CN110694682A - Heteropolyacid type ionic liquid catalyst and preparation method and application thereof - Google Patents

Heteropolyacid type ionic liquid catalyst and preparation method and application thereof Download PDF

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CN110694682A
CN110694682A CN201910924076.6A CN201910924076A CN110694682A CN 110694682 A CN110694682 A CN 110694682A CN 201910924076 A CN201910924076 A CN 201910924076A CN 110694682 A CN110694682 A CN 110694682A
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ionic liquid
liquid catalyst
reaction
type ionic
heteropolyacid
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王建英
宁原锋
李智
胡永琪
曹超文
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Hebei University of Science and Technology
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Hebei University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0278—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 containing nitrogen as cationic centre
    • B01J31/0281—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 containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—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 containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues

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Abstract

The invention provides a heteropoly acid type ionic liquid catalyst and a preparation method and application thereof. Compared with the prior art, the method does not use an organic solvent and a phase transfer agent, has mild operation conditions and environmental friendliness, uses a catalyst with high stability, can keep higher catalytic activity for a long time, does not generate toxic nitrogen oxides compared with the prior art for producing adipic acid, and is a green production method.

Description

Heteropolyacid type ionic liquid catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of imidazole ionic liquids, in particular to a heteropoly acid type ionic liquid catalyst, and also relates to a preparation method and application of the catalyst.
Background
Adipic acid is an important organic chemical raw material, is closely related to the life of people, can perform various reactions such as salification, anhydride formation, amidation, esterification and the like, and can be widely applied to the fields of polyurethane, nylon, medicine, polyester foam synthetic resin and the like.
Currently, most of the conventional industrial methods for producing adipic acid use a nitric acid oxidation method, i.e., oxidation using cyclohexane and cyclohexanone as raw materials and nitric acid as an oxidizing agent. A large amount of N is generated in the nitric acid oxidation process2O, and N2O causes greenhouse effect and global warming, and also causes global pollution, ozone layer destruction, and acid rain. Using cyclohexene as raw material and H2O2Used as an oxidant for the adipic acid oxidation reaction, is a green process for synthesizing adipic acid, H2O2Is a green oxidant, and the byproduct after the decomposition reaction is only water. In recent years, the formula H2O2The reaction of synthesizing adipic acid as oxidant is widely regarded.
Chinese patent CN102766037A discloses a method for preparing adipic acid from cyclohexene, which is to contact cyclohexene and hydrogen peroxide with a catalyst under certain reaction conditions, wherein the catalyst comprises a component a and a component B, the component a is a titanium-silicon molecular sieve, and the component B is one or more of polymetallic oxyacid and polymetallic oxyacid salt. The method has high selectivity on adipic acid, which can reach 90% at most, and the titanium silicalite molecular sieve is used as a catalyst, so that the method has the advantages of mild reaction conditions, good selectivity of a target product, simple process and the like, but cannot show excellent performance when the titanium silicalite molecular sieve is introduced into a reaction for preparing adipic acid from cyclohexene.
Chinese patent CN102614920A discloses the synthesis of adipic acid by catalytic oxidation of cyclohexene using silica or polystyrene resin immobilized decatungstate catalyst. The synthesis method has the advantages that the reaction is carried out for 10-30h at 60-110 ℃, the yield of the adipic acid can reach 94.38%, and after the reaction is finished, the hot suction filtration is carried out, so that the analysis of the catalyst and the adipic acid is facilitated, and the difficulty in recovering the catalyst is greatly reduced. However, the supported catalyst is leached out in a large amount in a high-temperature reaction solution, so that the activity and the recycling performance of the catalyst are reduced.
Chinese patent CN102698808A discloses a composite catalyst and a method for synthesizing adipic acid by cleanly catalyzing and oxidizing cyclohexene by the composite catalyst, hydrogen peroxide and the composite catalyst are added into cyclohexene, the mixture reacts for 4 to 10 hours at 65 to 75 ℃, then the temperature is increased to 85 to 100 ℃ and the reaction is carried out for 10 to 24 hours, and the total yield of the adipic acid can reach 90.15 percent. The compound catalyst used in the method is amino acid salt ionic liquid containing carboxyl, the catalyst has the characteristics of high activity, high selectivity, high yield and the like, and the catalyst is clean and environment-friendly and has good application prospect. However, the method has too long reaction time and low efficiency, and is not suitable for industrial production.
Chinese patent CN103254060A discloses a method for preparing adipic acid by co-catalytic oxidation of six-carbon oxygen-containing compound and cyclohexane, wherein cyclohexane is inert, and generally strict reaction conditions are adopted for activating cyclohexane, but adipic acid is also degraded. In order to activate cyclohexane as much as possible and avoid degrading adipic acid, one or more mixtures of transition metal salts or oxides, N-hydroxyphthalimides and the like, metal phthalocyanines and metal porphyrins are selected as catalysts, and a co-oxidation system of six-carbon oxygen-containing compounds is selected. However, the whole reaction of the method is a high-pressure batch reaction, the cyclohexene conversion rate is low, the operation safety is low, and the used catalyst is expensive and is not suitable for industrial application.
Chinese patent CN106380375A discloses a method for continuously synthesizing adipic acid by a microchannel reactor, which is divided into two stages, namely cyclohexene oxidation to 1, 2-cyclohexanediol and 1, 2-cyclohexanediol oxidation to adipic acid. In the first stage, hydrogen peroxide and a tungsten-containing catalyst are mixed to form peroxytungstic acid, a cyclohexene and peroxytungstic acid mixed solution is respectively filled into a microreactor by two pumps, the microreactor is heated to the reaction temperature and then enters a reaction area A for reaction, and after the reaction is completed, the cyclohexene and peroxytungstic acid mixed solution flows out of the reaction area A to form 1, 2-cyclohexanediol. In the second stage, the 1, 2-cyclohexanediol reaction solution is heated to the reaction temperature and then directly enters the reaction zone B for reaction, and the effluent liquid is the crude product of adipic acid. The method overcomes the defects of the prior art, and provides the method which has simple process, short reaction time, high reaction efficiency and easy industrial production. However, the method needs to accurately control the residence time, short or overlong residence time can directly influence the yield of adipic acid, and cyclohexene is easy to gasify and cannot cause feeding difficulty through a metering pump, so that strict control of the residence time and solving of the feeding problem are all factors to be considered.
Chinese patent CN103193616A discloses a method for preparing adipic acid by oxidizing cyclohexene with air under the catalysis of non-metallic carbon, cyclohexene and a non-metallic carbon material are dissolved in an organic solvent and react for 12 hours at 120 ℃, and the highest selectivity of the adipic acid is 92%. However, the reaction conditions of the method are harsh, and the method must be carried out in a high-pressure reaction kettle, so that certain potential safety hazards are caused.
Disclosure of Invention
In view of the above, the invention aims to provide a heteropoly acid type ionic liquid catalyst which has the characteristics of high catalytic activity, low pollution and low toxicity and can be used for preparing adipic acid by catalytic oxidation of cyclohexene with hydrogen peroxide as an oxygen source.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a heteropoly acid type ionic liquid catalyst is composed of a binuclear ionic liquid shown as a general formula A,
wherein R is hydrogen or unsubstituted C1～10Alkyl, or straight-chain C substituted by substituent1～10The substituent is amino, carboxyl or sulfonic group;
x is a heteropolyacid radical.
Further, R is a straight chain C substituted by a substituent1～3Alkane, wherein the substituent is hydroxyl, carboxyl or sulfonic group.
Further, R is a straight chain C substituted by a sulfonic acid group1～3An alkane.
Further, X is PW12O40 3-、SiW12O40 3-、PMo12O40 3-One kind of (1).
The invention also provides a preparation method of the heteropoly acid type ionic liquid catalyst, which comprises the following steps:
step a: synthesis of intermediate [ C4(Mim)2]Imidazole, sodium hydroxide and dimethyl sulfoxide are used as raw materials, stirring and reacting are carried out for 0.5-2h at the temperature of 40-70 ℃, 1, 4-dibromobutane is dropwise added, the reaction is continued for 2h, and recrystallization, filtration and drying are carried out after the reaction is finished to obtain a white solid [ C ]4(Mim)2]；
Step b: synthesis of intermediate [ C4(Rim)2]Dissolving the white solid obtained in the step a in distilled water, adding a toluene solution containing 1, 3-propyl sultone, heating the mixture solution to 40-65 ℃, stirring for reaction for 12-36h, cooling, washing, and removing water by rotary evaporation to obtain a viscous liquid [ C4(Rim)2]；
Step c: synthesizing an ionic liquid catalyst, reacting the binuclear ionic liquid obtained in the step b with a heteropoly acid aqueous solution, stirring and reacting for 1-4h at 15-30 ℃, filtering and drying to obtain a heteropoly acid type ionic liquid catalyst [ C4(Rim)2][X]。
Further, the heteropoly acid is one of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
Further, in the step a, the reaction temperature is 60 ℃, and the stirring time is 1 h; in the step b, the heating temperature is 50 ℃, and the stirring time is 24 hours; in the step c, the reaction temperature is 25 ℃, and the reaction time is 1 h.
In addition, the invention also provides an application of the heteropoly acid type ionic liquid catalyst, and the heteropoly acid type ionic liquid catalyst is used for preparing adipic acid by catalytic oxidation of cyclohexene.
Further, dissolving the heteropolyacid catalyst in hydrogen peroxide at room temperature, adding the solution into a container filled with cyclohexene, heating to 50-80 ℃, reacting for 0.5-2.5h, continuously heating to 83 ℃, reacting for 6-13h, cooling after the reaction is finished, freezing for 5h at 0 ℃, filtering, washing and drying to obtain the adipic acid.
Further, the molar ratio of the heteropoly acid type ionic liquid catalyst to cyclohexene is 1: 60-1: 10, the molar ratio of hydrogen peroxide to cyclohexene is 4-6.5: 1, and the pH value of a reaction solution after the heteropoly acid type ionic liquid catalyst is added is 1.0-2.5.
Compared with the prior art, the invention has the following advantages:
the heteropoly acid type ionic liquid catalyst has the key active components of the catalyst because the Keggin structure of heteropoly acid is maintained, and in addition, cations of the heteropoly acid type ionic liquid can provide an acid environment required by reaction and promote contact of reaction substrates, so the heteropoly acid type ionic liquid has high catalytic activity. Compared with the prior art, the invention avoids using corrosive oxidants such as nitric acid and the like, and can radically solve the problem of discharging N2The method for preparing adipic acid has the advantages of no need of adding an organic solvent and a phase transfer agent during preparation by using the ionic liquid containing the heteropoly acid structure as a catalyst, low pollution, low toxicity, and capability of realizing clean production, thereby providing a direction for green synthesis of adipic acid.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example one
The embodiment relates to the preparation of a heteropoly acid type ionic liquid catalyst, and the specific preparation example is as follows:
example 1.1
Certain amounts of imidazole (4.3 g), sodium hydroxide (2.0 g) and dimethyl sulfoxide (10 ml) were added to a vessel (e.g. a flask), the reaction was stirred at 60 ℃ for 1 hour, 6.477g of 1, 4-dibromobutane was added dropwise, the reaction was continued for 2 hours, and then recrystallization, filtration and drying were carried out to obtain a white solid. Weighing 0.15mol of white solid, dissolving in distilled water, adding 20ml of toluene solution containing 0.3mol of 1, 3-propyl sultone, heating the mixture solution to 50 ℃, stirring for reaction for 24h, cooling, washing, and removing water by rotary evaporation to obtain the binuclear imidazole ionic liquid. Reacting the obtained binuclear ionic liquid (10mmol) with an aqueous solution of phosphotungstic acid (6.6mmol), stirring and reacting at 25 ℃ for 1h, filtering, and drying to obtain the bis- (3-sulfopropyl-1-imidazole) phosphotungstate, which has the following structural formula:
Figure BDA0002218473580000051
example 1.2
A certain amount of imidazole, 4.3g, sodium hydroxide, 2.0g and 10ml of dimethyl sulfoxide are added into a flask, stirred and reacted for 1 hour at 60 ℃, 6.477g of 1, 4-dibromobutane is added dropwise, the reaction is continued for 2 hours, and then recrystallization, filtration and drying are carried out to obtain a white solid. Weighing 0.15mol of white solid, dissolving in distilled water, adding 20ml of toluene solution containing 0.3mol of 1, 3-propyl sultone, heating the mixture solution to 50 ℃, stirring for reaction for 24h, cooling, washing, and removing water by rotary evaporation to obtain the binuclear imidazole ionic liquid. Reacting the obtained binuclear ionic liquid (5mmol) with a silicotungstic acid (3.3mmol) aqueous solution, stirring and reacting at 25 ℃ for 1h, filtering, and drying to obtain the bis- (3-sulfopropyl-1-imidazole) silicotungstate, which has the following structural formula:
Figure BDA0002218473580000061
example 1.3
A certain amount of imidazole, 4.3g, sodium hydroxide, 2.0g and 10ml of dimethyl sulfoxide are added into a flask, stirred and reacted for 1 hour at 60 ℃, 6.477g of 1, 4-dibromobutane is added dropwise, the reaction is continued for 2 hours, and then recrystallization, filtration and drying are carried out to obtain a white solid. Weighing 0.15mol of white solid, dissolving in distilled water, adding 20ml of toluene solution containing 0.3mol of 1, 3-propyl sultone, heating the mixture solution to 50 ℃, stirring for reaction for 24h, cooling, washing, and removing water by rotary evaporation to obtain the binuclear imidazole ionic liquid. Reacting the obtained binuclear ionic liquid (10mmol) with an aqueous solution of phosphomolybdic acid (6.67mmol), stirring and reacting at 25 ℃ for 1h, filtering, and drying to obtain bis- (3-sulfopropyl-1-imidazole) silicotungstate, which has the following structural formula:
example two
The embodiment relates to a method for preparing adipic acid by catalyzing and oxidizing cyclohexene with the ionic liquid catalyst prepared in the first embodiment, which comprises the following specific preparation steps:
example 2.1
Using bis- (3-sulfopropyl-1-imidazole) phosphotungstate as a catalyst, adding 3.313g of the catalyst and 21.43ml of 30% hydrogen peroxide into a flask at room temperature, stirring for 10 minutes until the pH value of a reaction solution is 1.0, adding 5.06ml of cyclohexene at one time, simultaneously heating to 75 ℃ for reaction for 2 hours, and then continuously heating to 83 ℃ for reaction for 11 hours. After the reaction is finished, cooling to room temperature, separating out a large amount of adipic acid crystals, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The total yield of adipic acid was found to be 93.1%.
Example 2.2
Using bis- (3-sulfopropyl-1-imidazole) silicotungstate as a catalyst, adding 3.310g of the catalyst and 22.43ml of 30% hydrogen peroxide into a flask at room temperature, stirring for 10 minutes until the pH value of the solution is 1.62, adding 5.06ml of cyclohexene at one time, simultaneously heating to 75 ℃ for reaction for 2 hours, and then continuously heating to 83 ℃ for reaction for 11 hours. After the reaction is finished, cooling to room temperature, separating out a large amount of adipic acid crystals, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The total yield of adipic acid was found to be 91.7%.
Example 2.3
Using bis- (3-sulfopropyl-1-imidazole) phosphomolybdate as a catalyst, adding 2.258g of the catalyst and 21.43ml of 30% hydrogen peroxide into a flask at room temperature, stirring for 10 minutes, adjusting the pH value of the solution to 1.9, adding 5.06ml of cyclohexene once again, simultaneously heating to 75 ℃ for reaction for 2 hours, and then continuously heating to 83 ℃ for reaction for 11 hours. After the reaction is finished, cooling to room temperature, separating out a large amount of adipic acid crystals, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The total yield of adipic acid was found to be 88.7%.
Example 2.4
Using bis- (3-sulfopropyl-1-imidazole) phosphotungstate as a catalyst, adding 2.219g of the catalyst and 23.45ml of 30% hydrogen peroxide into a flask at room temperature, stirring for 10 minutes, then adding 5.06ml of cyclohexene, simultaneously heating to 75 ℃ for reaction for 2 hours, and then continuously heating to 85 ℃ for reaction for 11 hours, wherein the pH of the solution is 1.37. After the reaction is finished, cooling to room temperature, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The total yield of adipic acid was found to be 86.5%.
Example 2.5
Using bis- (3-sulfopropyl-1-imidazole) phosphotungstate as a catalyst, adding 6.626g of the catalyst and 20.92ml of 30% hydrogen peroxide into a flask at room temperature, stirring for 10 minutes, adjusting the pH value of a reaction solution to 0.85, adding 5.06ml of cyclohexene, simultaneously heating to 75 ℃ for reaction for 2 hours, and then continuously heating to 80 ℃ for reaction for 10 hours. After the reaction is finished, cooling to room temperature, separating out adipic acid crystals, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The total yield of adipic acid was determined to be 78.5%.
EXAMPLE III
The present example relates to the investigation of the catalytic activity of the ionic liquid catalyst prepared in the first example, and the specific investigation method is as follows:
example 3.1
The preparation method comprises the steps of adding 21.43ml of 30% hydrogen peroxide and 1mmol of heteropolyacid (namely phosphotungstic acid, silicotungstic acid or phosphomolybdic acid) into a flask at room temperature, stirring for 10 minutes, adding 5.06ml of cyclohexene at one time, simultaneously heating to 75 ℃ for reaction for 2 hours, and continuously heating to 83 ℃ for reaction for 11 hours. After the reaction is finished, cooling to room temperature, freezing for 5 hours at the temperature of 0 ℃, filtering, washing and drying to obtain white crystals, namely adipic acid. The yields of the adipic acid after the preparation were determined to be shown in table 1:
TABLE 1 adipic acid preparation yield from heteropoly acids
Heteropolyacid species Phosphotungstic acid Silicotungstic acid Phosphomolybdic acid
Adipic acid yield 50.6％ 15.42％ 18.57％
Comparing the adipic acid yields in table 1 with the yields measured in examples 2.1-2.5 of example two, it was found that the yields were much higher when using the ionic liquid catalyst of the present invention for the preparation of adipic acid than when using the corresponding heteropolyacid.
Example 3.2
The recycled bis- (3-sulfopropyl-1-imidazole) phosphotungstate catalyst was repeatedly recycled under the conditions of example 2.1 in example two, and the reusability of the catalyst was examined, and the results are shown in table 2:
TABLE 2 reusability of phosphotungstic acid ionic liquid catalysts
Number of repeated use Adipic acid yield/%)
0 93.1
1 92.5
2 89.7
3 86.8
4 83.5
The results obtained by the method show that the catalyst prepared by the invention has high stability and can maintain higher catalytic activity for a long time.
Example 3.3
The reusability of the recovered bis- (3-sulfopropyl-1-imidazole) silicotungstate catalyst was examined by repeated recycling under the conditions of example 2.2 in example two, and the results are shown in table 3:
TABLE 3 reusability of silicotungstic acid ionic liquid catalysts
Number of repeated use Adipic acid yield/%)
0 91.7
1 90.1
2 87.7
3 83.8
4 80.6
The results obtained by the method show that the catalyst prepared by the invention has high stability and can maintain higher catalytic activity for a long time.
Example 3.4
The reusability of the recovered bis- (3-sulfopropyl-1-imidazole) phosphomolybdate catalyst was examined by repeated recycling under the conditions of example 2.3 in example two, and the results are shown in table 4:
TABLE 4 reusability of phosphomolybdic acid ionic liquid catalysts
Number of repeated use Adipic acid yield/%)
0 88.7
1 86.9
2 83.2
3 80.5
4 78.9
The results obtained by the method show that the catalyst prepared by the invention has high stability and can maintain higher catalytic activity for a long time.
In conclusion, the binuclear heteropoly acid type ionic liquid catalyst synthesized by taking imidazole as a raw material is used for preparing adipic acid by catalyzing and oxidizing cyclohexene by the catalyst, so that the use of toxic and harmful organic solvents and phase transfer agents can be avoided, the influence on the environment can be eliminated, the yield of the obtained adipic acid is much higher than that of the corresponding heteropoly acid, and the catalyst has a good application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A heteropoly acid type ionic liquid catalyst is characterized in that: consists of binuclear ionic liquid shown as a general formula A,
Figure FDA0002218473570000011
wherein R is hydrogen or unsubstituted C1～10Alkyl, or straight-chain C substituted by substituent1～10The substituent is amino, carboxyl or sulfonic group;
x is a heteropolyacid radical.
2. The heteropolyacid-type ionic liquid catalyst according to claim 1, characterized in that: r is a straight chain C substituted by a substituent1～3Alkane in which the substituent is hydroxyl,Or a carboxyl group, or a sulfonic acid group.
3. The heteropolyacid-type ionic liquid catalyst according to claim 2, characterized in that: r is a straight chain C substituted by sulfonic acid group1～3An alkane.
4. The heteropolyacid-type ionic liquid catalyst according to claim 1, characterized in that: x is PW12O40 3-、SiW12O40 3-、PMo12O40 3-One kind of (1).
5. A preparation method of a heteropoly acid type ionic liquid catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
step a: synthesis of intermediate [ C4(Mim)2]Imidazole, sodium hydroxide and dimethyl sulfoxide are used as raw materials, stirring and reacting are carried out for 0.5-2h at the temperature of 40-70 ℃, 1, 4-dibromobutane is dropwise added, the reaction is continued for 2h, and recrystallization, filtration and drying are carried out after the reaction is finished to obtain a white solid [ C ]4(Mim)2]；
Step b: synthesis of intermediate [ C4(Rim)2]Dissolving the white solid obtained in the step a in distilled water, adding a toluene solution containing 1, 3-propyl sultone, heating the mixture solution to 40-65 ℃, stirring for reaction for 12-36h, cooling, washing, and removing water by rotary evaporation to obtain a viscous liquid [ C4(Rim)2]；
Step c: synthesizing an ionic liquid catalyst, reacting the binuclear ionic liquid obtained in the step b with a heteropoly acid aqueous solution, stirring and reacting for 1-4h at 15-30 ℃, filtering and drying to obtain a heteropoly acid type ionic liquid catalyst [ C4(Rim)2][X]。
6. The method for preparing a heteropolyacid-type ionic liquid catalyst according to claim 5, characterized in that: the heteropoly acid is one of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
7. The method for preparing a heteropolyacid-type ionic liquid catalyst according to claim 5, characterized in that: in the step a, the reaction temperature is 60 ℃, and the stirring time is 1 h; in the step b, the heating temperature is 50 ℃, and the stirring time is 24 hours; in the step c, the reaction temperature is 25 ℃, and the reaction time is 1 h.
8. The application of the heteropoly acid type ionic liquid catalyst is characterized in that: the heteropoly acid type ionic liquid catalyst is used for preparing adipic acid by catalytic oxidation of cyclohexene.
9. Use of a heteropolyacid-type ionic liquid catalyst according to claim 8, characterized in that: dissolving a heteropoly acid type catalyst in hydrogen peroxide at room temperature, adding the solution into a container filled with cyclohexene, heating to 50-80 ℃, reacting for 0.5-2.5h, continuously heating to 83 ℃, reacting for 6-13h, cooling after the reaction is finished, freezing for 5h at 0 ℃, filtering, washing and drying to obtain the adipic acid.
10. The use of a heteropolyacid-type ionic liquid catalyst according to claim 9 for the catalytic oxidation of cyclohexene to adipic acid, wherein: the molar ratio of the heteropolyacid type ionic liquid catalyst to cyclohexene is 1: 60-1: 10, the molar ratio of hydrogen peroxide to cyclohexene is 4-6.5: 1, and the pH value of a reaction solution after the addition of the heteropolyacid type ionic liquid catalyst is 1.0-2.5.
CN201910924076.6A 2019-09-27 2019-09-27 Heteropolyacid type ionic liquid catalyst and preparation method and application thereof Pending CN110694682A (en)

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