CN112745252B - H catalysis with ionic liquid as catalyst2Method for synthesizing high-added-value mercaptoacid by addition reaction of S and olefine acid - Google Patents
H catalysis with ionic liquid as catalyst2Method for synthesizing high-added-value mercaptoacid by addition reaction of S and olefine acid Download PDFInfo
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Abstract
Use of amido functionalized hydrophobic ionic liquid as catalyst for alpha, beta-unsaturated carboxylic acid and H2A method for producing beta-mercapto carboxylic acid by S addition integrates catalysis, reaction and separation. Activation of H by the basic site of a tertiary amine contained in an ionic liquid2S is subjected to an addition reaction with the double bond of an alpha, beta-unsaturated carboxylic acid to realize H2And (4) recycling the S. The product obtained after the reaction can be separated from the catalyst by a water phase liquid-liquid extraction method, and the ionic liquid can be recycled. In the system, the ionic liquid is used as a catalytic medium and a reaction medium, and no other organic solvent is involved, so that H is generated2S is efficiently utilized, and meanwhile, products with high added value, such as mercaptoacid, are obtained.
Description
Technical Field
Relates to a method for using amido functionalized hydrophobic ionic liquid as a catalyst for alpha, beta-unsaturated carboxylic acid and H2The invention discloses a method for integrating catalysis, reaction and separation for generating beta-mercaptocarboxylic acid by S addition, belonging to the field of green chemical industry.
Background
Hydrogen sulfide (H)2S) is a flammable, explosive gas with high toxicity and corrosiveness. It is widely used in various chemical fields such as natural gas, flue gas, refinery gas and the like. The existence of the catalyst can cause the problems of catalyst deactivation, pipeline corrosion, environmental pollution and the like, and the research on how to effectively utilize the hydrogen sulfide has very important practical significance.
The ionic liquid is an organic molten salt which consists of organic cations and organic or inorganic anions and is in a liquid state at the room temperature. It is considered to be a new type of green media by virtue of its almost no vapor pressure, high thermal stability, structural designability, and excellent dissolving power, etc., which receive wide attention. The organic synthesis reaction carried out in the ionic liquid can effectively reduce the pollution of the traditional volatile organic solvent to the environment and the damage to operators, and the ionic liquid provides a novel reaction environment, can improve the speed, the selectivity and the like of the reaction, and has good application prospect in the field of catalysis.
Wubicantin et al reported H mediated by ionic liquids or eutectic solvents2New S resource method (CN 108840311A). In view of the ionic liquid pair H2S and SO2All have the characteristic of excellent affinity, the liquid-phase Claus process is explored, and the ion liquid is used as a medium to realize the high-efficiency capture and conversion of H2And (S) a new idea. However, the molar ratio of catalyst to substrate is comparable or even excessive for such processes and the catalytic activity of the medium is to be investigated further. International patent publication WO 2009/038232A 2 proposes the use of an alpha, beta-unsaturated carboxylic acid and H2A method for producing beta-mercapto carboxylic acid by S addition. However, the method uses solid strong base as a catalyst, and the method has the problems that reaction products exist in a sodium salt form, a large amount of acid and base are needed for neutralization reaction, the process is long, the catalyst cannot be recycled, organic solvents such as ethanol, tetrahydrofuran or N-methylpyrrolidone are needed as reaction media in the reaction process, the green color property of the reaction process is poor, and the method does not conform to the concept of green chemistry and chemical engineering.
The invention develops an amido functionalized hydrophobic ionic liquid with simple structure, and activates H through tertiary amine groups in the ionic liquid2S is subjected to an addition reaction with the double bond of an alpha, beta-unsaturated carboxylic acid to realize H2And (5) converting and utilizing downstream high value-added products. The product obtained after the reaction can be separated by a method of liquid-liquid extraction with water, and the ionic liquid can be recycled. In the system, the ionic liquid is used as a catalytic medium and a reaction medium, and no other organic solvent is involved, so that H is generated2S is efficiently utilized, and meanwhile, products with high added values, such as mercaptoacid, are obtained, the development concept of green chemical industry is met, and a new idea is provided for preparing fine chemicals with high added values, such as mercaptoacid.
Disclosure of Invention
The invention aims to provide a method for preparing H by taking ionic liquid as a catalytic system2S, a method for preparing a high value-added product. The ionic liquid used in the method consists ofA series of amino functionalized cations and bis (trifluoromethyl) sulfimide, bis (fluorosulfonyl) imide, hexafluorophosphoric acid, bis (p-toluenesulfonyl) amine and the like are used as anions to form the cationic ion-exchange resin, and the cationic ion-exchange resin has the advantages of hydrophobic property, simple structure and simple and convenient synthesis. By catalytic action of ionic liquid, so that H2S is activated and reacts with the double bond of the alpha, beta-unsaturated carboxylic acid to form H2And (5) recycling S. The mercaptan acid product obtained after the reaction can be separated by a water phase liquid-liquid extraction method, and the ionic liquid can be recycled. The method can obtain crude product of mercaptan acid by aqueous phase liquid-liquid extraction, and the crude product can obtain the mercaptan acid product with high added value after unit operations such as column chromatography, distillation, drying and purification and the like, and has high economic benefit.
The specific technical scheme of the invention is as follows:
one type is an anion having a hydrophobic function, the anion having the following structure:
the above ionic liquid has a cation structure formula shown in general formulas (A), (B) and (C), and is characterized in that one end of the ionic liquid contains a tertiary amine group, and the other end of the ionic liquid is composed of quaternary amine or pyridine or imidazole cation.
Wherein the central atom in the group X may be C, N, O such as: [ -CH2-]，[-O-]，[-N-(CH3)-]Etc.; subscripts p and q represent the number of carbon atoms, and the sum of p + q is equal to or more than 1 and equal to or less than 6; r1May be an alkyl group having a carbon number (n) of not more than 6; r2，R3Can be hydrogen or alkyl (n is more than or equal to 0 and less than or equal to 6); r4Can be straight-chain alkyl (n is more than or equal to 1 and less than or equal to 10); r5Can be methoxy or alkyl (0 ≦ n ≦ 6)
By way of example, and not limitation, with respect to formula (A), the following structures are included:
morpholine and triazine compounds can also be derived as cations:
taking formula (B) as an example, the following structures are included, but not limited to:
(3) by way of example, and not limitation, formula (C) includes the following structures:
for the ionic liquid, the applicability of the substrate is expanded, and the substrate comprises the following substrates:
1) acrylic acid:
2) and crotonic acid:
3) α -methacrylic acid:
4) maleic acid:
5) cinnamic acid:
6) 3-butenoic acid:
7) 2-methyl-3-butenoic acid:
8) 4-Enopentanoic acid:
9) α -methyl cinnamic acid:
application of ionic liquid in catalytic activation of H2S and carrying out addition reaction with double bond of alpha, beta-unsaturated carboxylic acid to realize H2And (4) converting and utilizing S. The mercaptan acid product obtained after the reaction can be separated by a water phase liquid-liquid extraction method, and the ionic liquid can be recycled. The method can obtain crude product of mercaptan acid by using water for liquid phase extraction, and the crude product can obtain the mercaptan acid product with high added value after unit operations such as column chromatography, distillation, drying and purification and the like. The amido functionalized hydrophobic ionic liquid is used as a catalyst for alpha, beta-unsaturated carboxylic acid and H2The integrated catalysis, reaction and separation method for producing beta-mercapto carboxylic acid by S addition takes alpha-methacrylic acid as an example, and the reaction formula is as follows:
the method comprises the following steps:
step 1, adding a certain amount of alpha-methacrylic acid into a reactor, adding amino functionalized hydrophobic ionic liquid (IL-Cat.) with the molar weight equivalent to that of the alpha-methacrylic acid, and reacting at room temperature to 120 ℃ under the condition of H2The S partial pressure is 0-400 kPa, and after the reaction is finished, a mixture of the target mercapto acid and the ionic liquid catalyst is obtained;
step 3, collecting the water phase obtained in the step 2 and evaporating to dryness to obtain a crude product of the mercapto acid;
step 4, for further purification, a chromatography method can be adopted for developing the crude mercaptoacid product obtained in the step 3 by using a mixed solvent of ethyl acetate and petroleum ether as a developing solvent, and the collected mercaptoacid product is subjected to GC analysis, so that the purity can reach 97%;
Detailed Description
The invention is further illustrated by the following examples.
Example 1: with bis (2-dimethylaminoethyl) ether&Bis (trifluoromethyl) sulfonimide ([ BDMAEEH)][Tf2N]) The ionic liquid is used as a catalyst, the substrate is acrylic acid, and the 3-mercaptopropionic acid is prepared.
The following reactions were carried out in a reaction kettle: acrylic acid (8.0mmol, 0.5765g) was weighed and bis (2-dimethylaminoethyl) ether was added&Bis (trifluoromethyl) sulfonimide ([ BDMAEEH)][Tf2N]) Ionic liquid (0.80mmol, 0.2819g) was reacted for 12h at 70 ℃ in a glycol bath. After the reaction was complete, the reaction mixture was cooled to room temperature and 5mL of the solution was added to the reaction mixture for deionizationAnd (3) carrying out liquid-liquid extraction on the son water, standing for 20min, collecting supernatant, and repeating for three times to ensure that the product 3-mercaptopropionic acid does not remain in the lower phase, namely the ionic liquid phase. Respectively drying the upper product phase and the lower ionic liquid phase, and carrying out GC analysis on the upper phase, wherein the conversion rate is 97 percent, and the selectivity is 99 percent; the lower phase is fresh ionic liquid and can be put into H again2S catalytic activation stage for recycling. The crude 3-mercaptopropionic acid is further purified and subjected to a silica gel column chromatography using a system of ethyl acetate and petroleum ether for development and collection of the product, which can be recovered by distillation for the next use. The yield of the purified 3-mercaptopropionic acid product is 95%, the product purity is 97% by GC analysis, and the product is determined to be the target product by nuclear magnetic characterization.
Example 2: with bis (2-dimethylaminoethyl) ether&Bis (trifluoromethyl) sulfonimide ([ BDMAEEH)][Tf2N]) The ionic liquid is used as a catalyst, the substrate is alpha-methacrylic acid, and 3-mercaptoisobutyric acid is prepared.
The following reactions were carried out in a reaction kettle: crocenoic acid (10.0mmol, 0.8613g) was weighed and bis (2-dimethylaminoethyl) ether was added&Bis (trifluoromethyl) sulfonimide ([ BDMAEEH)][Tf2N]) Ionic liquid (1.0mmol, 0.4409g) was reacted for 12h at 90 ℃ in a glycol bath. After the reaction is finished, cooling to room temperature, adding 5mL of deionized water to perform aqueous phase liquid-liquid extraction, standing for 20min, collecting supernatant, and repeating for three times to ensure that the product 3-mercaptobutyric acid is not remained in the lower phase, i.e. the ionic liquid phase. Respectively drying the upper product phase and the lower ionic liquid phase, and carrying out GC analysis on the upper phase, wherein the conversion rate is 97 percent, and the selectivity is 99 percent; the lower phase is fresh ionic liquid and can be put into H again2S catalytic activation stage for recycling. The crude 3-mercaptopropionic acid was further purified, subjected to silica gel chromatography column, developed using ethyl acetate and petroleum ether system and the product collected, which could be recovered by distillation for the next use. The yield of the purified 3-mercaptobutyric acid product is 95%, the product purity is 97% by GC analysis, and the target product is determined by nuclear magnetic characterization.
Example 3: the 3-mercaptopropionic acid is prepared by using bis (2-dimethylaminoethyl) ether and bis (p-toluenesulfonyl) amine ionic liquid as a catalyst and taking acrylic acid as a substrate. .
The following reactions were carried out in a reaction kettle: acrylic acid (15.0mmol, 1.0815g) was weighed and bis (2-dimethylaminoethyl) ether was added&Bis (p-toluenesulfonyl) amine ionic liquid (1.5mmol, 0.7311g) was reacted for 12h at 90 ℃ in a glycol bath. After the reaction is finished, cooling to room temperature, adding 5mL of deionized water to perform aqueous phase liquid-liquid extraction, standing for 20min, collecting supernatant, and repeating for three times to ensure that the product 3-mercaptobutyric acid is not remained in the lower phase, namely the ionic liquid phase. Respectively drying the upper product phase and the lower ionic liquid phase, and carrying out GC analysis on the upper phase, wherein the conversion rate is 97 percent, and the selectivity is 99 percent; the lower phase is fresh ionic liquid and can be put into H again2S catalytic activation stage for recycling. The crude 3-mercaptopropionic acid was further purified, subjected to silica gel chromatography column, developed using ethyl acetate and petroleum ether system and the product collected, which could be recovered by distillation for the next use. The yield of the purified 3-mercaptobutyric acid product is 95%, the product purity is 97% by GC analysis, and the target product is determined by nuclear magnetic characterization.
Example 4: 3-mercaptoisobutyric acid was prepared using bis (2-dimethylaminoethyl) ether & bis (p-toluenesulfonyl) amine ionic liquid as a catalyst and α -methacrylic acid as a substrate.
The following reactions were carried out in a reaction kettle: alpha-methacrylic acid (10.0mmol, 0.8613g) was weighed and bis (2-dimethylaminoethyl) ether was added&Bis (p-toluenesulfonyl) amine ionic liquid (1.0mmol, 0.4859g) was reacted for 12h at 90 ℃ in a glycol bath. After the reaction is finished, cooling to room temperature, adding 5mL of deionized water to perform aqueous phase liquid-liquid extraction, standing for 20min, collecting supernatant, and repeating for three times to ensure that the product 3-mercaptobutyric acid is not remained in the lower phase, i.e. the ionic liquid phase. Respectively drying the upper product phase and the lower ionic liquid phase, and carrying out GC analysis on the upper phase, wherein the conversion rate is 97 percent, and the selectivity is 99 percent; the lower phase is fresh ionic liquid and can be put into H again2S catalytic activation stage for recycling. The crude 3-mercaptopropionic acid is further purified and subjected to a silica gel column chromatography using a system of ethyl acetate and petroleum ether for development and collection of the product, which can be recovered by distillation for the next use. The yield of the purified 3-mercaptobutyric acid product is 95%, the product purity is 97% by GC analysis, and the target product is determined by nuclear magnetic characterization.
Examples 5 to 16: the procedure is analogous to example 1, using different hydrophobic ionic liquids as catalysts, the results being shown in Table 1.
TABLE 1
| Examples | IL-Cat. | Amount of IL-Cat | Substrate | Conversion rate% | Yield% |
| 5 | [BDMAEEH][Tf2N] | 10mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 6 | [BDMAEEH][FSI] | 10mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 7 | [BDMAEEH][PF6] | 10mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 8 | [TMPDAH][Tf2N] | 10mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 9 | [DMDEEH][Tf2N] | 10mmol％ | Alpha-methacrylic acid | 82 | 74 |
| 10 | [EMIM][Tf2N] | 10mmol％ | Alpha-methacrylic acid | 91 | 88 |
| 11 | [TMHDAH][Tf2N] | 10mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 12 | [PMDETAH][Tf2N] | 5mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 13 | [TDMAPHTH][Tf2N] | 2mmol％ | Alpha-methacrylic acid | 97 | 95 |
| 14 | [BDMAEEH][Tf2N] | 10mmol％ | 3-butenoic acid | 97 | 95 |
| 15 | [BDMAEEH][Tf2N] | 10mmol％ | 2-methyl-3-butenoic acid | 97 | 95 |
| 16 | [BDMAEEH][Tf2N] | 10mmol％ | Maleic acid | 97 | 95 |
Examples 17 to 27: in order to highlight that the amino functionalized hydrophobic ionic liquid has good catalytic activity on the substrate, the method is similar to example 1, the non-hydrophilic substrate is adopted for optimizing the catalytic substrate, different hydrophobic ionic liquids are taken as catalysts, and the result is shown in table 2, so that the ionic liquid has better catalytic activity.
TABLE 2
| Examples | IL-Cat. | Amount of IL-Cat | Substrate | Percent conversion% |
| 17 | [BDMAEEH][Tf2N] | 10mmol％ | Alpha-methyl cinnamic acid | 63 |
| 18 | [BDMAEEH][Tf2N] | 10mmol％ | 4-Envaleric acid | 83 |
| 19 | [BDMAEEH][Tf2N] | 10mmol％ | Cinnamic acid | 58 |
| 20 | [BDMAEEH][PF6] | 10mmol％ | Cinnamic acid | 61 |
| 21 | [BDMAEEH][FSI] | 10mmol％ | Cinnamic acid | 53 |
| 22 | [TMPDAH][Tf2N] | 10mmol％ | Cinnamic acid | 55 |
| 23 | [DMDEEH][Tf2N] | 10mmol％ | Cinnamic acid | 39 |
| 24 | [EMIM][Tf2N] | 10mmol％ | Cinnamic acid | 64 |
| 25 | [TMHDAH][Tf2N] | 10mmol％ | Cinnamic acid | 57 |
| 26 | [PMDETAH][Tf2N] | 5mmol％ | Cinnamic acid | 63 |
| 27 | [TDMAPHTH][Tf2N] | 2mmol％ | Cinnamic acid | 66 |
Example 28: the process is shown in figure 1. The raw material is 2-methyl-3-butenoic acid, and the catalyst is [ BDMAEEH][Tf2N]The catalyst accounts for 10mol percent of the raw materials, and H is blown into the bottom of the reactor2And S. The operating temperature of the reaction unit was 120 ℃ and the operating pressure was 1 MPa. After 6H of reaction, the feed liquid containing the catalyst and the product is pumped into a flash tower, and H dissolved in the system is added2The S gas is distilled out for recycling, and then the residual mixture is led into an extraction tower to be added with water for aqueous phase liquid-liquid extraction. Liquid-liquid extractionThen standing and phase splitting is carried out for 1h, and the ionic liquid in the lower oil phase can be recycled; and the water phase on the upper layer is a target product water solution, and the target product water solution is introduced into a vacuum rectification system unit for vacuum rectification operation, so that water, raw materials and a small amount of ionic liquid obtained by rectification can be recycled except that the target product is used as a high-added-value product with higher purity. And the target product water solution enters a vacuum rectification system to be distilled to obtain 3-mercapto-2-methylpropanoic acid and 2-mercapto-2-methylpropanoic acid. The temperature of the bottom of the vacuum distillation tower is 100 ℃, the temperature of the top of the vacuum distillation tower is 60 ℃, the pressure of the bottom of the vacuum distillation tower is 10kPa, and the pressure of the top of the vacuum distillation tower is 5 kPa.
And (4) analyzing results: the conversion of 2-methyl-3-butenoic acid was 90%, the selectivity for 4-mercapto-2-methylbutyric acid was 60%, and the selectivity for 3-mercapto-2-methylbutyric acid was 40%.
Drawings
FIG. 1 is a schematic process flow diagram for preparing a high value-added product by using an ionic liquid as a catalyst, provided by the invention, wherein: 1 is a reaction unit, 2 is a compressor, 3 is a flash evaporation unit, 4 is an extraction unit, and 5 is a deep rectification unit.
The method comprises the following steps:
firstly, H is put in2S, raw materials and a catalyst are added into a reaction kettle. After the reaction is finished, the mixed solution enters a flash tower together, and H dissolved in the mixed solution is removed2And the S evaporated mixture is pressurized by a gas compressor and then is recycled for the previous reaction, and then the residual mixture is introduced into a rotating disc extraction tower to be added with water for water phase liquid-liquid extraction. After extraction is finished, the ionic liquid in the lower oil phase can be recycled; and the water phase on the upper layer is a target product water solution, and the target product water solution is introduced into a vacuum rectification system unit for vacuum rectification operation, so that water, raw materials and a small amount of ionic liquid obtained by rectification can be recycled except that the target product is used as a high-added-value product with higher purity. The whole process has no emission of waste gas and waste liquid, is green and environment-friendly, and accords with the concept of sustainable development.
Claims (7)
1. For alpha, beta-unsaturated carboxylic acid and H2The method for producing beta-mercapto carboxylic acid by S addition integrates catalysis, reaction and separation, and is characterized in thatThe method comprises the following three steps: (1) adding alpha, beta-unsaturated carboxylic acid substrate and ionic liquid catalyst (IL-Cat.) into a reaction kettle, and blowing excessive H2S, mixing, and fully reacting the system for 2-10 hours under given conditions; (2) the mixture after the reaction is subjected to primary or secondary flash evaporation to remove H dissolved in a liquid phase2S, and recycling the reaction process in the first step; (3) to remove H2Adding a proper amount of water into the mixed solution after S to perform liquid-liquid extraction operation, so that the catalyst can be separated from the product;
the reaction formula in step (1) is as follows:
the ionic liquid catalyst in the step (1) is characterized by being an amino functionalized hydrophobic ionic liquid, wherein anions have hydrophobic characteristics and are bis (trifluoromethyl) sulfimide, bis (fluorosulfonyl) imide, hexafluorophosphoric acid and bis (p-toluenesulfonyl) amine anions; the cation structural formula is shown in general formulas (A), (B) and (C):
wherein the central atom in the group X may be C, N, O; subscripts p and q represent the number of carbon atoms, and the sum of p + q is equal to or more than 1 and equal to or less than 6; r1May be an alkyl group having a carbon number of not more than 6; r2，R3May be hydrogen or alkyl; r4May be straight chain alkyl; r5May be methoxy or alkyl.
2. The method according to claim 1, wherein the amount of the ionic liquid catalyst in the step 1 is 2 to 20% of the molar amount of the substrate.
3. The method of claim 1, wherein the α, β -unsaturated carboxylic acid in step 1 is acrylic acid, crotonic acid, α -methacrylic acid, maleic acid, 3-butenoic acid, 2-methyl-3-butenoic acid.
4. The method according to claim 1, wherein the conditions given in step 1 are: t is more than or equal to 25 ℃ and less than or equal to 120 ℃ and P is more than or equal to 0.1 and less than or equal to 1 Mpa.
5. The method according to claim 1, wherein the mixture after the reaction is subjected to flash degassing in step 2, which can be primary flash evaporation or secondary flash evaporation; if the first-stage flash evaporation is carried out, the flash evaporation temperature is 80-100 ℃, and the flash evaporation pressure is 0.2-0.6 bar; if the flash evaporation is the second-stage flash evaporation, the first-stage flash evaporation is normal-pressure flash evaporation, the flash evaporation temperature is 90-120 ℃, the second-stage flash evaporation is reduced-pressure flash evaporation, the flash evaporation pressure is 0.2-0.4 bar, and the flash evaporation temperature is 80-90 ℃.
6. The process of claim 5 wherein the H-containing product removed from the liquid phase in step 2 is2The S gas can be recycled to be used in the reaction of the first step after being pressurized by a compressor.
7. The method of claim 1, wherein the step 3 of feeding water for liquid-liquid extraction is performed continuously in a rotating disc extraction column, and water is fed from the lower part of the extraction column to remove H2Adding the mixed solution after S from the upper part of the extraction tower, extracting agent water and removing H2The volume flow rate ratio of the mixed solution after S is 0.5-3, the ionic liquid catalyst flows out from the bottom of the extraction tower and can be recycled to the reaction process in the step 1; the water phase flowing out from the top of the extraction tower is the water solution of the target product, the subsequent deep separation is carried out on the water phase, and the extraction process can also be intermittently operated for removing H2Extracting the mixed liquor after S with water of the same volume for three times, wherein the raffinate is an ionic liquid catalyst and can be recycled to the reaction process in the step 1, combining the three extracts for subsequent deep separation operation, and the deep separation is an integrated rectification process: simple atmospheric distillation to remove water, vacuum distillation to remove unreacted substrate material, vacuum distillation to recover product, and high-purity product towerAnd (4) collecting at the top, wherein part of the ionic liquid in the tower bottom can be recycled.
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