accounts for 25% of the mass of the benzyl alcohol, the molar ratio of the anisole to the benzyl alcohol is 9.6, and the using amount of the solid acid is 0.2 g/mL-1Based on the volume of benzyl alcohol. After reacting for 60min at 130 ℃, collecting liquid products by filtering solid acid, analyzing the content of each substance in the liquid products by adopting a gas chromatograph, and calculating the reaction rate of the benzyl alcohol, wherein the chromatographic conditions are that the temperature of a sample injector is 280 ℃, the temperature of a detector is 300 ℃, the temperature of a column chamber is 190 ℃, and a chromatographic column is a nonpolar column OV-101.
Figure BSA0000195616580000031
Formula 1 benzyl alcohol anisole alkylation reaction equation
The second method comprises the following steps: namely, limonene isomerization (see formula 2). Weighing solid acid, measuring limonene and naphthalene in a three-neck flask, wherein the naphthalene is an internal standard substance, the mass of the solid acid accounts for 4% of the total mass of the limonene, the mass of the naphthalene accounts for 5% of the total mass of the limonene, and reacting at 80 ℃ for 60min for sampling. The product adopts a gas chromatograph to analyze the content of each substance in the liquid product, and the reaction rate of the limonene is calculated, wherein the chromatographic conditions are that the temperature of a sample injector is 250 ℃, the temperature of a detector is 250 ℃, the temperature of a column chamber is 100 ℃, and a chromatographic column is a nonpolar column OV-101.
Formula 2 limonene isomerization equation
X-ray fluorescence spectroscopy (XRF) experimental procedure:
and (4) performing X-ray fluorescence spectrum analysis (XRF) by a Shenzhen Despectrum DX-320L XRF tester, and detecting the content of each element contained in the sample. Before testing, the sample is dried, the working environment temperature is 15-30 ℃, and the resolution is 139 eV.
Pyridine absorption infrared (Py-IR) experimental procedure:
pyridine absorption infrared (Py-IR) measurements were performed on a Nicolet 6700 spectrometer setup equipped with a diffuse reflectance accessory and an MCT detector. The tested powder was placed in the in situ chamber and smoothed. First, the powder was treated with He (30 mL. min)-1) Pretreating at 300 deg.C for 1h, cooling to room temperature, and collecting background. Thereafter, gaseous pyridine was adsorbed onto the powder until saturation of the adsorption and the powder was purged with pure He for 1 h. Finally, 1700cm was recorded-1To 1400cm-1Infrared spectrum in the range.
Ammonia adsorption temperature programmed desorption (NH)3TPD) experimental procedure:
NH on TP-5000 equipment (Tianjin Xianchao, China)3Temperature programmed desorption (NH)3TPD). First, the sample was pretreated for 1h under He atmosphere at 300 ℃. Subsequently, the sample was cooled to room temperature and then 5% NH was injected3the/He gas is evaporated until the adsorption is saturated. After switching to pure He, 30mL min-1Purging the flow rate of (1) for about half an hour to remove NH from the sample3The TPD signal is recorded as a function of the temperature, from 40 ℃ to 580 ℃, at a heating rate of 5 ℃ min-1。
HCl-3% SO prepared as described above4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction is 5.17 mmol/g-1·min-1And 3.62 mmol. multidot.g-1·min-1；HCl-3％SO4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 8.24 mmol-g-1·min-1And 5.11 mmol. multidot.g-1·min-1. XRF results showed HCl-3% SO4 2-/TiO2The molar ratio of the Cl element to the S element measured in the solid composite super acid is 0.076.
As shown in attached figure 1, the sulfuric acid-promoted solid super-strong composite acid HCl-3% SO prepared according to the invention4 2-/TiO2At 1490cm-1The corresponding B acid signal is obviously stronger than that of the conventional sulfuric acid-promoted solid acid with super-strong 3% SO4 2-/TiO2The sulfuric acid-promoted solid super-strong composite acid has more B acid; in addition, as shown in figure 2, the sulfuric acid-promoted solid super-strong complex acid HCl-3% SO4 2-/TiO2Has 3 percent SO compared with the conventional sulfuric acid-promoted solid superacid4 2-/TiO2The stronger TCD signal indicates that the sulfuric acid-promoted solid super-strong composite acid has more acid amount, and meanwhile, the desorption temperature of the sulfuric acid-promoted solid super-strong composite acid is higher in the desorption peak of a high-temperature section (more than 500 ℃), which indicates that the sulfuric acid-promoted solid super-strong composite acid has stronger acid strength.
Example 2:
according to the literature[1]Preparation of 2% SO4 2-/ZrO2The preparation method of the solid acid catalyst comprises the following steps: zr (OH)4Forming ZrO after roasting for 2 hours at 650 DEG C2Cooling and taking out the mixture to mix the sulfuric acid with the carrier ZrO2According to SO4 2-And ZrO2Mixing the materials according to the mass ratio of 2: 100, roasting the mixture at high temperature, and marking the finally obtained sample as 2% SO4 2-/ZrO2。
0.5g of the above 2% SO was weighed4 2-/ZrO2Adding solid super acid into a three-mouth flask, heating to 120 ℃, wherein an inlet of the three-mouth flask is connected with a hydrofluoric acid bubbler after being dried by a section of drying column, carrying hydrofluoric acid into the three-mouth flask through nitrogen bubbling, so that gas is fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 0.8h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 100 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing, wherein the sample is marked as HF-2% SO4 2-/ZrO2。
Weighing the prepared HF-2% SO4 2-/ZrO2Solid acid the procedure was as in example 1, method one and method two: and (3) carrying out performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene. And elemental content determination analysis was performed on the samples by XRF.
HF-2% SO prepared as described above4 2-/ZrO2And 2% SO4 2-/ZrO2The conversion rate of benzyl alcohol in the alkylation reaction was 4.39 mmol/g-1·min-1And 2.43 mmol. multidot.g-1·min-1；HF-2％SO4 2-/ZrO2And 2% SO4 2-/ZrO2The conversion rate of limonene in the isomerization reaction was 6.43 mmol-g, respectively-1·min-1And 3.46 mmol. multidot.g-1·min-1. XRF results showed HF-2% SO4 2-/ZrO2The molar ratio of the F element to the S element measured in the solid composite super acid is 0.089.
Example 3:
according to the literature[1]Preparation of 3% SO4 2-/ZrO2The preparation method of the solid acid comprises the following steps: zr (OH)4Forming ZrO after roasting for 2 hours at 650 DEG C2Cooling and taking out the mixture to mix the sulfuric acid with the carrier ZrO2According to SO4 2-And ZrO2Mixing the materials according to the mass ratio of 3: 100, and roasting the mixture at high temperature to finally obtain a sample marked as 3% SO4 2-/ZrO2。
Weighing0.5g of the above 3% SO4 2-/ZrO2And adding solid acid into the three-neck flask, raising the temperature to 120 ℃, wherein the inlet of the three-neck flask is connected with a tail gas treatment device after being dried by a section of drying column and then fully contacted, and the outlet of the three-neck flask is connected with a tail gas treatment device. Keeping for 2h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 150 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing with HBr-3% SO as sample4 2-/ZrO2。
HBr-3% SO prepared above was weighed4 2-/ZrO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) performing performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene, and performing element content determination analysis on the sample by XRF.
HBr-3% SO prepared as described above4 2-/ZrO2And 3% SO4 2-/ZrO2The conversion rate of benzyl alcohol in the alkylation reaction was 6.46 mmol/g-1·min-1And 3.88 mmol. multidot.g-1·min-1；HBr-3％SO4 2-/ZrO2And 3% SO4 2-/ZrO2The conversion rate of limonene in the isomerization reaction was 9.48 mmol-g-1·min-1And 7.10 mmol. multidot.g-1·min-1. XRF results showed HBr-3% SO4 2-/ZrO2The molar ratio of Br element to S element measured in the solid composite super acid was 3.67.
Example 4:
according to the literature[1]Preparation of 2% SO4 2-/TiO2The preparation method of the solid super acid comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing at a mass ratio of 2: 100, high-temperature roasting, and marking as 2% SO4 2-/TiO2。
0.5g of the above 2% SO was weighed4 2-/TiO2And adding the solid acid into a three-neck flask, adjusting the temperature to 20 ℃, wherein an inlet of the three-neck flask is dried by a section of drying column and then is connected with a perchloric acid bubbler, perchloric acid is entrained into the three-neck flask through nitrogen bubbling, so that the gas is fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 4h, stopping ventilation, collecting solid super acid, performing heat treatment at 40 deg.C to obtain final sulfuric acid-promoted solid super-strong composite acid, and storing in a drier, wherein the sample is marked as HClO4-2％SO4 2-/TiO2。
Weighing the HClO prepared above4-2％SO4 2-/TiO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) carrying out performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene. And elemental content determination analysis was performed on the samples by XRF.
HClO prepared as described above4-2％SO4 2-/TiO2And 2% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction was 5.79 mmol/g-1·min-1And 2.22 mmol. multidot.g-1·min-1；HClO4-2％SO4 2-/TiO2And 2% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 10.05 mmol-g-1·min-1And 3.96 mmol. multidot.g-1·min-1. XRF results showed HClO4-2％SO4 2-/TiO2The molar ratio of the F element to the S element in the solid composite super acid was 3.19.
Example 5:
according to the literature[1]Preparation of 3% SO4 2-/TiO2The preparation method of the solid acid comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing at a mass ratio of 3: 100, and high-temperature roasting to obtain 3% SO4 2-/TiO2。
0.5g of the above 3% SO was weighed4 2-/TiO2Solid super acid is added into a three-mouth flask, the temperature is adjusted to 10 ℃, wherein the inlet of the three-mouth flask is connected with a hypochlorous acid bubbler after being dried by a section of drying column, hypochlorous acid is carried into the three-mouth flask by nitrogen bubbling, so that gas is fully contacted with the solid super acid, and the outlet is connected with a tail gas treatment device. Keeping for 4h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 40 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing, wherein the sample is HClO-3% SO4 2-/TiO2。
Weighing HClO-3% SO prepared above4 2-/TiO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) carrying out performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene. And elemental content determination analysis was performed on the samples by XRF.
HClO-3% SO prepared as described above4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction was 9.10 mmol/g-1·min-1And 3.62 mmol. multidot.g-1·min-1；HClO4-3％SO4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 14.17 mmol-g, respectively-1·min-1And 6.76 mmol. multidot.g-1·min-1. XRF results showed HClO-3% SO4 2-/TiO2The molar ratio of the Cl element to the S element measured in the solid composite super acid was 6.28.
Example 6:
according to the literature[2]Preparation of 5% SO4 2-/Fe2O3-Al2O3The preparation method of the solid super acid comprises the following steps: weighing Al (NO) according to the molar ratio of 1: 13)3·9H2O and Fe2(SO4)3·6H2Dissolving the O in the deionized water, and then dissolving,added to vigorously stirred deionized water and, after sufficient cooling, the two solutions were combined. Under strong stirring, dropwise adding concentrated ammonia water to adjust the pH value of the solution to 8-9, allowing a large amount of precipitate to appear, aging, performing suction filtration, washing with water, and drying at 100 ℃. Drying, taking out, mixing sulfuric acid and carrier according to SO4 2-With Fe2O3-Al2O3Mixing at a mass ratio of 5: 100, roasting at high temperature, and marking as 5% SO4 2-/Fe2O3-Al2O3。
0.5g of the above 5% SO was weighed4 2-/Fe2O3-Al2O3Adding solid super acid into a three-mouth flask, heating to 60 ℃, wherein an inlet of the three-mouth flask is connected with a nitric acid bubbler after being dried by a section of drying column, carrying nitric acid into the three-mouth flask through nitrogen bubbling, so that gas is fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 6h, stopping ventilation, collecting solid super acid, performing heat treatment at 60 deg.C to obtain final sulfuric acid-promoted solid super-strong composite acid, and storing in a drier, wherein the sample is marked as HNO3-5％SO4 2-/Fe2O3-Al2O3。
Weighing the HNO prepared above3-5％SO4 2-/Fe2O3-Al2O3Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) performing performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene, and performing element content determination analysis on the sample by XRF.
HNO prepared as described above3-5％SO4 2-/Fe2O3-Al2O3And 5% SO4 2-/Fe2O3-Al2O3The conversion rate of benzyl alcohol in the alkylation reaction is respectively 13.18 mmol-g-1·min-1And 7.86 mmol. multidot.g-1·min-1；HCl-3％SO4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 20.19 mmol-g-1·min-1And 11.70 mmol. multidot.g-1·min-1. XRF results showed HNO3-5％SO4 2-/Fe2O3-Al2O3The molar ratio of the N element to the S element measured in the solid composite super acid was 9.86.
Example 7:
according to the literature[3]Preparation of 5% SO4 2-/SnO2The preparation method of the solid super acid comprises the following steps: crystalline SnCl4Dissolving in water to prepare a solution with the mass fraction of 5%, and dropwise adding SnCl into ammonia water with the mass fraction of 25%4Adjusting pH to about 8 to form colloid, aging for 12 hr, washing, filtering to obtain hydroxide, and mixing with Sn (OH)4And putting the mixture into an oven at 200 ℃ for drying for 4 hours to obtain a glassy solid. Drying, taking out, mixing sulfuric acid and carrier according to SO4 2-With SnO2Mixing the materials according to the mass ratio of 5: 100, and roasting the mixture at high temperature to obtain a sample labeled as 5% SO4 2-/SnO2。
0.5g of the above 5% SO was weighed4 2-/SnO2Adding solid super acid into a three-mouth flask, adjusting the temperature to 30 ℃, wherein an inlet of the three-mouth flask is connected with a high bromic acid bubbler after being dried by a section of drying column, carrying the high bromic acid into the three-mouth flask through nitrogen bubbling, enabling the gas to be fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 2h, stopping ventilation, collecting solid super acid, performing heat treatment at 100 deg.C to obtain final sulfuric acid-promoted solid super-strong composite acid, placing in a drier for storage, and labeling sample as HBrO4-5％SO4 2-/SnO2。
Weighing the HBrO prepared above4-5％SO4 2-/SnO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) performing performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene, and performing element content determination analysis on the sample by XRF.
HBrO prepared as described above4-5％SO4 2-/SnO2And 5% SO4 2-/SnO2The conversion rate of benzyl alcohol in the alkylation reaction was 13.55 mmol/g-1·min-1And 8.84 mmol. multidot.g-1·min-1；HBrO4-5％SO4 2-/SnO2And 5% SO4 2-/SnO2The conversion rate of limonene in the isomerization reaction was 20.85 mmol-g-1·min-1And 13.27 mmol. multidot.g-1·min-1. XRF results show that HBrO4-5％SO4 2-/SnO2The molar ratio of Br element to S element measured in the solid composite super acid was 4.45.
Example 8:
according to the literature[4]Preparation of 10% SO4 2-/HfO2The preparation method of the super-strong solid acid comprises the following steps: HfCl4Dissolving in water to prepare 10% solution, and dripping HfCl into 25% ammonia water4Adjusting pH value of the solution to 9, aging, washing, filtering to obtain corresponding hydroxide, and Obtaining Hf (OH)4Drying in 100 deg.C oven overnight, taking out, and mixing with carrier according to SO4 2-And HfO2Mixing the materials according to the mass ratio of 10: 100, roasting the mixture at high temperature, and marking the finally obtained sample as 10% SO4 2-/HfO2。
0.5g of the above-mentioned 10% SO was weighed4 2-/HfO2Adding solid super acid into a three-mouth flask, adjusting the temperature to-20 ℃, wherein the inlet of the three-mouth flask is connected with a hydriodic acid bubbler after being dried by a section of drying column, the hydriodic acid is carried into the three-mouth flask by nitrogen bubbling, so that the gas is fully contacted with the solid super acid, and the outlet is connected with a tail gas treatment device. Keeping for 4h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 30 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing with sample labeled HI-10% SO4 2-/HfO2。
Is weighed upHI-10% SO prepared as described above4 2-/HfO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) carrying out performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene. And elemental content determination analysis was performed on the samples by XRF.
HI-10% SO prepared as described above4 2-/HfO2And 10% SO4 2-/HfO2The conversion rate of benzyl alcohol in the alkylation reaction was 12.51 mmol/g-1·min-1And 8.53 mmol. multidot.g-1·min-1；HI-10％SO4 2-/HfO2And 10% SO4 2-/HfO2The conversion rate of limonene in the isomerization reaction was 21.09mmol · g, respectively-1·min-1And 14.42 mmol. multidot.g-1·min-1. XRF results showed HI-10% SO4 2-/HfO2The molar ratio of the I element to the S element measured in the solid composite super acid was 4.89.
Example 9:
according to the literature[1]Preparation of 3% SO4 2-/TiO2The preparation method of the solid super acid comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing at a mass ratio of 3: 100, roasting at high temperature, and marking as 3% SO4 2-/TiO2。
0.5g of the above 3% SO was weighed4 2-/TiO2Adding solid super acid into a three-mouth flask, adjusting the temperature to 60 ℃, wherein the inlet of the three-mouth flask is connected with a mixed liquid bubbler with the molar ratio of hydrochloric acid to nitric acid being 1: 1 after being dried by a section of drying column, mixed liquid gas is carried into the three-mouth flask through nitrogen bubbling, so that the gas is fully contacted with the solid super acid, and the outlet is connected with a tail gas treatment device. Keeping for 1.5h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 60 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing, wherein the sample is marked asHCl/HNO3-3％SO4 2-/TiO2。
HCl/HNO prepared as described above3-3％SO4 2-/TiO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) performing performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene, and performing element content determination analysis on the sample by XRF.
HCl/HNO prepared as described above3-3％SO4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction was 8.53 mmol/g-1·min-1And 3.62 mmol. multidot.g-1·min-1；HCl/HNO3-3％SO4 2-/TiO2And 3% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 12.52 mmol-g respectively-1·min-1And 5.19 mmol. multidot.g-1·min-1. XRF results showed HCl/HNO3-3％SO4 2-/TiO2The molar ratio of the Cl element to the S element measured in the solid composite super acid was 1.23, and the molar ratio of the N element to the S element was 1.16.
Example 10:
according to the literature[1]Preparation of 2% SO4 2-/TiO2The preparation method of the solid acid catalyst comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing at a mass ratio of 2: 100, high-temperature roasting, and marking as 2% SO4 2-/TiO2。
0.5g of the above 2% SO was weighed4 2-/TiO2Adding solid superacid into a three-neck flask, adjusting the temperature to 100 ℃, wherein the inlet of the three-neck flask is dried by a section of drying column and then connected with a mixed liquid bubbler with the molar ratio of hydrofluoric acid, hydrochloric acid and hydrobromic acid of 1: 1, and carrying mixed liquid gas into the three-neck flask by nitrogen bubbling to ensure that the gas and the solid superacid enter the three-neck flaskThe strong acid is fully contacted, and the outlet is connected with a tail gas treatment device. Keeping for 1h, stopping ventilation, collecting solid super strong acid, performing heat treatment at 60 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, storing in a drier, and marking the sample as HF/HCl/HBr-2% SO4 2-/TiO2。
HF/HCl/HBr-2% SO prepared as described above4 2-/TiO2Solid acid catalyst the procedure of method one and method two in example 1 was followed: and (3) performing performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene, and performing element content determination analysis on the sample by XRF.
HF/HCl/HBr-2% SO prepared as described above4 2-/TiO2And 2% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction was 6.77 mmol/g-1·min-1And 2.22 mmol. multidot.g-1·min-1；HF/HCl/HBr-2％SO4 2-/TiO2And 2% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 11.62 mmol-g, respectively-1·min-1And 3.96 mmol. multidot.g-1·min-1. XRF results showed HF/HCl/HBr-2% SO4 2-/TiO2The molar ratio of the Cl element to the S element measured in the solid composite super acid is 1.056, the molar ratio of the Cl element to the S element is 1.047, and the molar ratio of the Br element to the S element is 1.032.
Example 11:
according to the literature[1]Preparation of 0.5% SO4 2-/ZrO2The preparation method of the solid acid catalyst comprises the following steps: zr (OH)4Forming ZrO after roasting for 2 hours at 650 DEG C2Cooling and taking out the mixture to mix the sulfuric acid with the carrier ZrO2According to SO4 2-And ZrO2Mixing the materials according to the mass ratio of 0.5: 100, roasting the mixture at high temperature, and marking the finally obtained sample as 0.5 percent SO4 2-/ZrO2。
0.5g of the above-mentioned 0.5% SO was weighed out4 2-/ZrO2Adding solid super acid into a three-neck flask, and addingThe temperature is raised to 260 ℃, wherein an inlet of the three-mouth flask is connected with a nitric acid bubbler after being dried by a section of drying column, nitric acid is carried into the three-mouth flask through nitrogen bubbling, so that gas is fully contacted with solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 12h, stopping ventilation, collecting solid super acid, performing heat treatment at 500 deg.C to obtain final sulfuric acid-promoted solid super-strong composite acid, and storing in a drier, wherein the sample is marked as HNO3-0.5％SO4 2-/ZrO2。
Weighing the HNO prepared above3-0.5％SO4 2-/ZrO2Solid acid the procedure was as in example 1, method one and method two: and (3) carrying out performance evaluation on the alkylation reaction of benzyl alcohol and anisole and the isomerization reaction of limonene. And elemental content determination analysis was performed on the samples by XRF.
HNO prepared as described above3-0.5％SO4 2-/ZrO2And 0.5% SO4 2-/ZrO2The conversion rate of benzyl alcohol in the alkylation reaction is 1.50 mmol-g-1·min-1And 1.09 mmol. multidot.g-1·min-1；HNO3-0.5％SO4 2-/ZrO2And 0.5% SO4 2-/ZrO2The conversion rate of limonene in the isomerization reaction was 1.81 mmol-g-1·min-1And 1.40 mmol. multidot.g-1·min-1. XRF results showed HNO3-0.5％SO4 2-/ZrO2The molar ratio of the N element to the S element measured in the solid composite super acid was 4.82.
Example 12:
according to the literature[1]Preparation of 0.1% SO4 2-/TiO2The preparation method of the solid acid catalyst comprises the following steps: mixing Ti (OH)4Firstly putting the mixture into a muffle furnace to be roasted for 2h at the temperature of 450 ℃ to form TiO2Cooling, taking out, mixing sulfuric acid with carrier TiO2According to SO4 2-With TiO2Mixing at a mass ratio of 0.1: 100, high-temperature roasting, and marking as 0.1% SO4 2-/TiO2。
0.5g of the above-mentioned 0.1% SO was weighed4 2-/TiO2And adding the solid super acid into a three-neck flask, raising the temperature to 30 ℃, wherein an inlet of the three-neck flask is connected with a hydrochloric acid bubbler after being dried by a section of drying column, hydrochloric acid is carried into the three-neck flask by bubbling nitrogen to ensure that gas is fully contacted with the solid super acid, and an outlet is connected with a tail gas treatment device. Keeping for 0.2h, stopping ventilation, collecting solid super acid, performing heat treatment at 30 deg.C to obtain final sulfuric acid-promoted solid super strong composite acid, placing in a drier, and storing with a sample of HCl-0.1% SO4 2-/TiO2。
HCl-0.1% SO prepared as described above4 2-/TiO2Performance evaluation was performed by two methods, benzyl alcohol and anisole alkylation and limonene isomerization, and elemental content determination analysis was performed on the samples by XRF.
HCl-0.1% SO prepared as described above4 2-/TiO2And 0.1% SO4 2-/TiO2The conversion rate of benzyl alcohol in the alkylation reaction is 0.98 mmol/g-1·min-1And 0.26 mmol. multidot.g-1·min-1；HCl-0.1％SO4 2-/TiO2And 0.1% SO4 2-/TiO2The conversion rate of limonene in the isomerization reaction was 0.99 mmol-g-1·min-1And 0.35 mmol. multidot.g-1·min-1. XRF results showed HCl-0.1% SO4 2-/TiO2The molar ratio of the Cl element to the S element measured in the solid composite super acid is 0.98.
Comparative example 1:
a certain amount of HZSM-5 (a silicon-aluminum ratio of 25, catalyst works of southern Kai university) is taken, and the treatment method is as follows: weighing 5g of HZSM-5 in a crucible, putting the crucible into a muffle furnace for activation for 2h at 300 ℃, soaking the activated crucible in 0.5mol/L sulfuric acid for a certain time, filtering, washing with water, putting the activated crucible into a blast drying oven for drying, and grinding the activated crucible into powder for later use.
The HZSM-5 solid acid prepared as described above was evaluated for properties by the first and second methods of example 1Price: the conversion rate of the benzyl alcohol in the alkylation reaction is 2.57 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 2.12 mmol. multidot.g-1·min-1。
Comparative example 2:
0.5g of the HZSM-5 solid acid prepared in comparative example 1 was weighed and added to a three-necked flask, the temperature was controlled at 150 ℃, wherein a hydrochloric acid bubbler was connected to the inlet of the three-necked flask, and the solid acid catalyst was stirred in a hydrochloric acid vapor atmosphere by nitrogen purging, and the outlet was connected to a tail gas treatment apparatus. After 2h, the powder was collected and heat treated at 60 ℃ to produce the final product, labeled as HCl (g) -HZSM-5.
The HCl (g) -HZSM-5 solid acid prepared above was evaluated for properties according to methods one and two of example 1: the conversion rate of the benzyl alcohol in the alkylation reaction is 2.41 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 2.25 mmol-g-1·min-1。
Comparative example 3:
taking a certain amount of Amberlyst-15 solid acid catalyst (average pore diameter is 28.8nm, surface area is 42.5 m)2G, pore volume 0.4cm3Per g, Aladdin reagent (Shanghai) Co., Ltd.) Performance evaluation was performed as in example 1, methods one and two: the conversion rate of the benzyl alcohol in the alkylation reaction is 2.03 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 2.62mmol · g-1·min-1。
Comparative example 4:
0.5g of Amberlyst-15 solid acid prepared in comparative example 3 was weighed and added to a three-necked flask, the temperature was controlled at 150 ℃, wherein the inlet of the three-necked flask was connected to a hydrochloric acid bubbler, the solid acid catalyst was kept under stirring in a hydrochloric acid vapor atmosphere by nitrogen purge, and the outlet was connected to a tail gas treatment unit. After 2h, the powder was collected and heat treated at 60 ℃ to give the final product, labeled HCl (g) -Amberlyst-15.
Performance of the HCl (g) -Amberlyst-15 solid acid prepared above according to methods one and two of example 1Evaluation: the conversion rate of the benzyl alcohol in the alkylation reaction is 2.08 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 2.45 mmol. multidot.g-1·min-1。
Comparative example 5:
0.02mL of concentrated sulfuric acid was measured as a catalyst, and performance evaluation was performed according to the first and second methods in example 1: the conversion rate of the benzyl alcohol in the alkylation reaction is 0.68 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 0.45 mmol. multidot.g-1·min-1。
Comparative example 6:
0.02mL of concentrated hydrochloric acid was measured as a catalyst and performance evaluation was performed according to the first and second methods of example 1: the conversion rate of the benzyl alcohol in the alkylation reaction is 0.04 mmol-g-1·min-1The conversion rate of limonene in the isomerization reaction was 0.02 mmol. multidot.g-1·min-1。
Reference to the literature
[1] Qianqi, wangdian, wangyi, zhanxi, zhao, li xiao juan, li xiao, li cheng. 1610-1617.
[2]Zhaocai bin, grand charming, junk man, Guo Xiao Hua4 2-/Fe2O3-Al2O3-TiO2Preparation of solid superacid and catalytic activity study [ J]Chemical engineer 2008, (03): 1-3.
[3]Solid acid SO of Huoyangwei, Wangchunjie4 2-/SnO2Preparation of (1) and study of its catalytic Properties [ J]Jiangxi chemical industry 2018, (05): 113-115.
[4]K.Arata，H.Nakamura，M.Shouji，Friedel-Crafts acylation of toluenecatalyzed by solid superacids，Applied Catalysis A，General，197(2000).

Claims (9)

1. A high-activity sulfuric acid-promoted solid super-strong composite acid is characterized in that: fixation promoted by sulfuric acidBody super acid (SO)4 2-/MxOy) And assistant acid, wherein sulfate radical (SO) in the sulfuric acid-promoted solid super acid4 2-) The mass percentage content of the compound is 0.1-10 percent; the molar ratio of the auxiliary acid to the sulfate radical is 0.01-10.
2. The high-activity sulfuric acid-promoted solid super-strong complex acid according to claim 1, wherein: the carrier (M) of the sulfuric acid-promoted solid superstrong composite acidxOy) Is one or more metal oxides containing aluminum, zirconium, titanium, tin, iron and hafnium.
3. The high-activity sulfuric acid-promoted solid super-strong complex acid according to claim 1, wherein: the auxiliary acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, chloric acid, perchloric acid, hypochloric acid and nitric acid.
4. A method for preparing the high-activity sulfuric acid-promoted solid super-strong composite acid according to claim 1, which is characterized by comprising the following steps: adding an auxiliary acid into a bubbler, introducing nitrogen, introducing gas at the outlet of the bubbler into a closed container filled with sulfuric acid-promoted solid super strong acid for compounding after passing through a drying tube, controlling the compounding temperature and the compounding time, and performing heat treatment on the obtained sample to finally prepare the sulfuric acid-promoted solid super strong composite acid.
5. The method for preparing the high-activity sulfuric acid-promoted solid super-strong composite acid according to claim 5, wherein the method comprises the following steps: the compounding time is 0.2-12 h.
6. The method for preparing the high-activity sulfuric acid-promoted solid super-strong composite acid according to claim 5, wherein the method comprises the following steps: the compounding temperature is-20-260 ℃.
7. The method for preparing the high-activity sulfuric acid-promoted solid super-strong composite acid according to claim 5, wherein the method comprises the following steps: the heat treatment temperature is 30-500 ℃.
8. The use of the highly reactive sulfuric acid-promoted solid super-strong complex acid of claim 1 in alkylation reactions.
9. The use of the highly active sulfuric acid-promoted solid super-strong complex acid of claim 1 in an isomerization reaction.
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