CN108993602A - A kind of catalyst system and its application method of propionic acid synthesized methyl esters - Google Patents
A kind of catalyst system and its application method of propionic acid synthesized methyl esters Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
The present invention is the catalyst system and its application method of a kind of propionic acid synthesized methyl esters.The group of the catalyst system becomes ruthenium cluster carbonyl-complexes, glyoxaline ion liquid and inorganic salts promotor or ruthenium cluster carbonyl-complexes and glyoxaline ion liquid；Wherein, molar ratio glyoxaline ion liquid: ruthenium cluster carbonyl-complexes=100~250:1；When catalyst system includes promotor, molar ratio promotor: ruthenium cluster carbonyl-complexes=1~75:1；The promotor is carbonate, halogenation lithium salts or transition metal chlorate.The system consumes the water generated in reaction using glyoxaline ion liquid, and reaction is promoted to carry out to positive direction, and inorganic salts promotor is added and further increases catalytic activity, to be catalyzed ethylene, CO2Methyl propionate is prepared with methanol.The present invention is obviously shortened the reaction time, to improve methyl propionate yield.
Description
Technical field:
The invention belongs to hydrogen esterification reaction synthesis of organic chemical product field more particularly to a kind of ethenecarbonyl are propionic acid synthesized
The method of methyl esters.
Background technique:
Methyl propionate is a kind of colorless and transparent organic liquid, may be used as fragrance, solvent, extractant, organic centre
Body and plasticizer etc. are widely used in the industries such as adhesive, coating, weaving, rubber, plastics.Methyl propionate by esterification,
Hydrolysis, ester exchange reaction can produce the various products such as propionate, propionic acid, propionic ester (benzyl propionate, isoamyl propionate etc.),
So the exploitation of methyl propionate synthesis process is conducive to the progress and development of the technologies such as propionic acid, propionate, propionic ester.
The Reppe of Germany proposes the directly propionic acid synthesized methyl esters of ethylene hydrogen esterification process or ethyl propionate technique, uses Ni
Series catalysts, severe reaction conditions, the high requirements on the equipment；Patent (CN87110635) be related to palladium (II)/aryl replace phosphine/
Acid catalytic systems are catalyzed ethylene/methanol carbonylation activity with higher, but the Phosphine ligands in such ligand system are easy
Decomposition leads to catalyst inactivation；Document (R.F.Heck, J.A.m.Chem.Soc., 1963,85；W.Keim.J.Mol.Catal.,
1989,54 (1)) show that the complex catalysts such as ruthenium, nickel, cobalt carry out carbonylation synthesis methyl propionate to ethylene/CO/ methanol and have work
Property.But severe reaction conditions, conversion ratio is low, poor selectivity；Using palladium acetate as major catalyst in patent (CN103319337),
The metal ions such as cobalt, nickel or ruthenium are that the complex catalyst system of co-catalyst is catalyzed ethylene/CO/ methanol carbonylation, reaction
Mild condition, selectivity is high, but due to palladium metal valuableness, causes production cost higher；Hidai etc. (J.Mol.Catal.,
1987,40 (2): 243-254) discovery Ru3(CO)12In the case where ionic iodide makees co-catalyst, it is catalyzed ethylene/CO/ methanol-fueled CLC
Methyl propionate, selectivity is higher, but need to be using CO as raw material in these catalyst systems, toxic inflammable and difficult storage.Therefore, it seeks
Look for the key for replacing the carbonyl source of CO to become research during carbonylation of olefin.It is reported that new carbonyl source has CO2, methanol, first
Aldehyde, formic acid etc..Wherein, nontoxic, the stable and cheap CO being largely present in nature2As main research direction.
Tominaga etc. (Catal.Commun., 2000,1:1-3) uses ruthenium cluster carbonyl-complexes/LiCl catalyst system,
Catalyzed alkene and CO at 140 DEG C2It is carbonylated, yield is 86% after reacting 30h；Haukka etc. (Appl.Catal., A:
General,2003,247:95-100；Appl.Catal., A:General, 2009,365:130-134) with ruthenium cluster carbonyl complex
Object/LiCl catalyst system, catalyzed alkene and CO at 150 DEG C2It is carbonylated, yield is 80% after reacting 17h；LiPeng
Wu etc. (Nat.Commun., 2014,5 (2): 3091-3096) uses ruthenium cluster carbonyl-complexes catalyst system, in 160 DEG C of catalysis alkene
Hydrocarbon and CO2It is carbonylated, yield is only 11% after reacting 20h, and after LiCl is added, yield rises to 64%；Ionic liquid is added
After body [Bmim] Cl, yield reaches 92%, and uses ruthenium cluster carbonyl-complexes/[Bmim] Cl catalyst system, is catalyzed at 160 DEG C
Ethylene/CO2/ methanol is carbonylated, and the yield of methyl propionate is only 76% after reaction 20h；M.Ali etc. (ChemCatChem.,
2014,6:2224-2228) also report ruthenium cluster carbonyl-complexes/[Bmim] Cl catalyst system, at 120 DEG C catalyzed alkene and
CO2It is carbonylated, yield reaches 96% after reacting 17h；(Catal.Sci.Technol., the 2016,6:4712- such as Qi Wang
4717) ruthenium cluster carbonyl-complexes/[Bmim] Cl catalyst system, catalyzed alkene/scCO at 180 DEG C are also used2/ methanol carries out carbonyl
Base, yield reaches 95% after reacting 20h, but these catalyst systems are both needed to the reaction time of longer (being greater than 17h), and do not have
It is related to the recycling of catalyst.
Based on the above comprehensive analysis, the present invention devises a kind of catalyst system, is catalyzed ethylene, CO2Propionic acid is prepared with methanol
Methyl esters.This catalyst system has been introduced primarily into the glyoxaline ion liquid reacted with water, specifically includes: ruthenium cluster carbonyl-complexes,
Glyoxaline ion liquid, inorganic salts promotor.The catalyst system has the advantages that the reaction time is short, recycling is good.
Summary of the invention:
The purpose of the present invention is provide a kind of catalyst system of propionic acid synthesized methyl esters for step present in current techniques
And its application method.This method by the addition of glyoxaline ion liquid, have developed a kind of ruthenium cluster carbonyl-complexes/imidazoles from
Sub- liquid/inorganic salts promotor catalyst system, the system consume the water generated in reaction using glyoxaline ion liquid, promote
It is carried out into reaction to positive direction, inorganic salts promotor is added and further increases catalytic activity, to be catalyzed ethylene, CO2With methanol system
Standby methyl propionate.The present invention is obviously shortened the reaction time, to improve methyl propionate yield.
The technical solution of the present invention is as follows:
A kind of catalyst system of propionic acid synthesized methyl esters, the group of the catalyst system become ruthenium cluster carbonyl-complexes, imidazoles from
Sub- liquid and inorganic salts promotor or ruthenium cluster carbonyl-complexes and glyoxaline ion liquid；
Wherein, molar ratio glyoxaline ion liquid: ruthenium cluster carbonyl-complexes=100~250:1；When catalyst system includes promoting
Into when agent, molar ratio promotor: ruthenium cluster carbonyl-complexes=1~75:1.
The ruthenium cluster carbonyl-complexes are known substance, including 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 promotor is carbonate, halogenation lithium salts or transition metal chlorate；
The promotor is specially carbonate, halogenation lithium salts, transition metal chlorate etc., specifically include sodium bicarbonate,
Saleratus, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate；Lithium fluoride, lithium chloride, lithium bromide, iodate
Lithium；Sodium chloride, potassium chloride, cesium chloride, stannous chloride, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, chlorine
Change stannous, frerrous chloride, aluminium chloride or iron chloride.
The application method of the catalyst system of the propionic acid synthesized methyl esters, i.e.,
A kind of method of propionic acid synthesized methyl esters, includes the following steps:
Substance in the catalyst system is added in reaction kettle, closed reactor, 70 DEG C vacuumize and stir
Quantitative methanol and ethylene are added into reaction kettle under argon gas protection, is finally filled with CO by 0.5h23~5MPa of pressure, is warming up to
160~200 DEG C, after reacting 1.5~6h under magnetic agitation, obtain methyl propionate；
Wherein, molar ratio methanol: ethylene=25~100:1；Molar ratio methanol: ruthenium cluster carbonyl-complexes=2500~
5000:1.
The structural formula of a kind of glyoxaline ion liquid, the ionic liquid is as follows:
Wherein, R=CH3、CH3CH2Or COCH3；
X=Cl, Br, I, BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
The invention has the benefit that
Catalyst system of the present invention, including ruthenium cluster carbonyl-complexes, glyoxaline ion liquid and on a small quantity inorganic
Salt is catalyzed ethylene, CO as promotor2Methyl propionate is generated with methanol carbonylation.Carbon dioxide is the master of greenhouse effects
Gas is wanted, industrial utilization approach is but relatively narrow, and methanol, ethylene are also the chemicals raw material of abundance, by studying herein
Catalyst system by high-efficiency carbon dioxide be converted into methyl propionate, glyoxaline ion liquid is by generating in consumption system
Water promotes reaction to carry out to positive direction, hence it is evident that shorten the reaction time, inorganic salts promotor can further increase catalytic activity,
Increase methyl propionate yield, yield reaches 99% under optimum reaction condition, and yield is still up to after circulation 5 times
90%, the advantage that the catalyst system reaction time is short, recycling is good compared with traditional synthesis.
Detailed description of the invention
Fig. 1 is a kind of nucleus magnetic hydrogen spectrum for ionic liquid (Ionic liquid (1)) that embodiment uses；
Fig. 2 is the nucleus magnetic hydrogen spectrum for another ionic liquid (Ionic liquid (2)) that embodiment uses.
Specific embodiment
Foregoing invention content of the invention is described in further detail With reference to embodiment.But it should not incite somebody to action
This range for being interpreted as the above-mentioned theme of the present invention is only limitted to following embodiments.The above-mentioned technical idea situation of the present invention is not being departed from
Under, according to ordinary skill knowledge and customary means, various replacements and change are made, the scope of the present invention should all be included in
It is interior.
Operating procedure in following embodiment are as follows: the catalyst system is added in reaction kettle in glove box, it is close
Reaction kettle is closed, 70 DEG C are heated and vacuumized stirring 0.5h, make ruthenium cluster carbonyl-complexes (inorganic salts promotor) in ionic liquid
It is uniformly dissolved.5.6ml methanol is added into reaction kettle under argon gas protection, the ethylene of certain pressure is filled with into reaction kettle, later
It is filled with CO2Pressure is 3~5MPa, is warming up to 160~200 DEG C, stops heating after 1.5~6h is reacted under magnetic agitation, is cooled to
Room temperature takes liquid-like to do gas chromatographic analysis after releasing stress.
The catalyst used is ruthenium cluster carbonyl-complexes and glyoxaline ion liquid；The promotor used is carbonate, halogen
Change lithium salts or transition metal chlorate.
The process conditions of use: it is filled with ethylene 2mmol in reaction kettle, is filled with CO23~5MPa, reaction temperature 160~200
DEG C, 1.5~6h of reaction time, when promotor is added, promotor and ruthenium cluster carbonyl-complexes molar ratio=1~75:1.
Ruthenium cluster carbonyl-complexes of the present invention are known substance, mainly include 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。
Promotor used is carbonate, halogenation lithium salts, transition metal chlorate etc., specifically includes sodium bicarbonate, carbonic acid
Hydrogen potassium, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate；Lithium fluoride, lithium chloride, lithium bromide, lithium iodide；Chlorine
Change sodium, potassium chloride, cesium chloride, stannous chloride, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, protochloride
Tin, frerrous chloride, aluminium chloride or iron chloride, wherein it is preferred that lithium bromide, lithium iodide, magnesium chloride, copper chloride or nickel chloride.
The glyoxaline ion liquid primary structure are as follows:
Wherein, R=CH3、CH3CH2Or COCH3；
X=Cl, Br, I, BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
The two kinds of ionic liquids and preparation method thereof mainly used in embodiment are given below, specifically:
R=CH3, X=Cl is named as Ionic liquid (1)；R=CH3CH2, X=Cl is named as Ionic liquid
(2)。
Synthesize the operating procedure of Ionic liquid (1)；3- r-chloropropyl trimethoxyl silane is added into reaction kettle
(75mmol) and N- methylimidazole (75mmol), closed reactor, system pump drainage three times, react for 120 DEG C under protection of argon gas
12h.Cooling reaction kettle obtains nattierblue thick liquid after having reacted, backward reaction kettle in addition 15ml methanol product is complete
It dissolving and is transferred in single port bottle, 60 DEG C of vacuum rotate 20min, and last 120 DEG C of vacuum dryings to bubble-free occur, final
To nattierblue thick liquid.
Synthesize the operating procedure of Ionic liquid (2)；With Ionic liquid (1) synthesis step, difference 3-
R-chloropropyl trimethoxyl silane is changed to 3- chloropropyl triethoxysilane, finally obtains yellow viscous liquid.
Nucleus magnetic hydrogen spectrum (the 400MH of Ionic liquid (1)Z, DMSO): 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) proves to obtain this substance.
Nucleus magnetic hydrogen spectrum (the 400MH of Ionic liquid (2)Z, DMSO): 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), g=0.52 (d, 2H) prove to obtain this substance.
Embodiment 1
Ionic liquid (1) 5.6mmol, Ru is weighed in glove box3(CO)120.042mmol is added in reaction kettle,
Reaction kettle is put into the oil bath pan that temperature is 70 DEG C, vacuumizes 0.5h by closed reactor.Under protection of argon gas into reaction kettle
Methanol 5.6ml (150mmol), ethylene 2mmol is added, is filled with CO24MPa and balance pressure 3min, reaction kettle is warming up to 200
DEG C, mixing speed 500r/min, duration of the reaction 6h, liquid is transparent salmon liquid, methyl propionate in kettle after having reacted
Yield is 98.9%.The test method of yield: transparency liquid in reaction kettle is moved in 10ml cillin bottle, is added into cillin bottle
The normal heptane for entering certain mass is cooked internal standard, and record is added the quality of normal heptane, calculates methyl propionate by gas chromatogram fixative
Yield.
Embodiment 2
Other are 160 DEG C of reaction temperature, reaction time 20h with embodiment 1, difference, and methyl propionate yield is
99.7%.For under equal conditions in document, methyl propionate synthetic yield is 76.0%.
Embodiment 3
With embodiment 1, difference is that Ionic liquid (1) is changed to document intermediate ion liquid [Bmim] Cl for other, third
Sour methyl esters yield is 37.2%.
Embodiment 4
Other are with embodiment 1, and difference is that Ionic liquid (1) is changed to Ionic liquid (2), and methyl propionate is received
Rate is 94.8%.
Embodiment 5
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to H4Ru4(CO)120.042mmol, third
Sour methyl esters yield is 96.2%.
Embodiment 6
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to [PPN] [RuCl3(CO)3]
0.042mmol, methyl propionate yield are 97.7%.
Embodiment 7
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru3(CO)9(PPh3)3
0.042mmol, methyl propionate yield are 96.7%.
Embodiment 8
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru3(CO)11(PPh2py)
0.042mmol, methyl propionate yield are 97.1%.
Embodiment 9
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru (CO) HCl (PPh3)3
0.042mmol, methyl propionate yield are 97.3%.
Embodiment 10
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to RuH2(PPh3)40.042mmol, third
Sour methyl esters yield is 97.9%.
Embodiment 11
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru3(CO)11H(PPN)
0.042mmol, methyl propionate yield are 96.2%.
Embodiment 12
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru (acac)30.042mmol, third
Sour methyl esters yield is 97.4%.
Embodiment 13
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru (CO)3(PPh3)2
0.042mmol, methyl propionate yield are 98.1%.
Embodiment 14
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru (CO)3(PCy3)2
0.042mmol, methyl propionate yield are 98.0%.
Embodiment 15
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Et4N[Ru(CO)3I3]
0.042mmol, methyl propionate yield are 97.0%.
Embodiment 16
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Et4N[HRu3(CO)11]
0.042mmol, methyl propionate yield are 96.9%.
Embodiment 17
Other are the same as embodiment 1, difference Ru3(CO)120.042mmol is changed to Ru (OAc)2(Ph3P)2
0.042mmol, methyl propionate yield are 97.7%.
Embodiment 18
Other with embodiment 1, difference be 5h in the reaction time, methyl propionate yield is 86.4%.
Embodiment 19
Other with embodiment 1, difference be 4h in the reaction time, methyl propionate yield is 60.2%.
Embodiment 20
Other with embodiment 1, difference be 2h in the reaction time, methyl propionate yield is 42.5%.
Embodiment 21
Other are the same as embodiment 1, difference CO2Pressure is 3MPa, and methyl propionate yield is 81.2%.
Embodiment 22
, with embodiment 1, difference is that reaction temperature is 180 DEG C for other, and methyl propionate yield is 66.6%.
Embodiment 23
Other are with embodiment 1, and difference is that reaction temperature is 180 DEG C, CO2Pressure is 5MPa, and methyl propionate yield is
70.0%.
Embodiment 24
, with embodiment 1, difference is that reaction temperature is 160 DEG C for other, and methyl propionate yield is 46.6%.
Embodiment 25
Other are with embodiment 1, and difference is that reaction temperature is 160 DEG C, reaction time 9h, and methyl propionate yield is
57.1%.
Embodiment 26
Other are with embodiment 1, and difference is that reaction temperature is 160 DEG C, reaction time 12h, and methyl propionate yield is
76.2%.
Embodiment 27
, with embodiment 1, difference is that Ionic liquid (1) and Ru is being added for other3(CO)12While, it is additionally added
Inorganic salts sodium chloride 0.126mmol (opportunity that promotor is added in following embodiment is identical), reaction time 4h, methyl propionate is received
Rate is 74.0%.
Embodiment 28
Inorganic salts potassium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
74.3%.
Embodiment 29
Inorganic salts cesium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
75.2%.
Embodiment 30
Inorganic salts sodium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
82.4%.
Embodiment 31
, with embodiment 27, inorganic salts sodium chloride 2.52mmol is added in difference for other, and methyl propionate yield is 87.8%.
Embodiment 32
Inorganic salts sodium bicarbonate 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
78.7%.
Embodiment 33
Inorganic salts saleratus 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
77.8%.
Embodiment 34
Inorganic salts sodium carbonate 0.063mmol is added with embodiment 27, difference in other, and methyl propionate yield is
76.0%.
Embodiment 35
Inorganic salts lithium 0.063mmol is added with embodiment 27, difference in other, and methyl propionate yield is
75.3%.
Embodiment 36
Inorganic salts potassium carbonate 0.063mmol is added with embodiment 27, difference in other, and methyl propionate yield is
74.7%.
Embodiment 37
Inorganic salts cesium carbonate 0.063mmol is added with embodiment 27, difference in other, and methyl propionate yield is
75.5%.
Embodiment 38
Inorganic salts magnesium carbonate 0.126mmol is added with embodiment 27, difference in other, methyl propionate yield is
83.5%.
Embodiment 39
Inorganic salts calcium carbonate 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
84.2%.
Embodiment 40
Inorganic salts lithium fluoride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
89.0%.
Embodiment 41
Inorganic salts lithium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
76.9%.
Embodiment 42
Inorganic salts lithium chloride 3.150mmol is added with embodiment 27, difference in other, and methyl propionate yield is
97.4%.
Embodiment 43
Inorganic salts lithium bromide 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
96.7%.
Embodiment 44
Inorganic salts lithium iodide 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
99.1%.
Embodiment 45
Inorganic salts stannous chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
98.5%.
Embodiment 46
Inorganic salts magnesium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
99.0%.
Embodiment 47
Inorganic salts calcium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
84.8%.
Embodiment 48
Inorganic salts zinc chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
87.3%.
Embodiment 49
Inorganic salts nickel chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
97.7%.
Embodiment 50
Inorganic salts copper chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
96.5%.
Embodiment 51
Inorganic salts manganese chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
83.9%.
Embodiment 52
Inorganic salts stannous chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
78.0%.
Embodiment 53
Inorganic salts aluminium chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
74.5%.
Embodiment 54
Inorganic salts iron chloride 0.126mmol is added with embodiment 27, difference in other, and methyl propionate yield is
72.7%.
Embodiment 55
Inorganic salts potassium phosphate 0.042mmol is added with embodiment 27, difference in other, and methyl propionate yield is
75.7%.
Embodiment 56
, with embodiment 43, the difference reaction time is 2h for other, and methyl propionate yield is 77.7%.
Embodiment 57
, with embodiment 44, the difference reaction time is 2h for other, and methyl propionate yield is 92.1%.
Embodiment 58
, with embodiment 45, the difference reaction time is 2h for other, and methyl propionate yield is 69.8%.
Embodiment 59
, with embodiment 46, the difference reaction time is 2h for other, and methyl propionate yield is 97.1%.
Embodiment 60
, with embodiment 50, the difference reaction time is 2h for other, and methyl propionate yield is 92.4%.
Embodiment 61
, with embodiment 44, the difference reaction time is 1.5h for other, and methyl propionate yield is 69.0%.
Embodiment 62
, with embodiment 46, the difference reaction time is 1.5h for other, and methyl propionate yield is 67.8%.
Embodiment 63
, with embodiment 50, the difference reaction time is 1.5h for other, and methyl propionate yield is 51.3%.
Embodiment 64
The test of catalyst circulation service performance: first set reaction with embodiment 46, survey methyl propionate yield and be by gas-chromatography
99%；Second secondary response: the solution in reaction kettle is drained using vacuum pump, and residual catalyst stays in reaction kettle, again plus
Enter methanol 5.6ml, ethylene 2mmol is filled with CO24MPa simultaneously balances pressure 3 minutes, revolving speed 500r/min, 200 DEG C of reaction 4h, instead
After the completion of answering, gas-chromatography surveys methyl propionate yield.Second of step is repeated until the 5th secondary response, propionic acid first after reacting five times
Ester yield is 90%.This example illustrates that catalyst circulation usability is good.
In conclusion addition of the present invention by glyoxaline ion liquid, has developed a kind of ruthenium cluster carbonyl-complexes/imidazoles
Class ionic liquid/inorganic salts promotor catalyst system, which is consumed using glyoxaline ion liquid generates in reaction
Water promotes reaction to carry out to positive direction, to be catalyzed ethylene, CO2Methyl propionate is prepared with methanol.The catalyst system has reaction
The advantage that time is short, recycling is good.And the addition of inorganic salts promotor can further increase catalytic activity, make propionic acid first
Ester yield increases, wherein 200 DEG C, when reaction time 4h, and lithium bromide, lithium iodide, magnesium chloride, stannous chloride, nickel chloride and chlorination
So that methyl propionate yield reaches 95% or more, entire conceptual design has important application value for the addition of copper.
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of catalyst system of propionic acid synthesized methyl esters, it is characterized in that the group of the catalyst system becomes ruthenium cluster carbonyl-complexes, miaow
Azole ionic liquid and inorganic salts promotor or ruthenium cluster carbonyl-complexes and glyoxaline ion liquid；
Wherein, molar ratio glyoxaline ion liquid: ruthenium cluster carbonyl-complexes=100~250:1；When catalyst system includes promotor
When, molar ratio promotor: ruthenium cluster carbonyl-complexes=1~75:1；
The promotor is carbonate, halogenation lithium salts or transition metal chlorate.
2. the catalyst system of propionic acid synthesized methyl esters as described in claim 1, it is characterized in that the ruthenium cluster carbonyl-complexes are
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。
3. the catalyst system of propionic acid synthesized methyl esters as described in claim 1, it is characterized in that the promotor is specially carbonic acid
Salt, halogenation lithium salts, transition metal chlorate etc., specifically include sodium bicarbonate, saleratus, sodium carbonate, lithium carbonate, potassium carbonate,
Cesium carbonate, magnesium carbonate, calcium carbonate；Lithium fluoride, lithium chloride, lithium bromide, lithium iodide；Sodium chloride, potassium chloride, cesium chloride, protochloride
Copper, magnesium chloride, calcium chloride, zinc chloride, nickel chloride, copper chloride, manganese chloride, stannous chloride, frerrous chloride, aluminium chloride or chlorination
Iron.
4. a kind of method of propionic acid synthesized methyl esters, it is characterized in that this method comprises the following steps:
Substance in the catalyst system is added in reaction kettle, closed reactor, 70 DEG C vacuumize and stir 0.5h, argon
Methanol and ethylene is added under gas shielded into reaction kettle, is finally filled with CO23~5MPa of pressure is warming up to 160~200 DEG C, magnetic force
After 1.5~6h of the lower reaction of stirring, methyl propionate is obtained；
Wherein, molar ratio methanol: ethylene=25~100:1；Molar ratio methanol: ruthenium cluster carbonyl-complexes=2500~5000:1.
5. a kind of glyoxaline ion liquid, it is characterized in that the structural formula of the ionic liquid is as follows:
Wherein, R=CH3、CH3CH2Or COCH3；
X=Cl, Br, I, BF4、PF6、SCN、HSO4、HCO3、CF3SO3、CF3COO or Tf2N。
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