CN101134163A - Method for synthesizing formic ester and specific catalyzer thereof - Google Patents
Method for synthesizing formic ester and specific catalyzer thereof Download PDFInfo
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- CN101134163A CN101134163A CNA2007101757362A CN200710175736A CN101134163A CN 101134163 A CN101134163 A CN 101134163A CN A2007101757362 A CNA2007101757362 A CN A2007101757362A CN 200710175736 A CN200710175736 A CN 200710175736A CN 101134163 A CN101134163 A CN 101134163A
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Abstract
The present invention discloses nanometer metal catalyst catalyzed formic acid ester synthesizing process, in which alcohol is catalyzed for caronylation reaction in the presence of nanometer metal catalyst and CO. The nanometer metal catalyst with particle size of 1-10 nm is prepared through mixing metal salt and macromolecular stabilizer, dispersing in liquid medium and reducing with reductant. The nanometer metal catalyst has the following advantages: capacity of realizing 3D free rotation, excellent low temperature activity capable of catalyzing formic acid ester synthesis at 60-200 deg.c, high conversion efficiency and high selectivity of formic acid ester, stable performance, environment friendship, etc. The nanometer metal catalyst catalyzed formic acid ester synthesizing process of the present invention has broad application foreground.
Description
Technical field
The present invention relates to a kind of method of synthesizing formic ester, particularly relate to a kind of method of utilizing catalyst with metal nanoparticles catalysis synthesizing formic ester.
Background technology
Formic acid esters is that a big class is used carboxylic acid ester compound quite widely, and they are not only the important intermediate that important chemical products still is organic synthesis.For example, methyl formate is a kind of broad-spectrum low boiling point solvent, can directly be used as pesticide, bactericide and be used to handle the fumigant of cereal, fruit, dry fruit, tobacco.Be commonly used for the intermediate of medical science, agricultural chemicals and organic synthesis, the solvent of cellulose acetate.At present, industrial main as the intermediate products of producing dimethyl formamide and formic acid.Ethyl formate is important organic solvent, is used for organic synthesis, can also be used as system aroma material, bactericide such as cigarette, food industry, cereal, dry fruit product, and the raw material of medical industry.Butyl formate is used for spices manufacturing, organic synthesis, chemical reagent etc. as solvent.And the methyl isobutyl ester also is used to make spices, pesticide and is used for organic synthesis as the solvent of cellulose, resin and lacquer.
At present, the method that is used for synthetic methyl formate mainly contains methanol dehydrogenation method, methyl alcohol partial oxidation process, synthesis gas direct synthesis technique, esterification process, formaldehyde dimerization method, carbon dioxide/methanol hydrogenization method and methanol carbonylation etc.But all there are some shortcomings in these methods, and for example, esterification process is synthesized the cost height, equipment corrosion is serious; Formaldehyde dimerization method weak effect, cost height; Low, the poor selectivity of air factor during the methanol oxidation dehydriding; Space-time yield and selectivity that the synthesis gas direct synthesis technique prepares methyl formate are low, are difficult to realize industrialization.Methanol carbonylation is the production method of present state-of-the-art methyl formate, selects for use sodium formate to make catalyst, and under 80 ℃ of reaction temperatures, pressure 4-6MPa, CO and conversion of methanol are respectively 95% and 30%, the selectivity of methyl formate nearly 100%; But also there is following shortcoming: need to use the higher absolute methanol of price; Must be higher than 80% expensive CO by working concentration.In addition, water and CO in the reaction system
2Existence can bring operational issue, improved the technology cost greatly.Simultaneously, the easy corrosion reaction equipment of the strong basicity of catalyst has been violated the aim of Green Chemistry.Therefore, develop new catalyst system, realize the synthetic technology of carbonylation of efficient, green methyl formate and other formic acid esters, on academic and industrial production, all have considerable meaning.
Summary of the invention
The method and the special-purpose metal nanometer particle catalyst thereof that the purpose of this invention is to provide a kind of synthesizing formic ester.
The method for preparing catalyst with metal nanoparticles provided by the invention is slaine to be mixed with macromolecule stabilizer be scattered in the liquid medium, and the reducing agent reduction promptly obtains this catalyst with metal nanoparticles.
Slaine is selected from one or more in copper, silver, nickel, gold, zinc, palladium, platinum, rhodium, the molysite; Can be the inorganic salts of above-mentioned slaine, as in copper chloride, copper nitrate, copper sulphate, chlorination cuprammonium, copper carbonate, basic copper carbonate, copper bromide, silver nitrate, silver oxide, silver chlorate, silver carbonate, silver sulfate, silver bromide, nickel chloride, nickel oxide, nickel nitrate, nickelous sulfate, nickelous carbonate, gold chloride, zinc nitrate, zinc chloride, palladium bichloride, palladium nitrate, palladium bichloride, chloroplatinic acid, platinum chloride, potassium chloroplatinate, platinum oxide, radium chloride, the ammonium ferric sulfate one or more; The also organic salt of above-mentioned slaine is as in cupric acetylacetonate, copper acetate, silver thiocyanate, nickel formate, nickel oxalate, nickel acetate, acid chloride, four-(triphenylphosphine) palladium, two benzal acetone palladiums, ferric acetyl acetonade, the ferrocene one or more.Described macromolecule stabilizer is a polyvinylpyrrolidone.Slaine is 1 with the ratio of the amount of substance of macromolecule stabilizer: 1-1: 400, be preferably 1: 100; The concentration of slaine in liquid medium is 0.001-0.100mol/L, is preferably 0.01mol/L.
Liquid medium is alcohols, hydro carbons or ionic liquid; Reducing agent is NaBH
4, ethanol, ethylene glycol, formic acid or hydrogen; Reduction temperature is 10-250 ℃.
In the reaction of above-mentioned synthetic catalyst with metal nanoparticles, the optional methyl alcohol of alcohols, ethanol, isopropyl alcohol, the tert-butyl alcohol, octanol, phenmethylol, particular methanol, ethanol; Optional ion liquid general formula is [C
nMim] X, n=2-18 wherein, X=Cl
-, BF
4 -, PF
6 -, NTf
2 -
The catalyst with metal nanoparticles that utilizes method for preparing to obtain also belongs to protection scope of the present invention; Its particle diameter is 1-10nm, is preferably 2-4nm.
Another one purpose of the present invention provides a kind of method for preparing formic acid esters, is alcohol and carbon monoxide are carried out catalytic reaction under the catalytic action of catalyst with metal nanoparticles of the present invention, promptly obtains described formic acid esters.
Above-mentioned catalytic reaction is pure oxonation, and available alcohol compound can be various primary alcohols, secondary alcohol or tertiary alcohol, as methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol etc.
This reaction temperature is 60-200 ℃, preferred 150 ℃; CO pressure 0.1-10MPa, preferred 1.0MPa; Reaction time is 1-48 hour, preferred 12 hours.
The invention provides a kind of method of utilizing metal nano catalyst alcohol carbonylation synthesizing formic ester.This method has the following advantages: 1) this catalyst with metal nanoparticles can be dispersed in the liquid medium, form stable colloid, can under reaction condition, realize the 3 D auto rotation, thereby have good low temperature active, get final product the synthetic of catalysis formic acid esters down at 60-200 ℃; 2) with the reaction of this metal nano catalyst formic acid esters, have high transformation efficiency and selectivity; 3) the stable and environmental friendliness of this metal nano catalyst property is a green catalyst; 4) simple, the processing ease, with low cost of this method technology.Based on above-mentioned advantage, the synthetic method of formic acid esters provided by the invention will play a significant role in the production of ester chemicals, have the wide industrial application prospect, development potentiality is huge, and its rational exploitation and utilization will bring huge economic benefit and social benefit.
Description of drawings
Fig. 1 a is the electromicroscopic photograph of copper nano-particle catalyst in the embodiment of the invention 1; Fig. 1 b is the particle diameter distribution map of copper nano-particle catalyst.
The specific embodiment
The invention provides a kind of method of utilizing catalyst with metal nanoparticles catalysis synthesizing formic ester, be in reaction system, charge into the CO of certain pressure, under the appropriate reaction temperature, select for use the catalyst with metal nanoparticles catalyzing alcohols to react, promptly obtain formic acid esters; Reaction medium is the liquid medium that catalyst disperseed.
CO conversion ratio under the various reaction conditions is 5-50%, and GC/MS detects and finds that target product formic acid esters selectivity is 20-100%.
Below in conjunction with embodiment the present invention is described in further details, method therefor all carries out under the anhydrous and oxygen-free nitrogen protection among the described embodiment.
Embodiment 1, synthetic methyl formate
Successively 0.5mmol copper nitrate and 50.0mmol polyvinylpyrrolidone (PVP) are placed in the reaction bulb, add 20.0mL methyl alcohol, stir, drip the NaBH of 10.0mL0.5mol/L
4Methanol solution, room temperature reaction 30 minutes obtains the copper nano-particle catalyst.
This catalyst is placed the 100mL reactor, charge into 3.0MPaCO, 150 ℃ were reacted 12 hours.
The conversion ratio of CO is 45%, and GC/MS detects the selectivity 100% of target product methyl formate.
The photo of this copper nano-particle of electron microscopic observation as shown in Figure 1a, its particle diameter distributes shown in Fig. 1 b.As seen from the figure, the particle diameter narrow distribution of this nano particle is about 3.3 ± 0.5nm.Utilize this catalyst to synthesize methyl formate, can obtain higher CO conversion rate is 45%, and product selectivity is very high, is 100%.
Embodiment 2, synthetic methyl formate
Successively slaine copper chloride and PVP were placed in the reaction bulb in 1: 50 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.1mol/L
4Methanol solution, room temperature reaction 0.5 hour obtains nano-particle catalyst, and its particle diameter is 2-4nm.
This catalyst is placed the 100mL reactor, charge into 0.3MPaCO,, reacted 16 hours at 170 ℃.
The conversion ratio of CO is 25%, and GC/MS detects the selectivity 100% of target product methyl formate.
Embodiment 3, synthetic methyl formate
Successively slaine cupric acetylacetonate and PVP were placed in the reaction bulb in 1: 100 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.1mol/L
4Methanol solution, room temperature reaction 1 hour obtains nano-particle catalyst, and its particle diameter is 2-4nm.
This catalyst is placed the 100mL reactor, charge into 2.0MPaCO,, reacted 8 hours at 130 ℃.
The conversion ratio of CO is 38%, and GC/MS detects the selectivity 100% of target product methyl formate.
Embodiment 4, synthetic methyl formate
Successively slaine copper acetate and PVP were placed in the reaction bulb in 1: 20 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.1mol/L
4Methanol solution, room temperature reaction 1 hour obtains nano-particle catalyst, and its particle diameter is 2-4nm.
This catalyst is placed the 100mL reactor, charge into 3.0MPaCO,, reacted 24 hours at 100 ℃.
The conversion ratio of CO is 48%, and GC/MS detects the selectivity 100% of target product methyl formate.
Embodiment 5, synthetic methyl formate
Successively slaine copper acetate and PVP were placed in the reactor in 1: 50 in molar ratio, charge into 4.0MPaH
2, 250 ℃ were reacted 4 hours, reduced to room temperature, charged into 10.0MPaCO, at 100 ℃, reacted 10 hours.
Tell product, and the conversion ratio of measuring CO is 46%, the selectivity 77% of target product methyl formate.
Embodiment 6, synthetic methyl formate
Successively slaine copper acetate, platinum oxide and PVP were placed in the reaction bulb in 10: 1: 50 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH4 methanol solution of 10mL0.05mol/L, room temperature reaction 1 hour obtains nano-particle catalyst, and its particle diameter is 3-9nm.
This catalyst is placed the 100mL reactor, charge into 0.1MPaCO,, reacted 1 hour at 60 ℃.
The conversion ratio of CO is 5%, and GC/MS detects the selectivity 94% of target product methyl formate.
Successively slaine copper chloride, radium chloride and PVP were placed in the reaction bulb in 1: 2: 50 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH4 methanol solution of 10mL0.1mol/L, reaction is 1 hour under the room temperature, obtains nano-particle catalyst, and its particle diameter is 3-10nm.
This catalyst is placed the 100mL reactor, charge into 0.3MPaCO,, reacted 1 hour at 200 ℃.
The conversion ratio of CO is 18%, and GC/MS detects the selectivity 41% of target product methyl formate.
Embodiment 8, synthetic Ethyl formate
Successively with in 1: 10 in molar ratio reaction bulb of slaine silver nitrate and PVP, add 30mL ethanol, stir, drip 10mL ethylene glycol, 100 ℃ of reactions 1 hour down obtain nano-particle catalyst, and its particle diameter is 3-8nm.
This catalyst is placed the 100mL reactor, charge into 3.0MPaCO,, reacted 24 hours at 110 ℃.
The conversion ratio of CO is 35%, and GC/MS detects the selectivity 80% of target product Ethyl formate.
Embodiment 9, synthetic butyl formate
Successively slaine copper nitrate, zinc nitrate and PVP were placed in the reaction bulb in 5: 1: 50 in molar ratio, add the 30mL butanols, stir, drip the NaBH of 10mL0.02mol/L
4Butanol solution, reaction is 1 hour under the room temperature, obtains nano-particle catalyst, and its particle diameter is 3-6nm.
This catalyst is placed the 100mL reactor, charge into 5.0MPaCO,, reacted 48 hours at 100 ℃.
The conversion ratio of CO is 49%, and GC/MS detects the selectivity 90% of target product butyl formate.
Embodiment 10, synthetic iso-butyl formate
Successively slaine copper nitrate, palladium nitrate and PVP were placed in the reaction bulb in 2: 1: 50 in molar ratio, add the 30mL isobutanol, stir, drip the NaBH of 10mL0.1mol/L
4Isobutanol solution, 80 ℃ were reacted 2 hours down, obtained nano-particle catalyst, and its particle diameter is 4-6nm.
This catalyst is placed the 100ml reactor, charge into 3.0MPaCO,, reacted 24 hours at 150 ℃.
The conversion ratio of CO is 27%, and GC/MS detects the selectivity 78% of target product iso-butyl formate.
Embodiment 11, synthetic octyl formate
Successively slaine copper carbonate and PVP were placed in the reaction bulb in 1: 50 in molar ratio, add the 30mL octanol, stir, drip the NaBH of 10mL0.1mol/L
4Octanol solution, 50 ℃ were reacted 1 hour down, obtained nano-particle catalyst, and its particle diameter is 3-6nm.
This catalyst is placed the 100mL reactor, charge into 10.0MPaCO,, reacted 24 hours at 80 ℃.
The conversion ratio of CO is 12%, and GC/MS detects the selectivity 87% of target product octyl formate.
Embodiment 12, synthetic methyl formate
Successively slaine nickel acetate and PVP were placed in the reaction bulb in 1: 100 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.001mol/L
4Methanol solution, reaction is 1 hour under the room temperature, obtains nano-particle catalyst.
This catalyst is placed the 100mL reactor, charge into 6.0MPaCO,, reacted 16 hours at 180 ℃.
The conversion ratio of CO is 6%, and GC/MS detects the selectivity 58% of target product methyl formate.
Embodiment 13, synthetic methyl formate
Successively slaine gold chloride and PVP were placed in the reaction bulb in 1: 100 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.02mol/L
4Methanol solution, reaction is 1 hour under the room temperature, obtains nano-particle catalyst, and its particle diameter is 2-4nm.
This catalyst is placed the 100mL reactor, charge into 4.0MPaCO,, reacted 24 hours at 150 ℃.
The conversion ratio of CO is 21%, and GC/MS detects the selectivity 89% of target product methyl formate.
Embodiment 14, synthetic methyl formate
Successively slaine ammonium ferric sulfate and PVP were placed in the reaction bulb in 1: 100 in molar ratio, add 30mL methyl alcohol, stir, drip the NaBH of 10mL0.03mol/L
4Methanol solution, reaction is 1 hour under the room temperature, obtains nano-particle catalyst.
This catalyst is placed the 100mL reactor, charge into 6.0MPaCO,, reacted 12 hours at 170 ℃.
The conversion ratio of CO is 18%, and GC/MS detects the selectivity 65% of target product methyl formate.
Embodiment 15, synthetic methyl formate
Successively slaine copper nitrate and PVP were placed in the reaction bulb in 1: 10 in molar ratio, add 30mL[C
4Min] BF
4, stir, drip the NaBH of 10mL0.1mol/L
4Methanol solution, room temperature reaction 1 hour obtains nano-particle catalyst, and its particle diameter is 3-8nm.
This catalyst is placed the 100mL reactor, charge into 3.0MPaCO, 120 ℃ were reacted 24 hours.
The conversion ratio of CO is 35%, and GC/MS detects the selectivity 95% of target product methyl formate.
Embodiment 16, synthetic Ethyl formate
Successively slaine copper nitrate and PVP were placed in the reaction bulb in 1: 100 in molar ratio, add 30mL ethanol, stir, drip the NaBH of 20mL0.1mol/L
4Ethanolic solution, room temperature reaction 30 minutes obtains nano-particle catalyst, and its particle diameter is 2-8nm.
This catalyst is placed the 100mL reactor, charge into 3.0MPaCO, 120 ℃ were reacted 24 hours.
The conversion ratio of CO is 39%, and GC/MS detects the selectivity 100% of target product Ethyl formate.
Embodiment 17, synthetic methyl formate
Successively slaine copper nitrate and PVP were placed in the reaction bulb in 1: 50 in molar ratio, add 30mL methyl alcohol, stir, drip 10mL formic acid, room temperature reaction 1 hour obtains nano-particle catalyst, and its particle diameter is 3-5nm.
This catalyst is placed the 100mL reactor, charge into 4.0MPaCO, 130 ℃ were reacted 48 hours.
The conversion ratio of CO is 24%, and GC/MS detects the selectivity 90% of target product methyl formate.
Above result shows that metal nano catalyst provided by the invention has good catalytic activity and high formic acid esters selectivity at 60-200 ℃, is a kind of green catalyst; Utilize the method for this catalyst synthesizing formic ester, technology is simple, and is with low cost, and environment-friendly high-efficiency has favorable industrial application prospect.
Claims (10)
1. a method for preparing catalyst with metal nanoparticles is slaine to be mixed with macromolecule stabilizer be scattered in the liquid medium, and the reducing agent reduction promptly obtains described metal nano catalyst.
2. preparation method according to claim 1 is characterized in that: described slaine is selected from one or more in copper, silver, nickel, gold, zinc, palladium, platinum, rhodium, the molysite; Described macromolecule stabilizer is a polyvinylpyrrolidone.
3. preparation method according to claim 1 is characterized in that: described liquid medium is alcohols, hydro carbons or ionic liquid; Described reducing agent is NaBH
4, ethanol, ethylene glycol, formic acid or hydrogen; Described reduction temperature is 10-250 ℃.
4. preparation method according to claim 3 is characterized in that: described alcohols is methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, octanol, phenmethylol, particular methanol, ethanol; Described ion liquid general structure is [C
nMim] X, n=2-18 wherein, X=Cl
-, BF
4 -, PF
6 -Or NTf
2 -
5. preparation method according to claim 1 is characterized in that: described slaine is 1 with the ratio of the amount of substance of described macromolecule stabilizer: 1-1: 400, be preferably 1: 100; The concentration of described slaine in described liquid medium is 0.001-0.100mol/L, is preferably 0.01mol/L.
6. the catalyst with metal nanoparticles that obtains of the arbitrary described preparation method of claim 1-5.
7. catalyst according to claim 6 is characterized in that: the particle diameter of described catalyst is 1-10nm, is preferably 2-4 nm.
8. the method for a synthesizing formic ester is that alcohol and carbon monoxide are carried out catalytic reaction under the catalytic action of the described catalyst with metal nanoparticles of claim 6, promptly obtains described formic acid esters.
9. method according to claim 8 is characterized in that: described alcohol is primary alcohol, secondary alcohol, tertiary alcohol, particular methanol, ethanol, isopropyl alcohol or the tert-butyl alcohol.
10. method according to claim 8 is characterized in that: described reaction temperature is 60-200 ℃, preferred 150 ℃; The pressure of described carbon monoxide is 0.1-10MPa, preferred 1.0MPa; The described reaction time is 1-48 hour, preferred 12 hours.
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| WO2008134939A1 (en) * | 2007-05-08 | 2008-11-13 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
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| CN103694116A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Method for synthesizing methyl formate by gas-phase carbonylation of methyl alcohol |
| CN103691451A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst |
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| WO2015103851A1 (en) * | 2014-01-07 | 2015-07-16 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | A process for vapor-phase methanol carbonylation to methyl formate, a catalyst used in the process and a method for preparing the catalyst |
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| CN100548476C (en) * | 2008-05-19 | 2009-10-14 | 中国科学院山西煤炭化学研究所 | A kind ofly be suitable for used for slurry bed nanocatalyst and method for making and application |
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| CN103691451A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst |
| CN103694116A (en) * | 2014-01-07 | 2014-04-02 | 中国科学院福建物质结构研究所 | Method for synthesizing methyl formate by gas-phase carbonylation of methyl alcohol |
| US9944587B2 (en) | 2014-01-07 | 2018-04-17 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Process for vapor-phase methanol carbonylation to methyl formate, a catalyst used in the process and a method for preparing the catalyst |
| CN107445149A (en) * | 2016-05-31 | 2017-12-08 | 嘉泉大学校产学协力团 | Graphene metal nanoparticle complex |
| CN107445149B (en) * | 2016-05-31 | 2021-02-02 | 嘉泉大学校产学协力团 | Graphene metal nanoparticle composite |
| CN113042069A (en) * | 2021-03-31 | 2021-06-29 | 泉州师范学院 | Synthetic method and application of palladium-copper nano catalyst for formic acid reduction |
| CN113731504A (en) * | 2021-09-09 | 2021-12-03 | 天津理工大学 | Catalyst and preparation method and application thereof |
| CN113731504B (en) * | 2021-09-09 | 2023-08-29 | 天津理工大学 | Catalyst and preparation method and application thereof |
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