CN112387308A - Self-supporting solid acidic ionic liquid catalyst and preparation method thereof - Google Patents
Self-supporting solid acidic ionic liquid catalyst and preparation method thereof Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a self-supporting solid acidic ionic liquid catalyst. Dissolving ammonia as a starting material in a solvent to form an ammonia solution, and reacting the ammonia solution with 1, 3-propane sultone or 1, 4-butane sultone to obtain the self-supporting solid acidic ionic liquid. The self-supporting solid acidic ionic liquid prepared by the invention has very high catalytic activity and catalytic stability when used as a heterogeneous catalyst in the catalytic production of biodiesel, and is easy to separate and recover after being used. Meanwhile, the preparation method has simple process and mild condition, and the used raw materials have low price. Therefore, the self-supporting solid acidic ionic liquid prepared by the invention has a practical application prospect in biodiesel production.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a self-supporting solid acidic ionic liquid catalyst.
Background
Energy is an important foundation for national economic and social development and an important component of national strategic safety. Biodiesel is a novel clean fuel and is an important research direction for developing and utilizing renewable energy sources. At present, the preparation of the biodiesel is generally carried out by methods such as a biological enzyme catalysis method, a supercritical catalysis method, a catalytic hydrogenation method, an acid-base catalysis method and the like in industry. In recent years, research on acid-base catalytic production of biodiesel has gradually become a research hotspot due to the harsh conditions and high production cost of the first three methods, wherein two methods, namely transesterification of fatty acid ester and esterification of fatty acid, are most concerned by researchers. The base catalysis method is mainly used in the ester exchange reaction, and the traditional basic catalyst mainly comprises inorganic bases such as sodium hydroxide, potassium hydroxide and the like, and organic bases such as sodium methoxide, sodium ethoxide and the like. However, when the purity of the raw material is insufficient, the alkali catalyst is likely to cause saponification with the raw material, and thus the alkali catalyst requires a high level of raw material, which limits the scale of the reaction to some extent. In contrast, the acidic catalyst can catalyze both the transesterification and esterification reactions without causing saponification of the raw materials. Thus, acid catalysis has gained more attention in recent years than basic catalysis. The traditional acidic catalyst is mainly inorganic strong acid such as sulfuric acid, hydrochloric acid and the like, but has high corrosivity, high requirement on equipment and serious pollution and damage to the environment after being discharged. Therefore, there is an urgent need to develop an acidic catalyst having high catalytic performance and environmental friendliness for the production of biodiesel.
The ionic liquid is a liquid completely composed of ions, has the advantages of low vapor pressure, good ionic conductivity and thermal conductivity, wide liquid state temperature range, strong designability and the like, has no corrosiveness, and is a recognized green solvent. In recent years, the application of acidic ionic liquids as catalysts in the production of biodiesel catalysts has become a hot point of research.
Patent CN105732439A discloses a preparation method of acidic ionic liquid. Mixing tetraethylene diamine and 1, 3-propane sultone or 1, 4-butane sultone, reacting at room temperature until the system is changed from a liquid phase to a solid phase, fully washing the crude product with ethyl acetate, and performing suction filtration and vacuum drying to obtain an intermediate amphoteric salt; and dissolving the intermediate amphoteric salt in deionized water, placing the mixture in an ice water bath, and slowly dropwise adding sulfuric acid for acidification to obtain the target acidic ionic liquid.
Patent CN102120728A discloses a preparation method of acidic ionic liquid. Firstly, mixing and reacting caprolactam water solution and 1, 4-butyl sultone in an equimolar way to obtain a reaction intermediate, and then acidifying the intermediate by using sulfuric acid, p-toluenesulfonic acid, formic acid and phosphoric acid to obtain the acidic ionic liquid.
Patent CN104624242B discloses a preparation method of acidic ionic liquid. Reacting a nitrogen-containing heterocyclic compound with 1, 4-butanesultone to obtain yellowish solid precipitate, performing suction filtration, then cleaning with ethanol, performing vacuum drying to obtain an intermediate, finally adding the intermediate and concentrated sulfuric acid in equal molar amounts into deionized water to obtain a crude ionic liquid product, finally cleaning with ethyl acetate, and performing vacuum drying to obtain the acidic ionic liquid.
Although the acidic ionic liquid prepared by the method has good catalytic performance as a catalyst, the method has the problem of difficult separation and recovery after the reaction, which causes great limitation on the practical application of the acidic ionic liquid. In view of the problems of the conventional acidic ionic liquids, many studies are now directed to the development of solid acidic ionic liquids, and particularly, the development of immobilized acidic ionic liquids is most concerned. The common preparation method of the supported acidic ionic liquid is to load the acidic ionic liquid on a solid carrier to prepare the supported acidic ionic liquid, so as to solve the problem of difficult separation and recovery of the traditional acidic ionic liquid in practical use.
Patent CN110548540A discloses a preparation method of immobilized acidic ionic liquid. The preparation method comprises the following steps of carrying out coupling reaction on an amino-containing silane coupling agent and a silicon hydroxyl-containing carrier such as silica gel, attapulgite or a molecular sieve to obtain a coupling agent functionalized carrier, carrying out quaternization treatment on the amino on the carrier by adopting lactone sulfonate as a quaternization agent to obtain an immobilized functionalized ionic liquid intermediate, and finally carrying out acidification treatment on the immobilized ionic liquid intermediate by using sulfuric acid to obtain the immobilized acidic ionic liquid.
Patent CN107029784B discloses a preparation method of a polymer supported acidic ionic liquid catalyst. Vinyl benzyl chloride and styrene are used as polymerization monomers, divinylbenzene is used as a cross-linking agent, a polymer obtained through free radical polymerization is used as a carrier, then bis (2-chloroethyl) amine and benzimidazole are grafted on the carrier through nucleophilic substitution reaction with benzyl chloride, 1, 3-propane sultone is used for modification to obtain an immobilized ionic liquid intermediate, and finally concentrated sulfuric acid or trifluoromethanesulfonic acid is used for acidification treatment, so that immobilized acidic ionic liquid is obtained.
The immobilized acidic ionic liquid prepared by the method is essentially prepared by immobilizing the ionic liquid on a carrier to prepare a solid ionic liquid, namely, the carrier plays a role in supporting a final product and enables the final product to be in a solid state. Although the problem that the immobilized acidic ionic liquid is difficult to separate and recover in the using process of the immobilized acidic ionic liquid as a catalyst is effectively solved, the stability of the catalytic activity of the immobilized acidic ionic liquid is poor, and the requirement of long-term use cannot be met. This is mainly because the carrier for immobilizing the acidic ionic liquid does not have acidic catalytic performance by itself, and protons for exerting the acidic catalytic performance are derived from an additional acid such as sulfuric acid and trifluoromethanesulfonic acid. Generally, the immobilized acidic ionic liquid generally faces three more serious problems limited by the above self-structure: (1) the existence of the carrier reduces the number of acid sites of the immobilized acidic ionic liquid, thereby reducing the acid catalytic activity of a final product, (2) the external acid is connected with the carrier only through an ionic bond rather than a covalent bond, and the loss of the external acid is easy to occur in the use process, thereby causing the continuous reduction of the acid catalytic performance of the immobilized acidic ionic liquid along with the prolonging of the use time. (3) The preparation process is complicated, the time is long, the production efficiency is low, and the production cost is high, so that the large-scale application of the preparation is limited.
In view of the above, there is a need for a heterogeneous acid catalyst with high performance and high stability for the industrial production of biodiesel. Considering the advantages (high activity) and disadvantages (difficult separation and recovery) of the traditional acidic ionic liquid, the modification of the acidic ionic liquid to prepare the solid acidic ionic liquid has outstanding scientific and practical significance. Although the traditional immobilized acidic ionic liquid can avoid the problem of difficult separation and recovery in the use process, the preparation process of the traditional immobilized acidic ionic liquid is highly dependent on a carrier for playing a supporting role, and the introduction of the carrier not only increases the preparation cost, but also causes poor catalytic activity and stability of the final product. In view of the above, the development of a self-supporting (i.e. without support) solid acidic ionic liquid can not only overcome the problems of low catalytic activity and low catalytic stability of the immobilized acidic ionic liquid, but also greatly reduce the preparation cost of the catalyst, so that a heterogeneous acidic ionic liquid catalyst with low cost and good performance is expected to be prepared, thereby meeting the requirement of practical production of biodiesel.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting solid acidic ionic liquid catalyst, which overcomes the defects of the prior art and provides a high-efficiency and stable acidic catalyst for the industrial production of biodiesel.
In view of the above object, the following invention is proposed:
a preparation method of a self-supporting solid acidic ionic liquid catalyst comprises the following steps:
dissolving ammonia serving as a starting raw material in a solvent to form an ammonia solution, stirring and reacting the ammonia solution with 1, 3-propane sultone or 1, 4-butane sultone, and filtering, washing and drying after the reaction is finished to obtain a self-supporting solid acidic ionic liquid;
the solvent is water or an organic solvent which can form a uniform solution with ammonia, and preferably, the organic solvent can be one of methanol, ethanol, isopropanol, 1, 4-dioxane, dimethyl sulfoxide, acetone and acetonitrile;
the mass fraction of the solute of the ammonia solution is 1-100 wt%;
the molar ratio of the ammonia molecules of the ammonia solution to 1, 3-propane sultone or 1, 4-butane sultone is 1: 1-1: 20;
the reaction temperature is 20-80 ℃, and the reaction time is 0.1-24 h;
the drying temperature is 30-150 ℃, and the drying time is 2-48 h;
the preparation reaction formula is shown in figure 1.
Compared with the prior art, the invention has the remarkable advantages that:
(1) the self-supporting solid acidic ionic liquid prepared by the invention is prepared by one-step reaction of ammonia molecules and sultone. Compared with the traditional ionic liquid and immobilized ionic liquid, the self-supporting solid acidic ionic liquid prepared by the invention has the advantages of low price of raw materials, simple preparation process, and capability of avoiding environmental pollution and economic consumption of the use and treatment of additional acid.
(2) The self-supporting solid acidic ionic liquid prepared by the invention is characterized in that sultone ring opening is utilized to sulfonate ammonia, so that a large number of sulfonic acid groups are grafted on nitrogen atoms. In the process, part of sulfonic acid groups and ammonia molecules are combined to form zwitterion pairs (which can be regarded as inner salts in nature), and the rest of sulfonic acid groups play an acidic catalysis role. The self-supporting solid acidic ionic liquid can be used as a heterogeneous catalyst due to the existence of the zwitterion pair, and the problem of difficult separation and recovery after catalytic reaction does not exist. Compared with the traditional solid carrier ionic liquid, the self-supporting solid acidic ionic liquid can maintain the solid property without introducing a carrier for supporting, overcomes the problems of high cost and low activity caused by the use of the carrier, effectively reduces the preparation cost of the catalyst and improves the catalytic performance of the catalyst.
(3) The preparation process of the self-supporting solid acidic ionic liquid prepared by the invention does not need to use additional acid, thereby effectively simplifying the preparation process of the catalyst and reducing the manufacturing cost of the catalyst. Meanwhile, the proton of the self-supporting solid acidic ionic liquid which plays the role of acidic catalysis does not depend on an additional acid and can stably exist in the using process of the catalyst, so that the problem of reduction of catalytic activity does not exist.
Drawings
FIG. 1 is a schematic diagram of the reaction scheme of the present invention.
Detailed description of the invention
The invention is further illustrated by the following specific examples.
Example 1
Dropwise adding a methanol solution of ammonia with the mass fraction of 10wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 60 ℃ for 24h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.58 mmol/g.
The self-supporting solid acidic ionic liquid catalyst is used for catalyzing the production of biodiesel by oleate to verify the catalytic activity: adding methanol and oleic acid into a reaction kettle according to the molar ratio of 10:1 of alcohol acid, adding the self-supporting solid acidic ionic liquid as a catalyst, wherein the adding amount of the catalyst is 2.0 percent of the mass of the oleic acid, the reaction temperature is 50 ℃, the reaction time is 0.5h, obtaining a biodiesel crude product, then separating the methanol through reduced pressure distillation, obtaining a refined product biodiesel, and calculating the biodiesel yield through gas chromatography analysis, wherein the biodiesel yield is 99.52 percent.
The used catalyst is recovered by filtration and recycled for 6 times under the same reaction condition, and the catalytic activity of the catalyst is kept stable, which shows that the self-supporting solid ionic liquid of the invention has excellent catalytic stability in the production of biodiesel.
Comparative example 1
The acid values of the two optimal acidic ionic liquids disclosed in patent CN107866276B and patent CN109174179A are both 1.95mmol/g, and the experimental conditions of the two optimal acidic ionic liquids as an acidic catalyst applied to catalyzing the oleate to produce biodiesel are the same, specifically as follows: adding methanol and oleic acid into a reaction kettle according to the molar ratio of 10:1 of alcohol acid, adding the catalyst, wherein the adding amount of the catalyst is 2.0 percent of the mass of the oleic acid, the reaction temperature is 60 ℃, the reaction time is 1h, obtaining a crude biodiesel product, then separating the methanol through reduced pressure distillation, obtaining a refined product biodiesel, and calculating the yield of the biodiesel through gas chromatography analysis, wherein the results are 99.34 percent.
It can be seen that compared with the optimal acidic ionic liquid disclosed in patent CN107866276B and patent CN109174179A, the acid value of the self-supporting solid ionic liquid prepared by the invention is greatly improved (from 1.95mmol/g to 2.58 mmol/g). Meanwhile, when the catalyst prepared by the invention is used for catalyzing the esterification of oil to produce the biodiesel, the biodiesel with higher yield (99.34 percent is improved to 99.52 percent) can be obtained at lower temperature (60 ℃ is reduced to 50 ℃) in shorter time (1 h is shortened to 0.5 h) under the same other conditions. In summary, compared with the optimal acidic ionic liquid disclosed in patent CN107866276B and patent CN109174179A, the self-supporting solid ionic liquid prepared by the present invention has more acidic catalytic active sites, higher catalytic activity, and higher catalytic efficiency in biodiesel production.
Example 2
Dropwise adding a methanol solution of ammonia with the mass fraction of 10wt% into 1, 4-butanesultone (the molar ratio of ammonia molecules to 1, 3-propanesultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 150 ℃ for 12h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.50 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 99.23%.
Example 3
Dropwise adding an ethanol solution of ammonia with the mass fraction of 100wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 1), reacting at 20 ℃ for 24h, filtering, washing with methanol, and drying at 60 ℃ for 12h after the reaction is finished to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 1.34 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 91.07%.
Example 4
Dropwise adding an aqueous solution of ammonia with the mass fraction of 1wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 10), reacting at 80 ℃ for 0.1h, filtering after the reaction is finished, washing with methanol, and drying at 150 ℃ for 2h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 1.57 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 94.29%.
Example 5
Dropwise adding an isopropanol solution of ammonia with the mass fraction of 1wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 80 ℃ for 0.1h, filtering after the reaction is finished, washing with methanol, and drying at 30 ℃ for 48h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.45 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 98.77%.
Example 6
Dropwise adding a 1, 4-dioxane solution of ammonia with the mass fraction of 10wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 60 ℃ for 24h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.55 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the yield of the biodiesel is 99.35%.
Example 7
Dropwise adding a dimethyl sulfoxide solution of ammonia with the mass fraction of 10wt% into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 60 ℃ for 24h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.57 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the yield of the biodiesel is 99.48%.
Example 8
Dropwise adding 10wt% of ammonia acetone solution into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 60 ℃ for 24h to obtain the self-supporting solid acidic ionic liquid catalyst, wherein the acid value of the self-supporting solid acidic ionic liquid catalyst is 2.51 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the yield of the biodiesel is 99.27%.
Example 9
Dropwise adding 10wt% ammonia acetonitrile solution into 1, 3-propane sultone (the molar ratio of ammonia molecules to 1, 3-propane sultone is 1: 20), reacting at 40 ℃ for 12h, filtering after the reaction is finished, washing with methanol, and drying at 60 ℃ for 24h to obtain the self-supporting solid acidic ionic liquid catalyst with the acid value of 2.49 mmol/g.
The prepared self-supporting solid acidic ionic liquid is used as a catalyst for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the yield of the biodiesel is 99.04%.
The results of the above examples show that by using the preparation method of the present invention, through controlling various conditions in the catalyst preparation process, including the molar ratio of ammonia molecules to sultone, the kind and concentration of the solvent, and the temperature and time of the reaction, the properties of the prepared self-supporting solid acidic ionic liquid can be effectively controlled, and an acidic catalyst with excellent catalytic performance can be selected from the acidic ionic liquid, so that the acidic ionic liquid has the potential for practical production of biodiesel.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a self-supporting solid acidic ionic liquid catalyst is characterized by comprising the following steps:
dissolving ammonia as a starting raw material in a solvent to form an ammonia solution, then carrying out stirring reaction on the ammonia solution and 1, 3-propane sultone or 1, 4-butane sultone, and filtering, washing and drying after the reaction is finished to obtain the self-supporting solid acidic ionic liquid.
2. The method of claim 1, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the solvent is water or an organic solvent capable of forming a homogeneous solution with ammonia.
3. The method of claim 2, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the organic solvent is selected from one of methanol, ethanol, isopropanol, 1, 4-dioxane, dimethyl sulfoxide, acetone and acetonitrile.
4. The method of claim 1, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the mass fraction of the solute of the ammonia solution is 1-100 wt%.
5. The method of claim 1, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the molar ratio of the ammonia molecules of the ammonia solution to 1, 3-propane sultone or 1, 4-butane sultone is 1: 1-1: 20.
6. The method of claim 1, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the reaction temperature is 20-80 ℃.
7. The method of claim 1, wherein the acidic ionic liquid catalyst is selected from the group consisting of: the reaction time is 0.1-24 h.
8. The method of claim 1, wherein the ionic liquid catalyst is selected from the group consisting of: the drying temperature is 30-150 ℃.
9. The method of claim 1, wherein the ionic liquid catalyst is selected from the group consisting of: the drying time is 2-48 h.
10. A self-supporting solid-type ionic acidic liquid catalyst prepared by the method of any one of claims 1 to 9.
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| CN113181963A (en) * | 2021-05-14 | 2021-07-30 | 安庆精益精化工有限公司 | Preparation method of solid alkyl sulfonic acid catalyst |
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| CN111036294A (en) * | 2020-01-08 | 2020-04-21 | 福州大学 | Polyacid site ionic liquid catalyst based on polyethyleneimine and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181963A (en) * | 2021-05-14 | 2021-07-30 | 安庆精益精化工有限公司 | Preparation method of solid alkyl sulfonic acid catalyst |
| CN113181963B (en) * | 2021-05-14 | 2022-10-11 | 安庆精益精化工有限公司 | Preparation method of solid alkyl sulfonic acid catalyst |
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