CN103524337A - Preparation method of butyl levulinate by use of biomass based furfuryl alcohol - Google Patents
Preparation method of butyl levulinate by use of biomass based furfuryl alcohol Download PDFInfo
- Publication number
- CN103524337A CN103524337A CN201310474223.7A CN201310474223A CN103524337A CN 103524337 A CN103524337 A CN 103524337A CN 201310474223 A CN201310474223 A CN 201310474223A CN 103524337 A CN103524337 A CN 103524337A
- Authority
- CN
- China
- Prior art keywords
- furfuryl alcohol
- reaction
- temperature
- preparation
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000002028 Biomass Substances 0.000 title claims abstract description 18
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 title abstract description 6
- 229940005460 butyl levulinate Drugs 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000004821 distillation Methods 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 26
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 12
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 34
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 claims description 31
- 239000001117 sulphuric acid Substances 0.000 claims description 23
- 235000011149 sulphuric acid Nutrition 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000003377 acid catalyst Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229940058352 levulinate Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- -1 Butyl acetylpropanoate Chemical compound 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005522 oxopentanoic acid group Chemical group 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of butyl levulinate by use of biomass based furfuryl alcohol, the preparation method uses the furfuryl alcohol as a raw material, a mixed system of n-butyl alcohol and a little added water is used as a reactant and a reaction medium, a ultra low acid (<= 0.01mol/L) is used as a catalyst, a reaction is performed at 100-200 DEG C for 6-10 h; a reaction solution is adjusted to neutral, first a solvent, the reactant and low boiling point substances are evaporated out by two times of atmospheric distillation at the temperature of 120-180 DEG C, and then the butyl levulinate is obtained by vacuum distillation at the temperature of 190-210 DEG C under the pressure of 1000-2000Pa, according to the preparation method, the occurrence rate of a polymerization side reaction of the furfuryl alcohol is less, the target product butyl levulinate is high in yield, after the reaction, waste acid is easy to process, consumed neutralization chemicals and produced waste slag are less, environmental pollution and equipment corrosion are less, the production cost is low, and the preparation method has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of biomass-based furfuryl alcohol and prepare the method for Butyl acetylpropanoate, belong to the technical field of Biomass Energy Utilization.
Background technology
Butyl acetylpropanoate (Butyl Levulinate, CAS No:2052-15-5), have another name called oxopentanoic acid butyl ester, 4-ketone butyl valerate or 4-oxopentanoie acid butyl ester, it is a kind of colourless transparent liquid with aromatic odour, boiling point is higher, be soluble in ethanol, ether, the most organic solvent such as chloroform, from molecular structure, Butyl acetylpropanoate contains undersaturated carbonyl and ester group, can become enol-type structure by isomery, there is higher reactive behavior, can be used as reaction substrate is hydrolyzed, addition, replace, transesterify, the reactions such as redox, thereby derive the chemical with industrial significance of One's name is legion.Butyl acetylpropanoate is also a kind of very potential new forms of energy chemical, be widely used in the industries such as food, makeup, medicine, softening agent, in addition, its character is similar to biofuel, can be used as transportation propellant combination or the additives such as diesel oil, after interpolation, can effectively improve combustion cleaning degree, and possess good lubricity, flash-point stability and low-temperature fluidity.
The product that furfuryl alcohol comes authigenic material pentose class degraded product furfural to obtain after hydrogenation reaction, of many uses, except being used as selective solvent, flotation agent etc., also be one of raw material of producing the multiple important chemical such as furane resin, levulinate, under an acidic catalyst effect, furfuryl alcohol heats and can react generation levulinate in alcohol system.Tradition research is mainly usingd the mineral acids such as dilute sulphuric acid (1～5%) as catalyzer with application, yet under strong inorganic acid effect, the easy polymerization reaction take place of furfuryl alcohol forms oligopolymer, cause target product levulinate yield not high, conventionally need to add excessive alcohol medium and reduce furfuryl alcohol polymerization, in addition, after having reacted, spent acid is processed trouble, need to add more alkaline matter to neutralize, and produces waste residue many, and corrodibility is strong, to reactor material, require high, with solid acid, replace inorganic liquid acid to cause widely and paid close attention to as catalyzer in recent years, it is high that it has reactive behavior, easily and product separation, not etching apparatus and the plurality of advantages such as free from environmental pollution, but solid acid catalyst price is relatively costly, and because polymerization side reactions generation carbide can occur furfuryl alcohol, be adsorbed on solid acid surface in this reaction process, cause its catalytic activity obviously to reduce, be difficult to repeatedly reuse, cause production cost to increase, seriously hindered the actual mass-producing application of this technology, based on the problems referred to above, be necessary very much to develop a kind of method that economical and efficient conversion of biomass base furfuryl alcohol is prepared levulinate, thereby for its industrialization practical application provides Technical Reference.
Ultralow acid refers to that concentration is lower than the about 0.01mol/L of 0.1%() acid system, aspect cellulose hydrolysis, being subject to people pays close attention to more widely, at present the new type of continuous hydrocellulose reactor of exploitation is main mainly with extremely low acids hydrolysis, and it has the features such as little to equipment corrosion, product postprocessing is simple and environmental pollution is little.
Summary of the invention
The object of the present invention is to provide a kind of biomass-based furfuryl alcohol to prepare the method for Butyl acetylpropanoate, specifically comprise the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, the ratio that is 1:0.1:1:97.9 ~ 10:5:10:75 in sulphuric acid soln, water, furfuryl alcohol, propyl carbinol volume ratio is mixed sulphuric acid soln, water, furfuryl alcohol, propyl carbinol, reaction while stirring, wherein stir speed (S.S.) is 200～1000r/min, temperature is risen to 100～120 ℃, insulation reaction 6～10h;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product, then in the ratio of 0.056～0.56g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, and filtering separation obtains liquid substance and solid slag;
(3) liquid substance first boils off solvent, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 120～130 ℃, 170～180 ℃, then through underpressure distillation, obtain Butyl acetylpropanoate, vacuum distillation temperature is that 190～210 ℃, pressure are 1000～2000Pa.
Furfuryl alcohol of the present invention is commercially available furfuryl alcohol.
Sulfuric acid of the present invention volumetric molar concentration in reaction mixture is 0.001～0.01mol/L, is ultralow acid catalyst.
Beneficial effect of the present invention is:
(1) the present invention is usingd ultralow acid (volumetric molar concentration is 0.001～0.01mol/L) as catalyzer, and furfuryl alcohol generation polymerization side reactions obviously reduces, and has effectively improved target product Butyl acetylpropanoate yield;
(2) to react rear spent acid few in the present invention, easily processes, and consumes neutralization chemicals and produce waste residue few, and environmental pollution is little;
(3) the present invention changes into Butyl acetylpropanoate production cost by furfuryl alcohol and can significantly reduce, and economic benefit is improved, and possesses good prospects for commercial application.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 1mL, 0.1mL water, 1mL furfuryl alcohol and 97.9mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 200r/min, temperature is risen to 110 ℃, insulation reaction 10h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.001mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product 0.01g, then in the ratio of 0.056g/L, in filtrate, add in anhydrous calcium oxide and dry reaction liquid, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.017g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 120 ℃, 170 ℃, then through underpressure distillation, obtain 1.1g Butyl acetylpropanoate, purity is 97.3%(GC), molar yield is 53.5%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1000Pa.
Embodiment 2
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 10mL, 5mL water, 10mL furfuryl alcohol and 75mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 1000r/min, temperature is risen to 120 ℃, insulation reaction 6h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.005mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, and first filtering separation obtains furfuryl alcohol polymer/solid by product 0.54g, then in the ratio of 0.28g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.083g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 125 ℃, 175 ℃, then through underpressure distillation, obtain 5.6g Butyl acetylpropanoate, purity is 98.6%(GC), molar yield is 31.5%, and wherein vacuum distillation temperature is that 210 ℃, pressure are 2000Pa.
Embodiment 3
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 10mL, 5mL water, 1mL furfuryl alcohol and 84mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 600r/min, temperature is risen to 100 ℃, insulation reaction 8h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.01mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product 0.06g, then in the ratio of 0.56g/L, in filtrate, add in anhydrous calcium oxide and dry reaction liquid, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.165g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 130 ℃, 180 ℃, then through underpressure distillation, obtain 1.2g Butyl acetylpropanoate, purity is 98.2%(GC), molar yield is 60.9%, and wherein vacuum distillation temperature is that 190 ℃, pressure are 1000Pa.
Embodiment 4
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 8mL, 1mL water, 5mL furfuryl alcohol and 86mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 800r/min, temperature is risen to 120 ℃, insulation reaction 8h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.008mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product 0.25g, then in the ratio of 0.448g/L, in filtrate, add in anhydrous calcium oxide and dry reaction liquid, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.131g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 125 ℃, 180 ℃, then through underpressure distillation, obtain 6.2g Butyl acetylpropanoate, purity is 98.5%(GC), molar yield is 62.2%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1000Pa.
Embodiment 5
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 3mL, 3mL water, 8mL furfuryl alcohol and 86mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 400r/min, temperature is risen to 110 ℃, insulation reaction 10h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.003mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product 0.37g, then in the ratio of 0.168g/L, in filtrate, add in anhydrous calcium oxide and dry reaction liquid, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.049g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 130 ℃, 175 ℃, then through underpressure distillation, obtain 7.1g Butyl acetylpropanoate, purity is 98.4%(GC), molar yield is 43.7%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1500Pa.
Embodiment 6
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 5mL, 0.1mL water, 3mL furfuryl alcohol and 91.9mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 800r/min, temperature is risen to 110 ℃, insulation reaction 8h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.005mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, and first filtering separation obtains furfuryl alcohol polymer/solid by product 0.08g, in the ratio of 0.28g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.08g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 120 ℃, 180 ℃, then through underpressure distillation, obtain 4.7g Butyl acetylpropanoate, purity is 98.5%(GC), molar yield is 78.4%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1000Pa.
Embodiment 7
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, specifically comprises the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 5mL, 0.1mL water, 1mL furfuryl alcohol and 93.9mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 800r/min, temperature is risen to 110 ℃, insulation reaction 8h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.005mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, and first filtering separation obtains furfuryl alcohol polymer/solid by product 0.02g, in the ratio of 0.28g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.08g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 120 ℃, 180 ℃, then through underpressure distillation, obtain 1.8g Butyl acetylpropanoate, purity is 98.8%(GC), molar yield is 92.6%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1000Pa.
Embodiment 8
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then measuring successively the above-mentioned sulphuric acid soln of 5mL, 2mL water, 1mL furfuryl alcohol and 92mL propyl carbinol joins in 250mL there-necked flask and mixes, obtain 100mL reaction mixture, there-necked flask is placed in to magnetic agitation oil bath pan, turn on agitator, reaction while stirring, wherein stir speed (S.S.) is 800r/min, temperature is risen to 110 ℃, insulation reaction 8h;
In this enforcement, in reaction mixture, sulfuric acid volumetric molar concentration is 0.005mol/L, is ultralow acid catalyst;
(2) after reaction finishes, reaction solution is cooled to room temperature, and first filtering separation obtains furfuryl alcohol polymer/solid by product 0.02g, in the ratio of 0.28g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, filtering separation obtains liquid substance and solid slag, wherein solid slag 0.09g;
(3) liquid substance first steams except desolventizing, reactant and low-boiling products through twice air distillation, twice air distillation temperature is followed successively by 120 ℃, 180 ℃, then through underpressure distillation, obtain 1.9g Butyl acetylpropanoate, purity is 97.8%(GC), molar yield is 96.5%, and wherein vacuum distillation temperature is that 200 ℃, pressure are 1000Pa.
Embodiment 9(simultaneous test)
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, and concrete steps are with embodiment 6, and difference is: in mixed solution, sulfuric acid volumetric molar concentration is 0.2mol/L, is diluted acid catalyzer; Obtain furfuryl alcohol polymer/solid by product 0.38g, need in filtrate, add in anhydrous calcium oxide and dry reaction liquid in the ratio of 11.2g/L, produce solid slag 3.38g; Obtain 4.2g Butyl acetylpropanoate, purity is 97.7%(GC), molar yield is 69.5%.
Embodiment 10(simultaneous test)
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, and concrete steps are with embodiment 7, and difference is: in mixed solution, sulfuric acid volumetric molar concentration is 0.2mol/L, is diluted acid catalyzer; Obtain furfuryl alcohol polymer/solid by product 0.12g, need in filtrate, add in anhydrous calcium oxide and dry reaction liquid in the ratio of 11.2g/L, produce solid slag 3.25g; Obtain 1.6g Butyl acetylpropanoate, purity is 98.1%(GC), molar yield is 80.5%.
Embodiment 11(simultaneous test)
Described in the present embodiment, biomass-based furfuryl alcohol is prepared the method for Butyl acetylpropanoate, and concrete steps are with embodiment 8, and difference is: in mixed solution, sulfuric acid volumetric molar concentration is 0.2mol/L, is diluted acid catalyzer; Obtain furfuryl alcohol polymer/solid by product 0.11g, need in filtrate, add in anhydrous calcium oxide and dry reaction liquid in the ratio of 11.2g/L, produce solid slag 3.44g; Obtain 1.7g Butyl acetylpropanoate, purity is 97.7%(GC), molar yield is 84.8%.
Claims (1)
1. biomass-based furfuryl alcohol is prepared a method for Butyl acetylpropanoate, it is characterized in that comprising the steps:
(1) take propyl carbinol is first equipped with the sulphuric acid soln that volumetric molar concentration is 0.1mol/L as solvent, then the ratio that is 1:0.1:1:97.9 ~ 10:5:10:75 in sulphuric acid soln, water, furfuryl alcohol, propyl carbinol volume ratio is mixed sulphuric acid soln, water, furfuryl alcohol, propyl carbinol, reaction while stirring, wherein stir speed (S.S.) is 200～1000r/min, temperature is risen to 100～120 ℃, insulation reaction 6～10h;
(2) after reaction finishes, reaction solution is cooled to room temperature, first filtering separation obtains furfuryl alcohol polymer/solid by product, then in the ratio of 0.056～0.56g/L, adds in anhydrous calcium oxide and dry reaction liquid in filtrate, and filtering separation obtains liquid substance and solid slag;
(3) liquid substance first through twice air distillation, boil off desolventize, reactant and low-boiling products, twice air distillation temperature is followed successively by 120～130 ℃, 170～180 ℃, then through underpressure distillation, obtain Butyl acetylpropanoate, vacuum distillation temperature is that 190～210 ℃, pressure are 1000～2000Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310474223.7A CN103524337A (en) | 2013-10-12 | 2013-10-12 | Preparation method of butyl levulinate by use of biomass based furfuryl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310474223.7A CN103524337A (en) | 2013-10-12 | 2013-10-12 | Preparation method of butyl levulinate by use of biomass based furfuryl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103524337A true CN103524337A (en) | 2014-01-22 |
Family
ID=49926747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310474223.7A Pending CN103524337A (en) | 2013-10-12 | 2013-10-12 | Preparation method of butyl levulinate by use of biomass based furfuryl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524337A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945446A (en) * | 2015-05-20 | 2015-09-30 | 中国科学院广州能源研究所 | Method for preparing formate, acetate and levulinate from straw biomass |
| CN110963914A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing alkyl levulinate by controlling water content |
-
2013
- 2013-10-12 CN CN201310474223.7A patent/CN103524337A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张玉兰 等: "4-氧代戊酸酯类缩酮的合成研究", 《兰州大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945446A (en) * | 2015-05-20 | 2015-09-30 | 中国科学院广州能源研究所 | Method for preparing formate, acetate and levulinate from straw biomass |
| CN104945446B (en) * | 2015-05-20 | 2017-11-14 | 中国科学院广州能源研究所 | A kind of method that formic acid esters, acetic acid esters, levulinate are prepared using stalk biomass |
| CN110963914A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing alkyl levulinate by controlling water content |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012334B (en) | Method for preparing gamma-valerolactone with high selectivity under mild condition | |
| Zhuo et al. | Hydrolysis of cellulose catalyzed by novel acidic ionic liquids | |
| CN100497526C (en) | Method for synthesizing biologic diesel oil based on ion liquid | |
| Zhang et al. | Catalytic performance of a novel amphiphilic alkaline ionic liquid for biodiesel production: Influence of basicity and conductivity | |
| Shi et al. | Esterification of acidified oil with methanol by SPES/PES catalytic membrane | |
| CN103288643B (en) | The method of ethyl levulinate is prepared based on the alcoholysis of carbon-based solid acid catalysis furfuryl alcohol | |
| CN202643671U (en) | Biodiesel counter-flow continuous esterification reaction system | |
| He et al. | Continuous biodiesel production from acidic oil using a combination of cation-and anion-exchange resins | |
| CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| CN103467435B (en) | A kind of method preparing glycerol carbonate | |
| CN103274942A (en) | Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis | |
| CN101376818A (en) | Method for preparing biodiesel by synergic ion liquid catalysis under cavitation effect | |
| Shi et al. | Multiple-SO3H functionalized ionic liquid as efficient catalyst for direct conversion of carbohydrate biomass into levulinic acid | |
| CN103044237A (en) | Method for preparing levulinic acid by converting cellulose efficiently | |
| CN107188802A (en) | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type | |
| Han et al. | Novel self-solidifying double-site acidic ionic liquid as efficient and reusable catalyst for green biodiesel synthesis | |
| CN103666773A (en) | Method for producing biodiesel in micro-structure reactor | |
| Song et al. | Brønsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers | |
| CN102504891B (en) | Preparation method of glyceryl biological fuel additives | |
| CN101869847B (en) | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof | |
| CN103524337A (en) | Preparation method of butyl levulinate by use of biomass based furfuryl alcohol | |
| Luo et al. | Regeneration of caprolactam-based Brønsted acidic ionic liquid during transesterification of Jatropha oil | |
| Xu et al. | Aluminum chloride‐catalyzed conversion of levulinic acid to methyl levulinate: optimization and kinetics | |
| CN108440462A (en) | A method of 5 hydroxymethyl furfural being prepared by fructose under no acid system | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140122 |