CN112808305A - Catalytic system for catalyzing olefin isomerization reaction and application thereof - Google Patents
Catalytic system for catalyzing olefin isomerization reaction and application thereof Download PDFInfo
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- CN112808305A CN112808305A CN202110036534.XA CN202110036534A CN112808305A CN 112808305 A CN112808305 A CN 112808305A CN 202110036534 A CN202110036534 A CN 202110036534A CN 112808305 A CN112808305 A CN 112808305A
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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
- B01J31/0279—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 cationic portion being acyclic or nitrogen being a substituent on a ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2562—Catalytic processes with hydrides or organic compounds
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Abstract
The invention relates to a catalytic system for catalyzing olefin isomerization reaction, which comprises choline chloride ionic liquid and protonic acid. The invention also relates to a method for applying the catalytic system for catalyzing the olefin isomerization reaction. In the catalytic system, the choline chloride ionic liquid can react with protonic acid to form hydrogen bond, so that the catalytic system with high selectivity is generated. Therefore, the catalyst system of the invention can simply, conveniently and efficiently promote the isomerization reaction of the olefin to generate the isoolefin. Meanwhile, when the catalytic system is used for catalyzing the olefin isomerization reaction, the reaction system is two-phase, after the reaction is finished, the mixture is layered and separated, the isoolefin can be obtained, the catalytic system can be recovered and reused, the post-treatment is simple and economic, and the industrialization is easy to realize.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a catalytic system for catalyzing olefin isomerization reaction and application thereof.
Background
Olefin is a common organic compound skeleton structure and is widely applied to various fields of petrochemical industry, fine chemical industry, biological medicine and the like. Due to their wide range of applications, the great demand for olefin compounds has prompted many scientists to investigate various methods for synthesizing olefins, such as elimination, reduction, coupling, condensation, addition, and isomerization reactions, etc. Among them, the isomerization of olefins is a method for constructing a novel olefin compound by C ═ C position migration or cis-trans isomerization, and is very attractive due to its atom economy.
Potassium tert-butoxide is often used as a catalyst for catalyzing the isomerization of olefins, but its application is greatly limited because it is strongly basic. Many studies have shown that transition metal complexes have a very good catalytic effect on the isomerization of olefins, such as metal complex materials of nickel and ruthenium (Chemical Reviews,2015,115(11), 5462-.
The acid-catalyzed olefin isomerization reaction means that under the participation of an acidic catalyst, a carbon-carbon double bond of the olefin interacts with a dissociated proton of the catalyst to generate an active carbocation intermediate (carbonium ions), and the ortho-position proton is induced to be dissociated to generate a new productEctopic carbon-carbon double bonds, resulting in thermodynamically more stable mixed olefins with a certain cis-trans (Z/E) ratio. For example, Asinger et al homogeneously catalyze the isomerization of alpha-undecene to mixed internal olefins using a medium and strong acid such as sulfuric acid, perchloric acid, and the like. Wherein, when perchloric acid/anhydride is used as a catalyst, the isomerization reaction can be promoted to be carried out efficiently at 100 ℃, the polymerization reaction of olefin is less, but the acid catalyst is difficult to recycle and has the problem of equipment corrosion; and with BF3、HBF4Or AlCl3As a catalyst, a large amount of olefin polymerization takes place in a relatively short reaction time (Chemische Berichte,1963,96(3), 716-735).
Patent CN110201713A discloses a catalyst for olefin isomerization reaction, which contains ionic liquid and metal loaded thereon, and is prepared by four steps of reactions such as substitution, alkylation, acidification and metal loading of pentaerythrityl tetrabromo and butyl lithium, and the preparation process is complicated, the post-treatment is complex, and the catalyst is not beneficial to industrialization.
Disclosure of Invention
Therefore, it is necessary to provide a catalytic system for catalyzing olefin isomerization reaction and applications thereof, which can promote olefin isomerization reaction to generate isoolefin simply and efficiently, and is easy for industrialization.
A catalytic system for catalyzing an olefin isomerization reaction, the catalytic system comprising a choline base ionic liquid and a protonic acid.
In one embodiment, the mass ratio of the choline chloride ionic liquid to the protonic acid is 10:1-1000: 1.
In one embodiment, the choline chloride ionic liquid includes at least one of choline chloride-urea ionic liquid, choline chloride-thiourea ionic liquid, choline chloride-acetamide ionic liquid, choline chloride-phenol ionic liquid, choline chloride-ethylene glycol ionic liquid, choline chloride-p-hydroxybenzaldehyde ionic liquid, choline chloride-p-methylphenol ionic liquid, choline chloride-polyethylene glycol ionic liquid, choline chloride-benzoic acid ionic liquid, choline chloride-citric acid ionic liquid, choline chloride-oxalic acid ionic liquid, choline chloride-malonic acid ionic liquid, choline chloride-imidazole ionic liquid, and choline chloride-trifluoroacetic acid ionic liquid.
In one embodiment, the protonic acid comprises at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, and phosphoric acid.
Use of a catalytic system as described above for catalysing an isomerisation reaction of olefins, comprising:
(1) mixing a catalytic system with olefin to enable the olefin to have isomerization reaction to obtain a mixture;
(2) separating the isoolefin from the mixture.
In one embodiment, the olefin comprises at least one of 1-pentene, 1-hexene, 1-octene, 4-methyl-1, 3-pentadiene, 3-methyl-1-butene.
In one embodiment, the olefin is subjected to isomerization reaction at a temperature of 30 ℃ to 200 ℃ and a pressure of 1atm to 10atm for 0.5h to 6 h.
In one embodiment, the mass ratio of the catalytic system to the olefin is from 0.008:1 to 1.5: 1.
In one embodiment, the catalytic system is also recovered when the isoolefin is separated from the mixture.
In one embodiment, the method further comprises recycling the recovered catalyst system to step (1) to be mixed with the olefin.
In the catalytic system of the invention, choline chloride ionic liquid (represented by IL) can react with protonic acid to form hydrogen bond (IL … H)+) And a catalytic system with high selectivity is generated.
Furthermore, when the catalytic system is used for catalyzing olefin isomerization reaction to generate isoolefin, the hydrogen atom nucleus forming the hydrogen bond attacks the electrons of the double bond in the olefin to be added to the double bond to form a carbonium ion, and the carbonium ion and the ionic liquid are subjected to electrostatic attraction and complexing together. The carbocation has a delocalization effect and can resonate to the adjacent carbon atom,making adjacent carbon atoms into carbenium ions. Because of the abundant electrons on the ionic liquid, the hydrogen nucleus on the terminal alpha-C of the carbocation can be attracted by the ionic liquid, the electron cloud on the C-H bond is attracted by the carbocation, and finally, when the C-H bond is broken, the C-C double bond and IL … H+Bonds are formed simultaneously to form isoolefins.
Therefore, the catalyst system of the invention can simply, conveniently and efficiently promote the isomerization reaction of the olefin to generate the isoolefin. Meanwhile, when the catalytic system is used for catalyzing the olefin isomerization reaction, the product yield is high, the reaction system is two-phase, the mixture is layered after the reaction is finished, the isoolefin can be obtained by separation, the catalytic system can be recycled, the post-treatment is simple and economic, and the industrialization is easy to realize.
Detailed Description
The catalytic system for catalyzing olefin isomerization reaction and the application thereof provided by the present invention will be further described below.
The invention provides a catalytic system for catalyzing olefin isomerization reaction, which comprises choline chloride ionic liquid and protonic acid.
The choline chloride ionic liquid has low freezing point, low viscosity and good solubility. Therefore, in the catalytic system, choline chloride ionic liquid (expressed by IL) can react with protonic acid to form hydrogen bond (IL … H)+) And a catalytic system with high selectivity is generated.
When the catalytic system is used for catalyzing olefin isomerization reaction to generate isoolefin, hydrogen nuclei forming hydrogen bonds can attack electrons of double bonds in the olefin and add the electrons to the double bonds to form a carbonium ion, and the carbonium ion and the ionic liquid are subjected to electrostatic attraction and complexing. The carbocation has a delocalization effect and can resonate to adjacent carbon atoms, so that the adjacent carbon atoms become the carbocation. Because abundant electrons exist on the chlocholine ionic liquid, hydrogen atomic nucleus on terminal alpha-C of the carbocation ion can be attracted by the ionic liquid, electron cloud on C-H bond is attracted by the carbocation, and finally, when the C-H bond is broken, the C-C double bond and IL … H are bonded+Bonds are formed simultaneously to form isoolefins. Reaction thereofThe principle is as follows:
in one or more embodiments, the mass ratio of the choline chloride ionic liquid to the protonic acid in the catalytic system is 10:1-1000:1, preferably 20:1-100:1, so that the acid ratio can be greatly reduced to avoid or slow down the corrosion of the catalytic system to equipment.
In addition, the choline chloride ionic liquid has the characteristics of simple preparation, low cost, low toxicity and the like. Therefore, the catalytic system consisting of the choline chloride ionic liquid and the protonic acid has the advantages of environmental protection, no toxicity, low cost and the like.
In one or more embodiments, the choline chloride-based ionic liquid includes at least one of choline chloride-urea ionic liquid, choline chloride-thiourea ionic liquid, choline chloride-acetamide ionic liquid, choline chloride-phenol ionic liquid, choline chloride-ethylene glycol ionic liquid, choline chloride-p-hydroxybenzaldehyde ionic liquid, choline chloride-p-methylphenol ionic liquid, choline chloride-polyethylene glycol ionic liquid, choline chloride-benzoic acid ionic liquid, choline chloride-citric acid ionic liquid, choline chloride-oxalic acid ionic liquid, choline chloride-malonic acid ionic liquid, choline chloride-imidazole ionic liquid, choline chloride-trifluoroacetic acid ionic liquid, preferably choline chloride-ethylene glycol ionic liquid, choline chloride-p-hydroxybenzaldehyde ionic liquid, choline chloride-p-methylphenol ionic liquid, choline chloride-, At least one of choline chloride-polyethylene glycol ionic liquid.
In one or more embodiments, the protic acid comprises at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, and preferably at least one of sulfuric acid, hydrobromic acid, and hydrochloric acid.
The present invention also provides the use of a catalytic system as described above for catalysing an isomerisation reaction of olefins, comprising:
(1) mixing a catalytic system with olefin to enable the olefin to have isomerization reaction to obtain a mixture;
(2) separating the isoolefin from the mixture.
In the step (1), the olefin comprises at least one of 1-pentene, 1-hexene, 1-octene, 4-methyl-1, 3-pentadiene and 3-methyl-1-butene, and correspondingly, the isoolefin comprises at least one of 2-pentene, 2-hexene, 2-octene, 2-methyl-1, 3-pentadiene and 2-methyl-2-butene, wherein the 2-methyl-1, 3-pentadiene can be used for reacting with acrolein to generate ligustral.
In one or more embodiments, when the catalytic system is mixed with the olefin, the mass ratio of the catalytic system to the olefin is 0.008:1 to 1.5:1, preferably 0.01:1 to 0.3:1, the temperature for isomerization reaction of the olefin is 30 ℃ to 200 ℃, preferably 90 ℃ to 110 ℃, the pressure is 1atm to 10atm, preferably 2atm to 3atm, and the time for isomerization reaction is 0.5h to 6h, preferably 2h to 3h, which can be selected according to the catalytic system and the components of the olefin.
When the catalytic system is used for catalyzing olefin isomerization reaction, the reaction system is two phases, a mixture is obtained after stirring reaction is completed, standing and layering are carried out, the upper layer is an isoolefin product layer, the lower layer is a catalytic system layer, and the isoolefin product can be obtained after liquid separation, water washing and distillation are carried out in the step (2).
In the separated isoolefin product, olefins which are not isomerized may exist, and the isoolefin can be obtained by further separation and purification.
When the isoolefin is obtained by separation, the catalytic system can be recovered. The recovered catalyst system can be recycled to step (1) and mixed with the olefin for catalyzing the olefin to perform isomerization reaction.
Therefore, the catalyst system of the invention can simply, conveniently and efficiently promote the isomerization reaction of the olefin to generate the isoolefin. Meanwhile, the product is simple in post-treatment, the catalytic system can be recycled and applied mechanically, the cost is low, and industrialization is easy to realize.
Hereinafter, the catalytic system for catalyzing olefin isomerization and the application thereof will be further described by the following specific examples.
Example 1
60g of choline chloride and 60g of ethylene glycol are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 0.12g of sulfuric acid was added to the flask and stirred uniformly to obtain the catalyst system.
15g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, adding 500g of 1-pentene into the autoclave, stirring and heating to 90 ℃, keeping the temperature for 1h under the pressure of 8atm, and carrying out isomerization reaction to obtain a mixture. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 460g of a mixed product of 1-pentene and 2-pentene is obtained (the GC contents of the 1-pentene and the 2-pentene are respectively 5% and 95%), wherein the yield of the product 2-pentene is 91.61%.
Example 2
60g of choline chloride and 100g of polyethylene glycol are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and is kept warm for 1h to completely dissolve the solid. After complete dissolution, 16.0g of hydrochloric acid was added to the flask and stirred uniformly to obtain the catalyst system.
4.0g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, 500g of 1-hexene is added into the autoclave, the mixture is stirred, heated to 150 ℃, the pressure is 5atm, the temperature is kept for 0.5h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, 480g of a mixed product of 1-hexene and 2-hexene is obtained after liquid separation, water washing and distillation are carried out on an upper product layer, wherein the GC content of the 1-hexene and the GC content of the 2-hexene are respectively 5% and 95%, and the yield of the 2-hexene is 95.80%.
Example 3
60g of choline chloride and 120g of phenol are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 5.2g hydrobromic acid was added to the flask and stirred well to obtain the catalyst system.
20g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, adding 500g of 1-octene into the autoclave, stirring and heating to 190 ℃, keeping the temperature at 10atm for 3h, and carrying out isomerization reaction to obtain a mixture. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and 486g of a mixed product of 1-octene and 2-octene (the GC content of 1-octene and 2-octene is 5% and 95% respectively) is obtained after liquid separation, water washing and distillation are carried out on the upper product layer, wherein the yield of 2-octene is 97.06%.
Example 4
100g of choline chloride and 300g of polyethylene glycol are sequentially added into a 500mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and is kept warm for 1h to completely dissolve the solid. After complete dissolution, 7.5g of hydrochloric acid was added to the flask and stirred uniformly to obtain the catalyst system.
25g of the prepared catalyst system was taken and added to a 1000mL titanium autoclave. After the temperature is constant, 500g of 4-methyl-1, 3-pentadiene is added into the autoclave, stirred and heated to 90 ℃, the pressure is 2atm, the temperature is kept for 3h, and a mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 492g (the GC contents of 4-methyl-1, 3-pentadiene and 2-methyl-1, 3-pentadiene are respectively 4% and 96%) of a mixed product of 4-methyl-1, 3-pentadiene and 2-methyl-1, 3-pentadiene is obtained, wherein the yield of the product 2-methyl-1, 3-pentadiene is 98.33%.
Test for recycling and applying catalyst system
After the mixture is subjected to liquid separation, the obtained lower layer is a catalytic system, the catalytic system obtained by liquid separation is directly added into a 1000mL titanium material autoclave for catalyzing the isomerization reaction of 4-methyl-1, 3-pentadiene, and the mixture is circularly used for 5 times, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, after the catalyst system is recycled for 5 times, the yield of the 2-methyl-1, 3-pentadiene is not obviously reduced, and the catalytic activity of the catalyst is stable.
Example 5
60g of choline chloride and 140g of p-hydroxybenzaldehyde are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 7.5g of hydrochloric acid was added to the flask and stirred uniformly to obtain the catalyst system.
50g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, adding 500g of 3-methyl-1-butene into the autoclave, stirring and heating to 70 ℃, keeping the temperature at 4atm for 5h, and carrying out isomerization reaction to obtain a mixture. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 487g of a mixed product of 3-methyl-1-butene and 2-methyl-2-butene is obtained (the GC contents of the 3-methyl-1-butene and the 2-methyl-2-butene are respectively 5% and 95%), wherein the yield of the product 2-methyl-2-butene is 97.27%.
Example 6
60g of choline chloride and 200g of malonic acid are sequentially added into a 500mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 0.4g hydriodic acid was added to the flask and stirred well to obtain the catalytic system.
100g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, 500g of 1-octene is added into the autoclave, the mixture is stirred and heated to 110 ℃, the pressure is 4atm, the temperature is kept for 1h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and the upper product layer is subjected to liquid separation, water washing and distillation to obtain 472g of a mixed product of 1-octene and 2-octene (the GC contents of 1-octene and 2-octene are 5% and 95%, respectively), wherein the yield of 2-octene is 94.12%.
Example 7
60g of choline chloride and 200g of p-methylphenol are sequentially added into a 500mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 0.4g hydriodic acid was added to the flask and stirred well to obtain the catalytic system.
250g of the prepared catalytic system is taken and added into a 1000mL titanium material autoclave. After the temperature is constant, 167g of 1-octene is added into the autoclave, the mixture is stirred and heated to 30 ℃, the pressure is 1atm, the temperature is kept for 6h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and 155g of a mixed product of 1-octene and 2-octene (the GC content of 1-octene and 2-octene is 5% and 95% respectively) is obtained after liquid separation, water washing and distillation are carried out on the upper product layer, wherein the yield of 2-octene is 92.46%.
Example 8
60g of choline chloride and 600g of benzoic acid are sequentially added into a 1000mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and is kept warm for 1h to completely dissolve the solid. After complete dissolution, 0.66g of nitric acid was added to the flask and stirred uniformly to obtain the catalytic system.
100g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, adding 500g of 3-methyl-1-butene into the autoclave, stirring and heating to 30 ℃, keeping the temperature at 2atm for 2h, and carrying out isomerization reaction to obtain a mixture. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 485g (the GC content of 3-methyl-1-butene and the GC content of 2-methyl-2-butene are respectively 5% and 95%) of a mixed product of 3-methyl-1-butene and 2-methyl-2-butene is obtained, wherein the yield of the product 2-methyl-2-butene is 96.85%.
Example 9
60g of choline chloride and 100g of imidazole are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 16g of phosphoric acid was added to the flask and stirred uniformly to obtain the catalytic system.
150g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, 500g of 1-hexene is added into the autoclave, the mixture is stirred, heated to 100 ℃ and the pressure is 5atm, the temperature is kept for 3h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and 482g (the GC content of 1-hexene and 2-hexene is respectively 5 percent and 95 percent) of a mixed product of 1-hexene and 2-hexene is obtained after liquid separation, water washing and distillation are carried out on the upper product layer, wherein the yield of the product 1-hexene is 96.22 percent.
Example 10
60g of choline chloride and 100g of trifluoroacetic acid are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept warm for 1h to completely dissolve the solid. After complete dissolution, 16g of phosphoric acid was added to the flask and stirred uniformly to obtain the catalytic system.
50g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, 500g of 1-hexene is added into the autoclave, the mixture is stirred, heated to 100 ℃ and the pressure is 5atm, the temperature is kept for 3h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and 490g (the GC content of 1-hexene and 2-hexene is 5 percent and 95 percent respectively) of a mixed product of 1-hexene and 2-hexene is obtained after liquid separation, water washing and distillation are carried out on an upper product layer, wherein the yield of the product 1-hexene is 97.90 percent.
Example 11
60g of choline chloride and 100g of oxalic acid are sequentially added into a 250mL three-neck round-bottom flask, and the mixture is heated to 100 ℃ and kept for 1h to completely dissolve the solid. After complete dissolution, 7.5g of hydrochloric acid was added to the flask and stirred uniformly to obtain the catalyst system.
10g of the prepared catalyst system was placed in a 1000mL titanium autoclave. After the temperature is constant, 500g of 1-hexene is added into the autoclave, the mixture is stirred, heated to 90 ℃, the pressure is 3atm, the temperature is kept for 4h, and the mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 488g (the GC content of 1-hexene and 2-hexene is 5% and 95% respectively) of a mixed product of 1-hexene and 2-hexene is obtained, wherein the yield of the product 1-hexene is 97.48%.
Comparative example 1:
and (3) sequentially adding 100g of choline chloride and 300g of polyethylene glycol into a 500mL three-neck round-bottom flask, heating to 100 ℃, and keeping the temperature for 1h to completely dissolve the solid to obtain the choline chloride-polyethylene glycol ionic liquid.
25g of the prepared choline chloride-polyethylene glycol ionic liquid is added into a 1000mL titanium material autoclave. After the temperature is constant, 500g of 4-methyl-1, 3-pentadiene is added into the autoclave, stirred and heated to 90 ℃, the pressure is 2atm, the temperature is kept for 3h, and a mixture is obtained through isomerization reaction. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, the upper product layer is subjected to liquid separation, water washing and distillation, and 495g of a mixed product of 4-methyl-1, 3-pentadiene and 2-methyl-1, 3-pentadiene is obtained, (the GC contents of the 4-methyl-1, 3-pentadiene and the 2-methyl-1, 3-pentadiene are respectively 98.93% and 1.07%), wherein the yield of the product 2-methyl-1, 3-pentadiene is 51.44%.
Comparative example 2
Into a 1000mL three-necked round-bottomed flask, 500g of 4-methyl-1, 3-pentadiene and 9.5g of hydrobromic acid were sequentially added, and after stirring them uniformly, they were placed in a 1000mL titanium autoclave. Stirring and heating to 90 deg.C, keeping the pressure at 1atm for 3h, and carrying out isomerization reaction to obtain the final product. Then, the temperature is reduced to room temperature, the mixture is discharged into a 1000mL separating funnel, standing and layering are carried out, liquid separation is carried out, and 298g (the GC contents of 4-methyl-1, 3-pentadiene and 2-methyl-1, 3-pentadiene are respectively 50% and 50%) of a mixed product of 4-methyl-1, 3-pentadiene and 2-methyl-1, 3-pentadiene is obtained after liquid separation, water washing and distillation are carried out on the upper product layer, wherein the yield of the product 2-methyl-1, 3-pentadiene is 42.45%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A catalytic system for catalyzing an olefin isomerization reaction, wherein the catalytic system comprises a choline chloride ionic liquid and a protonic acid.
2. The catalytic system for catalyzing isomerization of olefins according to claim 1, wherein the mass ratio of the choline chloride ionic liquid to the protonic acid is 10:1-1000: 1.
3. The catalytic system for catalyzing an olefin isomerization reaction of claim 1, the choline chloride ionic liquid comprises at least one of choline chloride-urea ionic liquid, choline chloride-thiourea ionic liquid, choline chloride-acetamide ionic liquid, choline chloride-phenol ionic liquid, choline chloride-ethylene glycol ionic liquid, choline chloride-p-hydroxybenzaldehyde ionic liquid, choline chloride-p-methylphenol ionic liquid, choline chloride-polyethylene glycol ionic liquid, choline chloride-benzoic acid ionic liquid, choline chloride-citric acid ionic liquid, choline chloride-oxalic acid ionic liquid, choline chloride-malonic acid ionic liquid, choline chloride-imidazole ionic liquid and choline chloride-trifluoroacetic acid ionic liquid.
4. The catalytic system of claim 1, wherein the protic acid comprises at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, and phosphoric acid.
5. Use of a catalytic system according to any one of claims 1 to 4 for catalysing an isomerisation reaction of olefins, comprising:
(1) mixing a catalytic system with olefin to enable the olefin to have isomerization reaction to obtain a mixture;
(2) separating the isoolefin from the mixture.
6. Use of a catalytic system for catalysing the isomerisation of olefins according to claim 5, characterised in that the olefins comprise at least one of 1-pentene, 1-hexene, 1-octene, 4-methyl-1, 3-pentadiene, 3-methyl-1-butene.
7. Use of a catalytic system for the catalytic isomerization of olefins according to claim 5, wherein the temperature of the isomerization of olefins is from 30 ℃ to 200 ℃ and the pressure is from 1atm to 10atm, and the time of the isomerization is from 0.5h to 6 h.
8. Use of a catalytic system for the catalytic isomerization of olefins according to claim 5, wherein the mass ratio of the catalytic system to the olefins is between 0.008:1 and 1.5: 1.
9. Use of a catalytic system for catalysing the isomerisation of olefins according to claim 5, wherein said isoolefin is separated from said mixture and recovered.
10. Use of a catalytic system for the catalytic isomerization of olefins according to claim 9, further comprising recycling the catalytic system recovered to step (1) for mixing with the olefins.
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| CN114539023A (en) * | 2022-02-15 | 2022-05-27 | 江苏瑞恒新材料科技有限公司 | Industrial production method for mutual conversion of cis-trans isomers |
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