CN103232418A - 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, relate in particular to a kind of preparation method of γ-Wu Neizhi.
Background technology
At present human society is depended 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 begin to seek new alternate resources.Biomass both can be used as the energy, also can be used as the source of organic carbon for the production of chemical and material, therefore were considered to most possibly replace the new resources of fossil feedstock.γ-Wu Neizhi is the very high biomass plateform molecules of a kind of potential using value, both can be used as New-type fuel and has used, and can be used as the source of organic carbon again for the synthesis of the chemical of high added value.
At present, the preparation of γ-Wu Neizhi is raw material with biomass plateform molecules levulinic acid mainly, by heterogeneous catalyst or homogeneous catalyst hydrogenating reduction and the acquisition that lactonizes.Patent application WO02074760 and US20030055270 disclose under the loaded noble metal catalyst effect, are 215 ℃ in temperature of reaction, can obtain γ-Wu Neizhi with 97% productive rate by the hydrogen reaction of levulinic acid and 700～800psi.Patent application CN101805316A discloses a kind of method for preparing γ-Wu Neizhi with supported iridium catalyst, it is 25～200 ℃ in temperature of reaction, when being 0.1～5MPa, hydrogen pressure can obtain γ-Wu Neizhi with the productive rate more than 99%, but use therein Preparation of catalysts needs hot conditions, for example after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour.Use heterogeneous catalyst can produce 2-methyltetrahydrofuran impurity in the reaction, it easily generates superoxide, causes existing hidden peril of explosion.It is that hydrogen source is when temperature of reaction is 100～200 ℃ 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, prepare γ-Wu Neizhi by catalytic hydrogenation, its productive rate is the highest can to reach 99%, though this method can directly be utilized biomass hydrolysate, need a large amount of inorganic or organic basess.Patent application CN102558108A discloses and has a kind ofly prepared the method for γ-Wu Neizhi with iridium-pincer ligand complex catalysis, mild condition, have higher productive rate and selectivity, but reaction system needs with an organic solvent, and catalyzer is poor to the tolerance of acid, and needs add in a large amount of mineral alkalis and the levulinic acid raw material.
Therefore, on the whole, exist severe reaction conditions (High Temperature High Pressure), problem that catalyst levels is bigger with existing prepared γ-Wu Neizhi, cause the production cost height, be difficult to large-scale production, also have 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 new method for preparing γ-Wu Neizhi, it can overcome the part or all of defective of prior art.
For this reason, the invention provides and a kind ofly prepare the method for γ-Wu Neizhi by homogeneous catalysis, it is characterized in that, with water as solvent, in the presence of water-soluble iridium catalyst, make the acetyl-propionic acid raw material of being represented by following formula I obtain the product γ-Wu Neizhi with the hydrogen source class raw material reaction of being represented by Formula Il:
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 ortho position, contraposition or a position of pyridine ring N atom; M represents to be selected from SO
4 2-, NO
3 -, Cl
-Or trifluoromethanesulfonic acid root (OTf
-) negatively charged ion.
In a preferred implementation, described acetyl-propionic acid raw material is levulinic acid, levulinate or the biomass hydrolysate that contains levulinic acid.
In a preferred implementation, described hydrogen source class raw material is hydrogen (H
2), formic acid or formate.
In a preferred implementation, described method need not additionally to add the pH value that mineral alkali or acid come conditioned reaction solution.
In a preferred implementation, 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 be H
2The time, the H of use
2Pressure be 1MPa-10MPa.
In a preferred implementation, the mole dosage of described water-soluble iridium catalyst is the 0.001%-1% of described acetyl-propionic acid raw material.
In a preferred implementation, the temperature of described reaction is room temperature to 200 ℃, and the pressure of described reaction is that normal pressure is to 10MPa.
In a preferred implementation, described method comprises also with organic solvent and extracting with the separated product γ-Wu Neizhi that wherein said organic solvent is selected from ether, methyl tertiary butyl ether, ethyl acetate or toluene.
In a preferred implementation, after separating described product γ-Wu Neizhi, the aqueous solution that contains described catalyzer is recycled.
It is little and can be recycled that the method that the present invention prepares γ-Wu Neizhi has a catalyst levels, and product yield height, reaction conditions are gentle relatively, advantages of environment protection, the industrial prospect with large-scale application.
Description of drawings
Fig. 1 shows the result that recycles according to water-soluble iridium catalyst of the present invention.
Embodiment:
The method that homogeneous catalysis of the present invention prepares γ-Wu Neizhi as solvent, in the presence of water-soluble iridium catalyst, makes the acetyl-propionic acid raw material of being represented by following formula I obtain the product γ-Wu Neizhi with the hydrogen source class raw material reaction of being represented by Formula Il with water.
Reaction formula is as follows:
In the methods of the invention, the acetyl-propionic acid raw material of being represented by formula I that uses can be levulinic acid, levulinate such as levulinic acid sodium salt or levulinic acid sylvite, the perhaps hydrolyzed solution that contains levulinic acid of biomass examples such as glucose, fructose, sucrose, Mierocrystalline cellulose, starch etc.In the methods of the invention, the hydrogen source class raw material of being represented by formula II that uses can be hydrogen, formic acid or formate such as sodium formiate or potassium formiate.Preferably, in the present invention, the mol ratio by formula I the acetyl-propionic acid raw material of representing and the hydrogen source class raw material of being represented by formula II is 1: 1-1: 2.More preferably, when the hydrogen source class raw material of being represented by formula II be H
2The time, the H of use
2Pressure be 1MPa-10MPa.
In the methods of the invention, employed catalyzer is water-soluble iridium catalyst, and it has following chemical formula:
In the formula, substituent R is H, hydroxyl, carboxyl or methoxyl group, and the position of substituent R is in ortho position, contraposition or a position of pyridine ring N atom; And substituent R can be only on the pyridine ring or simultaneously on two pyridine rings; The 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 of central atom Ir top is the five-membered ring structure (Cp with five methyl
*) (being the pentamethyl-cyclopentadienyl ligand).
The catalyzer that uses in the inventive method can be such as but not limited to being prepared as follows: by [Cp
*IrCl
2]
2And Ag
2SO
4, silver trifluoromethanesulfonate (AgOTf) reaction to be to produce [Cp
*Ir (H
2O)
3] SO
4Or [Cp
*Ir (H
2O)
3] (OTf)
2Use corresponding bipyridine ligand again
[Cp with above acquisition
*Ir (H
2O)
3] SO
4Or [Cp
*Ir (H
2O)
3] (OTf)
2Reaction and make the used water-soluble iridium catalyst of reaction.
The reaction solvent that uses in the methods of the invention is water, because use therein raw material itself can make reaction system be acidity or weakly alkaline, so catalyzer is to the no particular requirement of pH value, adaptability is good, and does not need additionally to add the pH value that mineral alkali or acid come the conditioned 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 ℃, is preferably 50-170 ℃, for example 120 ℃; The pressure of reaction is that normal pressure is to 10MPa; When using H
2During as reaction raw materials, be preferably 0.5-7MPa, for example 1MPa.
In the methods of the invention, after reaction was finished, available gas-chromatography (GC) detected reaction product, and testing conditions is as follows: use DM WAX post, 250 ℃ of gasification temperatures, post flow 1.37mL/min, linear velocity 25cm/s; The post case adopts temperature programming: 50 ℃ keep 3min, rise to 180 ℃ and keep 2min with the speed of 20 ℃/min, and the speed with 10 ℃/min rises to 240 ℃ again; 280 ℃ of detected temperatures.
The present invention has advantage and includes but not limited to following:
(1) catalyst activity height, good reaction selectivity, productive rate height (reaction yield reaches as high as 99%);
(2) reaction is easy, and mild condition has avoided using a large amount of mineral alkalis or acid, improves the economy of production system;
(3) make water as solvent, not with an organic solvent, environmental friendliness;
(4) product can separate by simple extraction process, and separation yield can reach 98%; And the remaining aqueous catalyst solution that contains can recycle behind the separated product, and catalytic performance is constant substantially.
Embodiment
The invention is further illustrated by the following examples, but should understand, scope of the present invention is not subjected to the restriction of these embodiment.
The preparation of water-soluble iridium catalyst
Under argon atmosphere, in the three-necked flask of whipping appts is housed, with [Cp
*IrCl
2]
2(480mg, 0.60mmol) and Ag
2SO
4(374mg 1.20mmol) joins in the 4mL water, with this mixture stirring reaction 12h at room temperature.By removing by filter the precipitate A gCl of generation, remaining solution decompression revolves and steams and vacuum-drying, obtains [the Cp of yellow powder shape
*Ir (H
2O)
3] SO
4(550mg, productive rate: 96%)
In the three-necked flask that whipping appts and reflux are housed, with [Cp
*Ir (H
2O)
3] SO
4(48mg 0.10mmol) is dissolved in the 12.5mL water, adds bipyridine ligand (0.11mmol) under argon atmosphere.Behind the back flow reaction 12h, filtering solution.The filtrate decompression that obtains is revolved steaming and obtained solid product, the i.e. catalyzer 1 of following formula 1 expression.
Similarly, the bipyridine ligand of (R be respectively carboxyl, hydroxyl, methoxyl group and at different positions) makes the catalyzer 2-8 that following formula 2-8 represents to have different substituents R by using respectively.
Embodiment 1-8
With the levulinic acid aqueous solution (1.25mmol/mL) 4mL of preparation in advance and the above-mentioned system of 1mL the aqueous solution (500 μ mol/L) of catalyzer 1-8 add in the reactor respectively, reactor is inner to be adjusted to 1MPa with behind the hydrogen exchange 3 times with hydrogen pressure, at 120 ℃ of following stirring reaction 4h.Reaction is cooled to room temperature with reaction system after finishing, then to the reaction soln sampling and with methyl alcohol to diluted sample after, detect the productive rate of product γ-Wu Neizhi by GC.The catalyzer that uses in the reaction and with respect to mole dosage, hydrogen source raw material type and the consumption of raw material levulinic acid, and the yield results of reaction is referring to the embodiment 1-8 in the table 1.
At last, prepared product for example can obtain easily by using ethyl acetate to carry out extracting and separating.
Embodiment 9
With the levulinic acid aqueous solution (1.25mmol/mL) 4mL of preparation in advance and the above-mentioned system of 1mL the aqueous solution (50 μ mol/L) of catalyzer 6 add in the reactor, reactor is inner to be adjusted to 1MPa with behind the hydrogen exchange 3 times with hydrogen pressure, at 120 ℃ of following stirring reaction 36h.Reaction is cooled to room temperature with reaction system after finishing, then to the reaction soln sampling and with methyl alcohol to diluted sample after, detect the productive rate of product γ-Wu Neizhi by GC.The catalyzer that uses in the reaction and with respect to mole dosage, hydrogen source raw material type and the consumption of raw material levulinic acid, and the yield results of reaction is referring to embodiment in the table 19.
At last, prepared product for example can obtain easily by using toluene to carry out extracting and separating.
Embodiment 10-13
The levulinic acid aqueous solution (1.25mmol/mL) 4mL of preparation in advance and the aqueous solution (500 μ mol/L) and the formic acid 7.5mmol of the above-mentioned catalyzer that makes 6 of 1mL are added in the reactor, 120 ℃ of following stirring reaction 4h (wherein the reaction times among the embodiment 13 is 6h).Reaction is cooled to room temperature with system after finishing, to the reaction soln sampling and with methyl alcohol to diluted sample after, detect the productive rate of product γ-Wu Neizhi by GC.The catalyzer that uses in the reaction and with respect to mole dosage, hydrogen source raw material type and the consumption of raw material levulinic acid, and the yield results of reaction is referring to embodiment 10-13 in the table 1.
At last, prepared product for example can obtain easily by using benzene to carry out extracting and separating.
Embodiment 14
The levulinic acid aqueous solution (1.25mmol/mL) 4mL of preparation in advance and the aqueous solution (500 μ mol/L) and the formic acid 7.5mmol of the above-mentioned catalyzer that makes 6 of 10mL are added in the reactor stirring reaction 24h under 25 ℃ (being normal temperature).Reaction is cooled to room temperature with system after finishing, to the reaction soln sampling and with methyl alcohol to diluted sample after, detect the productive rate of product γ-Wu Neizhi by GC.The catalyzer that uses in the reaction and with respect to mole dosage, hydrogen source raw material type and the consumption of raw material levulinic acid, and the yield results of reaction is referring to embodiment in the table 1 14.
At last, prepared product for example can obtain easily by using ethyl acetate to carry out extracting and separating.
Table 1
[a]
According to table 1 as can be seen, by method of the present invention the preparation γ-Wu Neizhi reaction process in, water is not used under any organic solvent as solvent, by using water-soluble iridium catalyst homogeneous catalysis to make the product γ-Wu Neizhi, its productive rate can be up to 99%, catalyzer does not need to use other soda acid to come the pH value of conditioned reaction system to the better tolerance of soda acid.
Embodiment 15-19
At first preparation contains the biomass hydrolysate of levulinic acid: 0.9g biomass (being respectively glucose, fructose, sucrose, starch and Mierocrystalline cellulose) and 5ml0.5mmol/L dilute sulphuric acid are added in the reactor, under the 1.0MPa nitrogen atmosphere, stir hydrolysis 4h at 170 ℃.After reaction is finished reaction system is cooled to room temperature, by the solids removed by filtration residue, filtrate being of acquisition contains the biomass hydrolysate of levulinic acid.To this hydrolyzed solution sampling and dilution back liquid chromatography (LC), wherein by the Waters1525 pump is housed, the high performance liquid phase of Nacalai tesque cosmail 5C18-AR-II post and Waters2414 differential refraction detector is measured.The temperature of column temperature phase is set at 30 ℃, and moving phase is the 5mmol aqueous sulfuric acid, and the flow velocity of setting moving phase is 1ml/min.Detect wherein levulinic acid and the content of formic acid, calculate productive rate thus, the results are shown in Table 2.
The biomass hydrolysate that contains levulinic acid with above acquisition prepares γ-Wu Neizhi as raw material then: the aqueous solution (500 μ mol/L) of 4mL said hydrolyzed liquid (directly using the hydrolyzed solution that obtains after the above-mentioned filtration) and 1mL catalyzer 6 is added in the reactor, reactor is inner to be adjusted to 1MPa with behind the hydrogen exchange 3 times with hydrogen pressure, at 120 ℃ of following stirring reaction 4h.Here be noted that because the formic acid in the hydrolyzed solution is not enough to make fully levulinic acid to transform, so also use other H
2React so that react completely, but the formic acid in the hydrolyzed solution has also participated in reaction.Reaction is cooled to room temperature with reaction system after finishing, dilute this sample to the reaction soln sampling and with methyl alcohol after, detect the productive rate of product γ-Wu Neizhi with GC.The result is as shown in table 2.
At last, prepared product for example can obtain easily by using ethyl acetate to carry out extracting and separating.
Table 2
[a]
According to table 2 as can be seen, can directly use biomass such as glucose, fructose, sucrose, starch and cellulosic hydrolyzed solution to prepare γ-Wu Neizhi as raw material by method of the present invention, avoid the required energy consumption of purification levulinic acid.And in reaction process, water is not used under any organic solvent as solvent, by using water-soluble iridium catalyst homogeneous catalysis to make the product γ-Wu Neizhi, its productive rate can be up to more than 60% with respect to initial biomass, and the yield of the levulinic acid that obtains with respect to biomass by hydrolyzation can be up to 99%.
Recycling of water-soluble iridium catalyst
According to above-described embodiment 6, with 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 the reactor, and reactor is inner to be adjusted to 1MPa with behind the hydrogen exchange 3 times with hydrogen pressure, at 120 ℃ of following stirring reaction 4h.After reaction is finished reaction system is cooled to room temperature, the reaction soln extracted with diethyl ether extracts the product γ-Wu Neizhi.To extracting behind the γ-Wu Neizhi in the remaining aqueous catalyst solution, add the 5mmol levulinic acid, and then drop in the reactor, prepare the product γ-Wu Neizhi with as hereinbefore reaction conditions.Such repetition 4 times is to investigate the performance that recycles of water-soluble iridium catalyst of the present invention, and result of experiment is seen Fig. 1.
Fig. 1 shows the result that recycles according to water-soluble iridium catalyst of the present invention, as can be seen from Figure 1, prepare in the method for γ-Wu Neizhi the not only catalytic activity height of employed catalyzer in homogeneous catalysis of the present invention, and consumption is few, and can repeatedly recycle.
By above embodiment, show 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, the reaction preference height, the reaction conditions gentleness, and catalyzer show to soda acid than height endurability, do not need a large amount of inorganic or organic bases neutralization reaction raw materials; Reaction solvent is water, environmental friendliness, and can directly react as raw material with biomass hydrolysate, demonstrate very high industrial application value.
Should be pointed out that for the professional and technical personnel who makes the art, under the prerequisite that does not break away from the principle of the invention, can realize the multiple modification to these embodiment, and these modifications should be considered as in protection scope of the present invention also.
Claims (10)
1. method for preparing γ-Wu Neizhi by homogeneous catalysis, it is characterized in that, as solvent, in the presence of water-soluble iridium catalyst, make the acetyl-propionic acid raw material of being represented by following formula I obtain the product γ-Wu Neizhi with the hydrogen source class raw material reaction of being represented by Formula Il with water:
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 ortho position, contraposition or a position of pyridine ring N atom; M represents to be 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 that contains levulinic acid.
3. method according to claim 1 is characterized in that, described hydrogen source class raw material is H2, formic acid or formate.
4. method according to claim 1 is characterized in that, described method need not additionally to add the pH value that mineral alkali or acid come conditioned reaction solution.
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
2The time, 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 ℃, 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 comprises also with organic solvent and extracting with the separated product γ-Wu Neizhi that 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 separating described product γ-Wu Neizhi, the aqueous solution that contains described catalyzer is recycled.
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Cited By (6)
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|---|---|---|---|---|
| CN105348229A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for catalyzing levulinic acid for conversion |
| CN105348230A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for preparing valerolactone |
| CN107337646A (en) * | 2016-05-03 | 2017-11-10 | 南京理工大学 | A kind of method using methanol as Material synthesis Quinazol derivative |
| CN107337648A (en) * | 2016-05-03 | 2017-11-10 | 南京理工大学 | A kind of method for synthesizing Tarceva |
| CN111423398A (en) * | 2020-04-13 | 2020-07-17 | 重庆科技学院 | Method for preparing gamma-valerolactone from levulinic acid |
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
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| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
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| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348229A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for catalyzing levulinic acid for conversion |
| CN105348230A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for preparing valerolactone |
| CN107337646A (en) * | 2016-05-03 | 2017-11-10 | 南京理工大学 | A kind of method using methanol as Material synthesis Quinazol derivative |
| CN107337648A (en) * | 2016-05-03 | 2017-11-10 | 南京理工大学 | A kind of method for synthesizing Tarceva |
| 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 |
| CN107337648B (en) * | 2016-05-03 | 2020-04-17 | 南京理工大学 | Method for synthesizing erlotinib |
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
| 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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