CN108993602B - Catalytic system for synthesizing methyl propionate and application method thereof - Google Patents
Catalytic system for synthesizing methyl propionate and application method thereof Download PDFInfo
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Abstract
The invention relates to a catalytic system for synthesizing methyl propionate and an application method thereof. The catalytic system comprises a ruthenium cluster carbonyl complex, imidazole ionic liquid and an inorganic salt promoter, or the ruthenium cluster carbonyl complex and the imidazole ionic liquid; wherein, the molar ratio of the imidazole ionic liquid: 100-250% of ruthenium cluster carbonyl complex: 1; when the catalytic system includes a promoter, the molar ratio of promoter: 1-75% of ruthenium cluster carbonyl complex: 1; the promoter is carbonate, lithium halide salt or transition metal chloride salt. The system utilizes imidazole ionic liquid to consume water generated in the reaction, promotes the reaction to be carried out in the positive direction, and adds inorganic salt promoter to further improve the catalytic activity to catalyze ethylene and CO2And methanol to produce methyl propionate. The invention obviously shortens the reaction time, thereby improving the yield of methyl propionate.
Description
The technical field is as follows:
the invention belongs to the field of organic chemical products synthesized by hydrogen esterification reaction, and particularly relates to a method for synthesizing methyl propionate by ethylene carbonyl.
Background art:
methyl propionate is a colorless and transparent organic liquid, can be used as a spice, a solvent, an extracting agent, an organic intermediate, a plasticizer and the like, and is widely applied to the industries of adhesives, coatings, textiles, rubber, plastics and the like. Methyl propionate can be used for preparing various products such as propionate, propionic acid, propionate (benzyl propionate, isoamyl propionate and the like) and the like through esterification reaction, hydrolysis reaction and ester exchange reaction, so the development of the methyl propionate synthesis process is beneficial to the progress and development of the process technologies such as propionic acid, propionate and the like.
Reppe of Germany proposes a process for directly synthesizing methyl propionate or ethyl propionate by an ethylene hydrogen esterification method, which uses a Ni catalyst, has rigorous reaction conditions and higher requirements on equipment; the patent (CN87110635) relates to that a palladium (II)/aryl substituted phosphine/acid catalytic system has higher activity in catalyzing ethylene/methanol carbonylation reaction, but phosphine ligands in the ligand system are easy to decompose to cause catalyst deactivation; the literature (R.F.heck, J.A.m.chem.Soc.,1963, 85; W.Keim.J.mol.Catal.,1989,54(1)) shows that ruthenium, nickel, cobalt and other complex catalysts are active for the oxo synthesis of methyl propionate from ethylene/CO/methanol. But the reaction conditions are harsh, the conversion rate is low, and the selectivity is poor; in the patent (CN103319337), a composite catalyst system using palladium acetate as a main catalyst and metal ions such as cobalt, nickel or ruthenium as an auxiliary catalyst catalyzes an ethylene/CO/methanol carbonylation reaction, the reaction conditions are mild, the selectivity is high, but the palladium metal is expensive, so the production cost is high; hidai et al (J.mol.Catal.,1987,40(2):243-254) found Ru3(CO)12Under the condition of taking ionic iodide as a promoter, the methyl propionate is synthesized by catalyzing ethylene/CO/methanol, so that the selectivity is high, but in the catalytic systems, CO is used as a raw material, and the catalytic systems are toxic, flammable and difficult to store. Therefore, the search for a carbonyl source to replace CO in olefin carbonylation processes has become a key issue. It is reported that a novel carbonyl source is CO2Methanol, formaldehyde, formic acid, and the like. Among them, a large amount of non-toxic, stable and inexpensive CO existing in nature2Have become the main research direction.
Tominaga et al (Catal. Commun.,2000,1:1-3) use a ruthenium cluster carbonyl complex/LiCl catalytic system to catalyze olefins and CO at 140 deg.C2Carbonylation is carried out, and the yield is 86% after 30 hours of reaction; haukka et al (applied. Catal., A: General,2003,247: 95-100; applied. Catal., A: General,2009,365:130-2Carbonylation is carried out, and the yield is 80% after 17 hours of reaction; LiPeng Wu et al (nat. Commun.,2014,5(2):3091-3096) use a ruthenium cluster carbonyl complex catalyst system to catalyze olefins and CO at 160 deg.C2Carbonylation is carried out, the yield is only 11% after 20h of reaction, and the yield is improved to 64% after LiCl is added; adding ionic liquid [ Bmim ]]After Cl, the yield reached 92%, while using the ruthenium cluster carbonyl complex/[ Bmim ]]Cl catalyst system, ethylene/CO catalysis at 160 DEG C2Methanol, the yield of methyl propionate after 20 hours of reaction is only 76%; al et al (ChemCatChem.,2014,6:2224-2228) also report a ruthenium cluster carbonyl complex/[ Bmim ]]Cl catalyst system for catalyzing olefin and CO at 120 deg.C2Carbonylation is carried out, and the yield reaches 96% after 17 hours of reaction; qi Wang et al (Catal. Sci. technol.,2016,6:4712-]Cl catalyst system, olefin/scCO catalysis at 180 DEG C2The carbonylation of methanol is carried out, the yield reaches 95 percent after 20 hours of reaction, but the catalytic systems all need longer reaction time (more than 17 hours), and the recycling property of the catalyst is not involved.
Based on the comprehensive analysis, the invention designs a catalytic system for catalyzing ethylene and CO2And methanol to produce methyl propionate. The catalytic system mainly introduces imidazole ionic liquid which reacts with water, and specifically comprises the following components: ruthenium cluster carbonyl complexes, imidazole ionic liquid and inorganic salt promoters. The catalyst system has the advantages of short reaction time and good recycling property.
The invention content is as follows:
the invention aims to provide a catalytic system for synthesizing methyl propionate and an application method thereof aiming at the steps in the prior art. The method develops a catalytic system of ruthenium cluster carbonyl complex/imidazole ionic liquid/inorganic salt promoter by adding imidazole ionic liquid, the system consumes water generated in the reaction by using the imidazole ionic liquid, the reaction is promoted to be carried out in the positive direction, and the imidazole ionic liquid is addedAdding inorganic salt promoter to further improve catalytic activity for catalyzing ethylene and CO2And methanol to produce methyl propionate. The invention obviously shortens the reaction time, thereby improving the yield of methyl propionate.
The technical scheme of the invention is as follows:
a catalytic system for synthesizing methyl propionate comprises a ruthenium cluster carbonyl complex, imidazole ionic liquid and an inorganic salt promoter, or the ruthenium cluster carbonyl complex and the imidazole ionic liquid;
wherein, the molar ratio of the imidazole ionic liquid: 100-250% of ruthenium cluster carbonyl complex: 1; when the catalytic system includes a promoter, the molar ratio of promoter: 1-75% of ruthenium cluster carbonyl complex: 1.
the ruthenium cluster carbonyl complex is a known substance and comprises Ru3(CO)12、H4Ru4(CO)12、[PPN][RuCl3(CO)3]、Ru3(CO)9(PPh3)3、Ru3(CO)11(PPh2py)、Ru(CO)HCl(PPh3)3、RuH2(PPh3)4、Ru3(CO)11H(PPN)、Ru(acac)3、Ru(CO)3(PPh3)2、Ru(CO)3(PCy3)2、Et4N[Ru(CO)3I3]、Et4N[HRu3(CO)11]Or Ru (OAc)2(Ph3P)2。
The promoter is carbonate, lithium halide salt or transition metal chloride salt;
the promoter is specifically carbonate, lithium halide salt, transition metal chloride salt and the like, and specifically comprises sodium bicarbonate, potassium bicarbonate, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate and calcium carbonate; lithium fluoride, lithium chloride, lithium bromide, lithium iodide; sodium chloride, potassium chloride, cesium chloride, cuprous chloride, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, stannous chloride, ferrous chloride, aluminum chloride, or ferric chloride.
The application method of the catalytic system for synthesizing the methyl propionate is that
A method for synthesizing methyl propionate, comprising the steps of:
adding the substances in the catalytic system into a reaction kettle, sealing the reaction kettle, vacuumizing at 70 ℃, stirring for 0.5h, adding quantitative methanol and ethylene into the reaction kettle under the protection of argon, and finally filling CO2Heating to 160-200 ℃ under the pressure of 3-5 MPa, and reacting for 1.5-6 h under magnetic stirring to obtain methyl propionate;
wherein, the mol ratio of methanol: 25-100% of ethylene: 1; the molar ratio of methanol: the ruthenium cluster carbonyl complex is 2500-5000: 1.
an imidazole ionic liquid, the structural formula of which is as follows:
wherein R is CH3、CH3CH2Or COCH3；
X＝Cl、Br、I、BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
The invention has the beneficial effects that:
the catalytic system comprises a ruthenium cluster carbonyl complex, imidazole ionic liquid and a small amount of inorganic salt as a promoter to catalyze ethylene and CO2And methanol carbonylation reaction to produce methyl propionate. Carbon dioxide is a main gas of greenhouse effect, an industrial utilization path is relatively narrow, methanol and ethylene are chemical raw materials with rich yield, the carbon dioxide is efficiently converted into methyl propionate through a catalytic system researched by the text, imidazole ionic liquid promotes the reaction to be carried out in the positive direction by consuming water generated in the system, the reaction time is obviously shortened, the catalytic activity can be further improved by the inorganic salt promoter, the yield of the methyl propionate is increased, the yield reaches 99% under the optimal reaction condition, the yield is still up to 90% after 5 times of circulation, and the method is the same as that of the traditional synthetic processCompared with the catalyst system, the catalyst system has the advantages of short reaction time and good cyclic usability.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of an Ionic liquid (Ionic liquid (1)) used in examples;
FIG. 2 shows nuclear magnetic hydrogen spectra of another Ionic liquid (Ionic liquid (2)) used in examples.
Detailed Description
The foregoing summary of the invention is described in further detail below with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention as described above, according to the common technical knowledge and conventional means in the field, and the scope of the invention is covered.
The operation steps in the following examples are: adding the catalytic system into a reaction kettle in a glove box, sealing the reaction kettle, heating at 70 ℃, vacuumizing and stirring for 0.5h to uniformly dissolve the ruthenium cluster carbonyl complex (inorganic salt promoter) in the ionic liquid. Adding 5.6ml of methanol into a reaction kettle under the protection of argon, filling ethylene with a certain pressure into the reaction kettle, and then filling CO into the reaction kettle2And (3) heating to 160-200 ℃ under the pressure of 3-5 MPa, reacting for 1.5-6 hours under magnetic stirring, stopping heating, cooling to room temperature, releasing the pressure, and taking a liquid sample for gas chromatography analysis.
The adopted catalysts are ruthenium cluster carbonyl complexes and imidazole ionic liquid; the adopted accelerant is carbonate, lithium halide salt or transition metal chloride salt.
The adopted process conditions are as follows: the reaction kettle is filled with 2mmol of ethylene and CO23-5 MPa, the reaction temperature is 160-200 ℃, the reaction time is 1.5-6 h, and when the promoter is added, the molar ratio of the promoter to the ruthenium cluster carbonyl complex is 1-75: 1.
the ruthenium cluster carbonyl complexes are all known substances and mainly comprise Ru3(CO)12、H4Ru4(CO)12、[PPN][RuCl3(CO)3]、Ru3(CO)9(PPh3)3、Ru3(CO)11(PPh2py)、Ru(CO)HCl(PPh3)3、RuH2(PPh3)4、Ru3(CO)11H(PPN)、Ru(acac)3、Ru(CO)3(PPh3)2、Ru(CO)3(PCy3)2、Et4N[Ru(CO)3I3]、Et4N[HRu3(CO)11]Or Ru (OAc)2(Ph3P)2。
The promoter is carbonate, lithium halide salt, transition metal chloride salt, etc., and specifically includes sodium bicarbonate, potassium bicarbonate, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, and calcium carbonate; lithium fluoride, lithium chloride, lithium bromide, lithium iodide; sodium chloride, potassium chloride, cesium chloride, cuprous chloride, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, stannous chloride, ferrous chloride, aluminum chloride, or ferric chloride, with lithium bromide, lithium iodide, magnesium chloride, copper chloride, or nickel chloride being preferred.
The main structure of the imidazole ionic liquid is as follows:
wherein R is CH3、CH3CH2Or COCH3；
X＝Cl、Br、I、BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
Two ionic liquids mainly adopted in the examples and the preparation method thereof are given below, specifically:
R＝CH3x ═ Cl, designated Ionic liquid (1); r is CH3CH2And X ═ Cl, designated Ionic liquid (2).
A step of synthesizing an Ionic liquid (1); adding 3-chloropropyltrimethoxysilane (75mmol) and N-methylimidazole (75mmol) into the reaction kettle, sealing the reaction kettle, pumping the system for three times, and reacting for 12 hours at 120 ℃ under the protection of argon. And cooling the reaction kettle after the reaction is finished to obtain light cyan viscous liquid, adding 15ml of methanol into the reaction kettle to completely dissolve the product, transferring the product into a single-mouth bottle, performing vacuum rotary evaporation at 60 ℃ for 20min, and finally performing vacuum drying at 120 ℃ until no bubbles appear, thereby finally obtaining the light cyan viscous liquid.
A step of synthesizing an Ionic liquid (2); the method is the same as the synthesis step of Ionic liquid (1), except that 3-chloropropyltrimethoxysilane is replaced by 3-chloropropyltriethoxysilane, and finally yellow viscous liquid is obtained.
Nuclear magnetic hydrogen Spectrum (400 MH) of Ionic liquid (1)ZDMSO): b ═ 10.56(s,1H), d ═ 7.74(s,1H), c ═ 7.47(s,1H), e ═ 4.43(t,2H), a ═ 4.12(d,3H), H ═ 3.57(d,9H), f ═ 2.02(t,2H), g ═ 0.63(t,2H).
Nuclear magnetic hydrogen Spectrum (400 MH) of Ionic liquid (2)ZDMSO): b ═ 9.41(s,1H), d ═ 7.83(s,1H), c ═ 7.78(s,1H), e ═ 4.16(t,2H), a ═ 3.88(s,3H), H ═ 3.76(t,6H), f ═ 1.80(s,2H), i ═ 1.13(t, H), and g ═ 0.52(d,2H).
Example 1
Weighing 5.6mmol of Ionic liquid (1) and Ru in a glove box3(CO)12Adding 0.042mmol of the mixture into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oil bath kettle at the temperature of 70 ℃, and vacuumizing for 0.5 h. Adding 5.6ml (150mmol) of methanol and 2mmol of ethylene into the reaction kettle under the protection of argon, and introducing CO24MPa, the equilibrium pressure is 3min, the temperature of the reaction kettle is raised to 200 ℃, the stirring speed is 500r/min, the reaction duration is 6h, the liquid in the reaction kettle is orange-red transparent liquid after the reaction is finished, and the yield of the methyl propionate is 98.9 percent. The test method of the yield is as follows: and (3) moving the transparent liquid in the reaction kettle out to a 10ml penicillin bottle, adding a certain mass of n-heptane as an internal standard into the Xilin bottle, recording the mass of the added n-heptane, and calculating the yield of the methyl propionate by a gas chromatography internal standard method.
Example 2
The process is otherwise the same as in example 1, except that the reaction temperature is 160 ℃, the reaction time is 20 hours, and the yield of methyl propionate is 99.7%. The synthesis yield of methyl propionate was 76.0% under the same conditions as in the literature.
Example 3
The procedure is as in example 1 except that Ionic liquid (1) is replaced with a literature Ionic liquid [ Bmim ] Cl and the yield of methyl propionate is 37.2%.
Example 4
The procedure is as in example 1 except that the yield of methyl propionate is 94.8% when Ionic liquid (1) is replaced by Ionic liquid (2).
Example 5
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for H4Ru4(CO)120.042mmol, yield of methyl propionate was 96.2%.
Example 6
The other part is the same as example 1 except that Ru3(CO)120.042mmol as [ PPN ]][RuCl3(CO)3]0.042mmol, methyl propionate yield 97.7%.
Example 7
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for Ru3(CO)9(PPh3)30.042mmol, yield of methyl propionate was 96.7%.
Example 8
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for Ru3(CO)11(PPh2py)0.042mmol, yield of methyl propionate was 97.1%.
Example 9
The other part is the same as example 1 except that Ru3(CO)120.042mmol as Ru (CO) HCl (PPh)3)30.042mmol, yield of methyl propionate was 97.3%.
Example 10
The other part is the same as example 1 except that Ru3(CO)120.042mmol as RuH2(PPh3)40.042mmol, methyl propionate yield 97.9%.
Example 11
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for Ru3(CO)11H (PPN)0.042mmol, methyl propionate yield 96.2%.
Example 12
The other part is the same as example 1 except that Ru3(CO)120.042mmol as Ru (acac)30.042mmol, yield of methyl propionate was 97.4%.
Example 13
The other part is the same as example 1 except that Ru3(CO)120.042mmol as Ru (CO)3(PPh3)20.042mmol, yield of methyl propionate 98.1%.
Example 14
The other part is the same as example 1 except that Ru3(CO)120.042mmol as Ru (CO)3(PCy3)20.042mmol, yield of methyl propionate 98.0%.
Example 15
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for Et4N[Ru(CO)3I3]0.042mmol, yield of methyl propionate was 97.0%.
Example 16
The other part is the same as example 1 except that Ru3(CO)120.042mmol exchanged for Et4N[HRu3(CO)11]0.042mmol, yield of methyl propionate was 96.9%.
Example 17
The other part is the same as example 1 except that Ru3(CO)120.042mmol as Ru (OAc)2(Ph3P)20.042mmol, methyl propionate yield 97.7%.
Example 18
The procedure is as in example 1 except that the reaction time is 5 hours and the yield of methyl propionate is 86.4%.
Example 19
The procedure is as in example 1 except that the reaction time is 4 hours and the yield of methyl propionate is 60.2%.
Example 20
The process was otherwise the same as in example 1, except that the reaction time was 2 hours and the yield of methyl propionate was 42.5%.
Example 21
The other point is the same as that of example 1 except that CO2The pressure was 3MPa and the yield of methyl propionate was 81.2%.
Example 22
The procedure is as in example 1 except that the reaction temperature is 180 ℃ and the yield of methyl propionate is 66.6%.
Example 23
The other steps are the same as example 1 except that the reaction temperature is 180 ℃ and CO is2The pressure was 5MPa and the yield of methyl propionate was 70.0%.
Example 24
The procedure is as in example 1 except that the reaction temperature is 160 ℃ and the yield of methyl propionate is 46.6%.
Example 25
The procedure is as in example 1 except that the reaction temperature is 160 ℃ and the reaction time is 9 hours, and the yield of methyl propionate is 57.1%.
Example 26
The process is otherwise the same as in example 1, except that the reaction temperature is 160 ℃, the reaction time is 12 hours, and the yield of methyl propionate is 76.2%.
Example 27
The other steps are the same as example 1 except that Ionic liquid (1) and Ru are added3(CO)12Simultaneously, 0.126mmol of inorganic salt sodium chloride (the time for adding the accelerator in the following examples is the same), the reaction time is 4h, and the yield of the methyl propionate is 74.0%.
Example 28
The same process as in example 27 except that 0.126mmol of potassium chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 74.3%.
Example 29
The same procedure as in example 27 except that 0.126mmol of cesium chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 75.2%.
Example 30
The same process as in example 27 except that 0.126mmol of sodium chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 82.4%.
Example 31
The same process as in example 27 except that 2.52mmol of sodium chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 87.8%.
Example 32
The procedure is as in example 27 except that 0.126mmol of sodium hydrogencarbonate, which is an inorganic salt, is added, and the yield of methyl propionate is 78.7%.
Example 33
The process is otherwise the same as in example 27, except that 0.126mmol of potassium hydrogencarbonate, which is an inorganic salt, is added, and the yield of methyl propionate is 77.8%.
Example 34
The procedure is as in example 27 except that 0.063mmol of the inorganic salt of sodium carbonate is added, and the yield of methyl propionate is 76.0%.
Example 35
The procedure is as in example 27 except that 0.063mmol of lithium carbonate as an inorganic salt is added, and the yield of methyl propionate is 75.3%.
Example 36
The procedure is as in example 27 except that 0.063mmol of the inorganic salt potassium carbonate is added, and the yield of methyl propionate is 74.7%.
Example 37
The same procedure as in example 27 was repeated, except that 0.063mmol of cesium carbonate as an inorganic salt was added, and the yield of methyl propionate was 75.5%.
Example 38
The procedure is as in example 27 except that 0.126mmol of magnesium carbonate, which is an inorganic salt, is added and the yield of methyl propionate is 83.5%.
Example 39
The procedure is as in example 27 except that 0.126mmol of calcium carbonate as an inorganic salt is added, and the yield of methyl propionate is 84.2%.
Example 40
The same procedure as in example 27 except that 0.126mmol of lithium fluoride as an inorganic salt was added was conducted, and the yield of methyl propionate was 89.0%.
EXAMPLE 41
The same procedure as in example 27 except that 0.126mmol of lithium chloride was added as an inorganic salt, the yield of methyl propionate was 76.9%.
Example 42
The same procedure as in example 27 except that 3.150mmol of lithium chloride as an inorganic salt was added was conducted, the yield of methyl propionate was 97.4%.
Example 43
The same procedure as in example 27 except that 0.126mmol of lithium bromide as an inorganic salt was added was conducted, and the yield of methyl propionate was 96.7%.
Example 44
The procedure is as in example 27 except that 0.126mmol of lithium iodide, which is an inorganic salt, is added and the yield of methyl propionate is 99.1%.
Example 45
The procedure is as in example 27 except that 0.126mmol of cuprous chloride, which is an inorganic salt, is added, and the yield of methyl propionate is 98.5%.
Example 46
The procedure is as in example 27 except that 0.126mmol of magnesium chloride as an inorganic salt is added, and the yield of methyl propionate is 99.0%.
Example 47
The same procedure as in example 27 except that 0.126mmol of calcium chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 84.8%.
Example 48
The procedure is as in example 27 except that 0.126mmol of zinc chloride, which is an inorganic salt, is added, and the yield of methyl propionate is 87.3%.
Example 49
The same process as in example 27 except that 0.126mmol of nickel chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 97.7%.
Example 50
The procedure is as in example 27 except that 0.126mmol of the inorganic salt copper chloride is added, and the yield of methyl propionate is 96.5%.
Example 51
The procedure is as in example 27 except that 0.126mmol of manganese chloride, an inorganic salt, is added and the yield of methyl propionate is 83.9%.
Example 52
The process is otherwise the same as in example 27, except that 0.126mmol of stannous chloride as an inorganic salt is added, and the yield of methyl propionate is 78.0%.
Example 53
The same process as in example 27 except that 0.126mmol of the inorganic salt aluminum chloride was added was conducted, and the yield of methyl propionate was 74.5%.
Example 54
The same process as in example 27 except that 0.126mmol of ferric chloride as an inorganic salt was added was conducted, and the yield of methyl propionate was 72.7%.
Example 55
The same procedure as in example 27 except that 0.042mmol of potassium phosphate, which is an inorganic salt, was added was conducted, and the yield of methyl propionate was 75.7%.
Example 56
The process is otherwise the same as in example 43, except that the reaction time is 2h, and the yield of methyl propionate is 77.7%.
Example 57
The process is otherwise the same as in example 44, except that the reaction time is 2h, and the yield of methyl propionate is 92.1%.
Example 58
The process is otherwise the same as in example 45, except that the reaction time is 2h, and the yield of methyl propionate is 69.8%.
Example 59
The process is otherwise the same as in example 46, except that the reaction time is 2h, and the yield of methyl propionate is 97.1%.
Example 60
The process is otherwise the same as in example 50, except that the reaction time is 2h and the yield of methyl propionate is 92.4%.
Example 61
The process is otherwise the same as in example 44, except that the reaction time is 1.5h, and the yield of methyl propionate is 69.0%.
Example 62
The process is otherwise the same as in example 46, except that the reaction time is 1.5h, and the yield of methyl propionate is 67.8%.
Example 63
The process is otherwise the same as in example 50, except that the reaction time is 1.5h and the yield of methyl propionate is 51.3%.
Example 64
And (3) testing the recycling performance of the catalyst: the first reaction was carried out as in example 46, giving a methyl propionate yield of 99% by gas chromatography; and (3) second reaction: pumping the solution in the reaction kettle by using a vacuum pump, keeping the residual catalyst in the reaction kettle, adding 5.6ml of methanol and 2mmol of ethylene again, and introducing CO24MPa, balancing the pressure for 3 minutes, rotating speed of 500r/min, reacting for 4 hours at 200 ℃, and measuring the yield of methyl propionate by gas chromatography after the reaction is finished. The second step was repeated until the fifth reaction, and the yield of methyl propionate was 90% after the fifth reaction. This example demonstrates good catalyst cycle performance.
In conclusion, the invention develops a catalytic system of ruthenium cluster carbonyl complex/imidazole ionic liquid/inorganic salt promoter by adding imidazole ionic liquid, the system consumes water generated in the reaction by using the imidazole ionic liquid, and the reaction is promoted to be carried out in a positive direction, thereby catalyzing ethylene and CO2And methanol to produce methyl propionate. The catalyst system has the advantages of short reaction time and good recycling property. The addition of the inorganic salt promoter can further improve the catalytic activity and increase the yield of methyl propionate, wherein the yield of methyl propionate can reach more than 95% by adding lithium bromide, lithium iodide, magnesium chloride, cuprous chloride, nickel chloride and copper chloride when the reaction time is 4 hours at 200 ℃, and the design of the whole scheme has important application value.
The invention is not the best known technology.
Claims (1)
1. A process for the synthesis of methyl propionate, characterized in that it comprises the following steps:
adding the substances in the catalytic system into a reaction kettle, sealing the reaction kettle, and 70oC, vacuumizing and stirring for 0.5h, adding methanol and ethylene into the reaction kettle under the protection of argon, and finally filling CO2The pressure is 3-5 MPa, and the temperature is raised to 160-200oC, reacting for 1.5-6 hours under magnetic stirring to obtain methyl propionate;
wherein, the mol ratio of methanol: ethylene =25 to 100: 1; the molar ratio of methanol: the ruthenium cluster carbonyl complex = 2500-5000: 1;
the catalytic system comprises a ruthenium cluster carbonyl complex, imidazole ionic liquid and an inorganic salt promoter, or the ruthenium cluster carbonyl complex and the imidazole ionic liquid;
wherein, the molar ratio of the imidazole ionic liquid: ruthenium cluster carbonyl complex =100 to 250: 1; when the catalytic system includes a promoter, the molar ratio of promoter: ruthenium cluster carbonyl complexes = 1-75: 1;
the ruthenium cluster carbonyl complex is Ru3(CO)12、H4Ru4(CO)12、[PPN][RuCl3(CO)3]、Ru3(CO)9(PPh3)3、Ru3(CO)11(PPh2py)、Ru(CO)HCl(PPh3)3、RuH2(PPh3)4、Ru3(CO)11H(PPN)、Ru(acac)3、Ru(CO)3(PPh3)2、Ru(CO)3(PCy3)2、Et4N[Ru(CO)3I3]、Et4N[HRu3(CO)11]Or Ru (OAc)2(Ph3P)2；
The promoter specifically comprises sodium bicarbonate, potassium bicarbonate, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate and calcium carbonate; lithium fluoride, lithium chloride, lithium bromide, lithium iodide; sodium chloride, potassium chloride, cesium chloride, cuprous chloride, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, stannous chloride, ferrous chloride, aluminum chloride, or ferric chloride;
the imidazole ionic liquid has the following structural formula:
wherein R = CH3、CH3CH2Or COCH3；
X=Cl、Br、I、BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
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