CN103232418B - Homogeneous catalytic preparation method of gamma-valerolactone - Google Patents
Homogeneous catalytic preparation method of gamma-valerolactone Download PDFInfo
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Abstract
The invention relates to a homogeneous catalytic preparation method of gamma-valerolactone. The method comprises the step of reacting an acetylpropionic acid raw material with a hydrogen source raw material to obtain the product of gamma-valerolactone by using water as a solvent and with the existence of a water soluble iridium catalyst. By adopting the method disclosed by the invention, the defect that the existing preparation method of the gamma-valerolactone needs harsh reaction conditions of high temperature, high pressure, a lot of organic acid, a lot of organic base, and a lot of organic solvent is conquered, the economical efficiency and safety of the preparation method are improved, reaction is simple, catalyst is small in dose and can be repeatedly used, and the product is high in yield, easy to separate, and is quite high in industrial application value.
Description
Technical field
The present invention relates to the preparation of chemical, particularly relate to a kind of preparation method of γ-valerolactone.
Background technology
Current human society depends on the required energy and chemical for existence and development mainly from traditional fossil feedstock, as coal, oil, Sweet natural gas etc.Along with the consumption gradually of these fossil feedstock, need to start to find new alternate resources.Therefore biomass both as the energy, also as the source of organic carbon for the production of chemical and material, can be considered to the new resources most possibly replacing fossil feedstock.γ-valerolactone is the biomass plateform molecules that a kind of potential using value is very high, both can use as New-type fuel, again can as the chemical of the source of organic carbon for the synthesis of high added value.
At present, the preparation of γ-valerolactone mainly with biomass plateform molecules levulinic acid for raw material, by heterogeneous catalyst or homogeneous catalyst hydrogenating reduction and the acquisition that lactonizes.Patent application WO02074760 and US20030055270 discloses under loaded noble metal catalyst effect, is 215 DEG C in temperature of reaction, can obtain γ-valerolactone by the hydrogen reaction of levulinic acid and 700 ~ 800psi with the productive rate of 97%.Patent application CN101805316A discloses a kind of method that supported iridium catalyst prepares γ-valerolactone, it is 25 ~ 200 DEG C in temperature of reaction, γ-valerolactone can be obtained with the productive rate of more than 99% when hydrogen pressure is 0.1 ~ 5MPa, but the preparation of the catalyzer wherein used needs hot conditions, such as under 400 DEG C of air atmospheres after roasting in 300 DEG C of hydrogen gas stream reductase 12 hour.Use heterogeneous catalyst can produce 2-methyltetrahydrofuran impurity in reaction, it easily generates superoxide, causes there is hidden peril of explosion.It is that hydrogen source is when temperature of reaction is 100 ~ 200 DEG C that patent application CN101376650 discloses with formic acid, be under the ruthenium-based catalyst of 0.1 ~ 0.2mol% of levulinic acid amount of substance in usage quantity, γ-valerolactone is prepared by catalytic hydrogenation, its productive rate is the highest can reach 99%, although the method directly can utilize biomass hydrolysate, need inorganic or organic bases in a large number.Patent application CN102558108A discloses the method that a kind of iridium-pincer ligand complex catalysis prepares γ-valerolactone, mild condition, there is higher productive rate and selectivity, but reaction system needs with an organic solvent, and the tolerance of catalyzer to acid is poor, need to add in a large amount of mineral alkalis and levulinic acid raw material.
Therefore, on the whole, prepare γ-valerolactone with existing technique and there is severe reaction conditions (High Temperature High Pressure), problem that catalyst levels is larger, cause production cost high, be difficult to large-scale production, also there is problem of environmental pollution simultaneously.
Summary of the invention
In view of above-mentioned, the object of the present invention is to provide a kind of method preparing γ-valerolactone newly, it can overcome the part or all of defect of prior art.
For this reason, the invention provides a kind of method being prepared γ-valerolactone by homogeneous catalysis, it is characterized in that, using water as solvent, under water-soluble iridium catalyst exists, make the acetyl-propionic acid raw material represented by following formula I and the hydrogen source class raw material reaction represented by Formula Il and obtain product γ-valerolactone:
Wherein said water-soluble iridium catalyst has following chemical formula:
In the formula, substituent R is H, hydroxyl, carboxyl or methoxyl group, and R is positioned at the ortho position of pyridine ring atom N, contraposition or a position; M represents and is selected from SO
4 2-, NO
3 -, Cl
-or trifluoromethanesulfonic acid root (OTf
-) negatively charged ion.
In a preferred embodiment, described acetyl-propionic acid raw material is levulinic acid, levulinate or the biomass hydrolysate containing levulinic acid.
In a preferred embodiment, described hydrogen source class raw material is hydrogen (H
2), formic acid or formate.
In a preferred embodiment, described method is without the need to additionally adding mineral alkali or acid to regulate the pH value of reaction soln.
In a preferred embodiment, the mol ratio of described acetyl-propionic acid raw material and described hydrogen source class raw material is 1: 1-1: 2.Preferably, when described hydrogen source class raw material is H
2time, the H of use
2pressure be 1MPa-10MPa.
In a preferred embodiment, the mole dosage of described water-soluble iridium catalyst is the 0.001%-1% of described acetyl-propionic acid raw material.
In a preferred embodiment, the temperature of described reaction is room temperature to 200 DEG C, and the pressure of described reaction is that normal pressure is to 10MPa.
In a preferred embodiment, described method also comprises to be carried out extracting with separated product γ-valerolactone with organic solvent, and wherein said organic solvent is selected from ether, methyl tertiary butyl ether, ethyl acetate or toluene.
In a preferred embodiment, after the described product γ-valerolactone of separation, the aqueous solution containing described catalyzer is recycled.
It is little and can be recycled that the method that the present invention prepares γ-valerolactone has catalyst levels, and product yield is high, and reaction conditions is relatively gentle, advantages of environment protection, has the industrial prospect of large-scale application.
Accompanying drawing explanation
Fig. 1 display recycles result according to water-soluble iridium catalyst of the present invention.
Embodiment:
Homogeneous catalysis of the present invention prepares the method for γ-valerolactone using water as solvent, under water-soluble iridium catalyst exists, makes the acetyl-propionic acid raw material represented by following formula I and the hydrogen source class raw material reaction represented by Formula Il and obtains product γ-valerolactone.
Reaction formula is as follows:
In the methods of the invention, the acetyl-propionic acid raw material represented by formula I used can for levulinic acid, levulinate be as levulinic acid sodium salt or levulinic acid sylvite, or biomass examples as glucose, fructose, sucrose, Mierocrystalline cellulose, starch etc. containing the hydrolyzed solution of levulinic acid.In the methods of the invention, the hydrogen source class raw material represented by formula II of use can for hydrogen, formic acid or formate be as sodium formiate or potassium formiate.Preferably, in the present invention, the acetyl-propionic acid raw material represented by formula I is 1: 1-1: 2 with the mol ratio of the hydrogen source class raw material represented by formula II.More preferably, when the hydrogen source class raw material represented by formula II is H
2time, the H of use
2pressure be 1MPa-10MPa.
In the methods of the invention, the catalyzer used is water-soluble iridium catalyst, and it has following chemical formula:
In the formula, substituent R is H, hydroxyl, carboxyl or methoxyl group, the position of substituent R at the ortho position of pyridine ring atom N, contraposition or a position; And substituent R can only on a pyridine ring or simultaneously on two pyridine rings; M negatively charged ion can be SO
4 2-, NO
3 -, Cl
-or OTf
-.Here be noted that in chemical formula as implied above, the part above central atom Ir is for having the five-membered ring structure (Cp of five methyl
*) (i.e. pentamethyl-cyclopentadienyl ligand).
The catalyzer used in the inventive method can such as but not limited to following preparation: by [Cp
*irCl
2]
2and Ag
2sO
4, silver trifluoromethanesulfonate (AgOTf) reaction to produce [Cp
*ir (H
2o)
3] SO
4or [Cp
*ir (H
2o)
3] (OTf)
2.Use corresponding bipyridine ligand again
with [the Cp obtained above
*ir (H
2o)
3] SO
4or [Cp
*ir (H
2o)
3] (OTf)
2react and obtain reaction water-soluble iridium catalyst used.
The reaction solvent used in the methods of the invention is water, because the raw material itself wherein used can make reaction system be acid or weakly alkaline, so catalyzer to pH value without particular requirement, adaptability is good, and does not need additionally to add mineral alkali or acid to regulate the pH value of reaction system.Preferably, the mole dosage of described water-soluble iridium catalyst is the 1%-0.001% of the amount of the acetyl-propionic acid raw material represented by formula I.
In the methods of the invention, the temperature of reaction is room temperature to 200 DEG C, is preferably 50-170 DEG C, such as 120 DEG C; The pressure of reaction is that normal pressure is to 10MPa; As use H
2during as reaction raw materials, be preferably 0.5-7MPa, such as 1MPa.
In the methods of the invention, after having reacted, available gas-chromatography (GC) detects reaction product, and testing conditions is as follows: use DM WAX post, gasification temperature 250 DEG C, post flow 1.37mL/min, linear velocity 25cm/s; Post case adopts temperature programming: 50 DEG C keep 3min, rise to 180 DEG C and keep 2min, then rise to 240 DEG C with the speed of 10 DEG C/min with the speed of 20 DEG C/min; Detected temperatures 280 DEG C.
The present invention has advantage and includes but not limited to following:
(1) catalyst activity is high, good reaction selectivity, productive rate high (reaction yield reaches as high as 99%);
(2) react easy, mild condition, avoid and use a large amount of mineral alkalis or acid, improve the economy of production system;
(3) use water as solvent, not with an organic solvent, environmental friendliness;
(4) product is separated by simple extraction process, and separation yield can reach 98%; And the remaining aqueous catalyst solution that contains can recycle after separated product, catalytic performance is substantially constant.
Embodiment
The invention is further illustrated by the following examples, but should understand, scope of the present invention is not by the restriction of these embodiments.
the preparation of water-soluble iridium catalyst
Under argon atmosphere, in the three-necked flask that whipping appts is housed, by [Cp
*irCl
2]
2(480mg, 0.60mmol) and Ag
2sO
4(374mg, 1.20mmol) joins in 4mL water, by this mixture at room temperature stirring reaction 12h.By crossing the precipitate A gCl filtering generation, remaining solution decompression revolves and steams and vacuum-drying, obtains [the Cp of yellow powder
*ir (H
2o)
3] SO
4(550mg, productive rate: 96%)
In the three-necked flask that whipping appts and reflux are housed, by [Cp
*ir (H
2o)
3] SO
4(48mg, 0.10mmol) is dissolved in 12.5mL water, adds bipyridine ligand (0.11mmol) under argon atmosphere.After back flow reaction 12h, filtering solution.The filtrate decompression obtained is revolved and steams and obtain solid product, be i.e. the catalyzer 1 of following formula 1 expression.
Similarly, by use respectively have different substituents R (R be respectively carboxyl, hydroxyl, methoxyl group and at different positions) bipyridine ligand obtain the catalyzer 2-8 that following formula 2-8 represents.
Embodiment 1-8
By the above-mentioned system of the levulinic acid aqueous solution (1.25mmol/mL) 4mL and 1mL prepared in advance the aqueous solution (500 μm of ol/L) of catalyzer 1-8 add respectively in reactor, hydrogen pressure is adjusted to 1MPa, stirring reaction 4h at 120 DEG C after reactor inside hydrogen exchange 3 times.After having reacted, reaction system is cooled to room temperature, then to reaction soln sampling and with methyl alcohol to after diluted sample, by the productive rate of GC detection product γ-valerolactone.The catalyzer used in reaction and relative to the mole dosage of raw material levulinic acid, hydrogen source raw material type and consumption, and the yield results of reaction is see the embodiment 1-8 in table 1.
Finally, prepared product such as easily can obtain by using ethyl acetate to carry out extracting and separating.
Embodiment 9
By the above-mentioned system of the levulinic acid aqueous solution (1.25mmol/mL) 4mL and 1mL prepared in advance the aqueous solution (50 μm of ol/L) of catalyzer 6 add in reactor, hydrogen pressure is adjusted to 1MPa, stirring reaction 36h at 120 DEG C after reactor inside hydrogen exchange 3 times.After having reacted, reaction system is cooled to room temperature, then to reaction soln sampling and with methyl alcohol to after diluted sample, by the productive rate of GC detection product γ-valerolactone.The catalyzer used in reaction and relative to the mole dosage of raw material levulinic acid, hydrogen source raw material type and consumption, and the yield results of reaction is see embodiment in table 19.
Finally, prepared product such as easily can obtain by using toluene to carry out extracting and separating.
Embodiment 10-13
The aqueous solution (500 μm of ol/L) of above-mentioned for the levulinic acid aqueous solution (1.25mmol/mL) 4mL and 1mL prepared in advance obtained catalyzer 6 and formic acid 7.5mmol are added in reactor, stirring reaction 4h (reaction times wherein in embodiment 13 is 6h) at 120 DEG C.After having reacted, system is cooled to room temperature, to reaction soln sampling and with methyl alcohol to after diluted sample, by the productive rate of GC detection product γ-valerolactone.The catalyzer used in reaction and relative to the mole dosage of raw material levulinic acid, hydrogen source raw material type and consumption, and the yield results of reaction is see embodiment 10-13 in table 1.
Finally, prepared product such as easily can obtain by using benzene to carry out extracting and separating.
Embodiment 14
The aqueous solution (500 μm of ol/L) of above-mentioned for the levulinic acid aqueous solution (1.25mmol/mL) 4mL and 10mL prepared in advance obtained catalyzer 6 and formic acid 7.5mmol are added in reactor, stirring reaction 24h under 25 DEG C (i.e. normal temperature).After having reacted, system is cooled to room temperature, to reaction soln sampling and with methyl alcohol to after diluted sample, by the productive rate of GC detection product γ-valerolactone.The catalyzer used in reaction and relative to the mole dosage of raw material levulinic acid, hydrogen source raw material type and consumption, and the yield results of reaction is see embodiment in table 1 14.
Finally, prepared product such as easily can obtain by using ethyl acetate to carry out extracting and separating.
Table 1
[a]
Can find out according to table 1, by method of the present invention in the reaction process preparing γ-valerolactone, under only using water not use any organic solvent as solvent, product γ-valerolactone has been obtained by using water-soluble iridium catalyst homogeneous catalysis, its productive rate can up to 99%, catalyzer, to the better tolerance of soda acid, does not need to use other soda acid to regulate the pH value of reaction system.
Embodiment 15-19
First preparation is containing the biomass hydrolysate of levulinic acid: add in reactor by 0.9g biomass (being respectively glucose, fructose, sucrose, starch and Mierocrystalline cellulose) and 5ml0.5mmol/L dilute sulphuric acid, under 1.0MPa nitrogen atmosphere, stir hydrolysis 4h at 170 DEG C.After having reacted, reaction system is cooled to room temperature, by solids removed by filtration residue, the filtrate of acquisition is the biomass hydrolysate containing levulinic acid.Sample this hydrolyzed solution and dilute rear liquid chromatography (LC), wherein by being equipped with Waters1525 pump, the high performance liquid phase of Nacalai tesque cosmail 5C18-AR-II post and Waters2414 differential refraction detector measures.The temperature of column temperature phase is set as 30 DEG C, and moving phase is 5mmol aqueous sulfuric acid, and the flow velocity of setting moving phase is 1ml/min.Detection levulinic acid wherein and the content of formic acid, calculate productive rate thus, the results are shown in Table 2.
Then the biomass hydrolysate containing levulinic acid obtained above is used as raw material to prepare γ-valerolactone: add in reactor by 4mL said hydrolyzed liquid (directly using the hydrolyzed solution that above-mentioned filtration obtains afterwards) and the aqueous solution (500 μm of ol/L) of 1mL catalyzer 6, hydrogen pressure is adjusted to 1MPa, stirring reaction 4h at 120 DEG C after reactor inside hydrogen exchange 3 times.Here be noted that because the formic acid in hydrolyzed solution is not enough to make levulinic acid transform completely, so also use other H
2react to make to react completely, but the formic acid in hydrolyzed solution also take part in reaction.After having reacted, reaction system is cooled to room temperature, to reaction soln sampling and with after this sample of methanol dilution, with the productive rate of GC detection product γ-valerolactone.Result is as shown in table 2.
Finally, prepared product such as easily can obtain by using ethyl acetate to carry out extracting and separating.
Table 2
[a]
Can find out according to table 2, biomass such as glucose, fructose, sucrose, starch and cellulosic hydrolyzed solution directly can be used to prepare γ-valerolactone as raw material by method of the present invention, avoid the energy consumption needed for purification levulinic acid.And in reaction process, under only using water not use any organic solvent as solvent, product γ-valerolactone has been obtained by using water-soluble iridium catalyst homogeneous catalysis, its productive rate can up to more than 60% relative to original biomass, and the yield of the levulinic acid obtained relative to biomass by hydrolyzation can up to 99%.
recycling of water-soluble iridium catalyst
According to above-described embodiment 6, by 5mmol levulinic acid and 5 × 10
-4the water-soluble iridium catalyst 6 of the above-mentioned preparation of mmol is made into the 5mL aqueous solution, drops in reactor, hydrogen pressure is adjusted to 1MPa, stirring reaction 4h at 120 DEG C after reactor inside hydrogen exchange 3 times.After having reacted, reaction system is cooled to room temperature, reaction soln extracted with diethyl ether, product γ-valerolactone is extracted.After extraction γ-valerolactone in remaining aqueous catalyst solution, add 5mmol levulinic acid, and then drop in reactor, prepare product γ-valerolactone with reaction conditions as hereinbefore.Such repetition 4 times recycles performance with what investigate water-soluble iridium catalyst of the present invention, experiment the results are shown in Figure 1.
Fig. 1 display recycles result according to water-soluble iridium catalyst of the present invention, as can be seen from Figure 1, prepare in the method for γ-valerolactone in homogeneous catalysis of the present invention, the not only catalytic activity of the catalyzer used is high, and consumption is few, and can repeatedly recycle.
By above embodiment, display in the method for the invention, water-soluble iridium catalyst shows excellent catalysis characteristics in the hydrogenating reduction of levulinic acid, not only catalyst levels is little, reaction preference is high, reaction conditions is gentle, and catalyzer shows the higher tolerance to soda acid, does not need a large amount of inorganic or organic bases neutralization reaction raw materials; Reaction solvent is water, environmental friendliness, and can directly react using biomass hydrolysate as raw material, demonstrates very high industrial application value.
It should be pointed out that the professional and technical personnel for making the art, under the premise without departing from the principles of the invention, the multiple amendment to these embodiments can be realized, and these amendments also should be considered as in protection scope of the present invention.
Claims (10)
1. prepared the method for γ-valerolactone by homogeneous catalysis for one kind, it is characterized in that, using water as solvent, under water-soluble iridium catalyst exists, make the acetyl-propionic acid raw material represented by following formula I and the hydrogen source class raw material reaction represented by Formula Il and obtain product γ-valerolactone:
Wherein said water-soluble iridium catalyst has following chemical formula:
In the formula, substituent R is H, hydroxyl, carboxyl or methoxyl group, and R is positioned at the ortho position of pyridine ring atom N, contraposition or a position; M represents and is selected from SO
4 2-, NO
3 -, Cl
-or OTf
-negatively charged ion.
2. method according to claim 1, is characterized in that, described acetyl-propionic acid raw material is levulinic acid, levulinate or the biomass hydrolysate containing levulinic acid.
3. method according to claim 1, is characterized in that, described hydrogen source class raw material is H
2, formic acid or formate.
4. method according to claim 1, is characterized in that, described method is without the need to additionally adding mineral alkali or acid to regulate the pH value of reaction soln.
5. method according to claim 1, is characterized in that, the mol ratio of described acetyl-propionic acid raw material and described hydrogen source class raw material is 1: 1-1: 2.
6. method according to claim 3, is characterized in that, when described hydrogen source class raw material is H
2time, the H of use
2pressure be 1MPa-10MPa.
7. method according to claim 1, is characterized in that, the mole dosage of described water-soluble iridium catalyst is the 0.001%-1% of described acetyl-propionic acid raw material.
8. method according to claim 1, is characterized in that, the temperature of described reaction is room temperature to 200 DEG C, and the pressure of described reaction is that normal pressure is to 10MPa.
9. method according to claim 1, is characterized in that, described method also comprises to be carried out extracting with separated product γ-valerolactone with organic solvent, and wherein said organic solvent is selected from ether, methyl tertiary butyl ether, ethyl acetate or toluene.
10. method according to claim 9, is characterized in that, after the described product γ-valerolactone of separation, the aqueous solution containing described catalyzer is recycled.
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| CN105348229A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for catalyzing levulinic acid for conversion |
| CN107337648B (en) * | 2016-05-03 | 2020-04-17 | 南京理工大学 | Method for synthesizing erlotinib |
| CN107337646B (en) * | 2016-05-03 | 2020-04-07 | 南京理工大学 | Method for synthesizing quinazolinone derivative by using methanol as raw material |
| CN111434657B (en) * | 2019-01-15 | 2023-06-16 | 吉林大学 | Preparation method of gamma-valerolactone and levulinate ester compound |
| CN111423398A (en) * | 2020-04-13 | 2020-07-17 | 重庆科技学院 | Method for preparing gamma-valerolactone from levulinic acid |
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Non-Patent Citations (1)
| Title |
|---|
| pH-Dependent Catalytic Activity and Chemoselectivity in Transfer Hydrogenation Catalyzed by Iridium Complex with 4,4’-Dihydroxy-2,2’-bipyridine;Yuichiro Himeda et al.;《Chem. Eur. J.》;20081106;第14卷(第35期);第11076-11081页 * |
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