CN102558108A - Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst - Google Patents
Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst Download PDFInfo
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- CN102558108A CN102558108A CN2011104345638A CN201110434563A CN102558108A CN 102558108 A CN102558108 A CN 102558108A CN 2011104345638 A CN2011104345638 A CN 2011104345638A CN 201110434563 A CN201110434563 A CN 201110434563A CN 102558108 A CN102558108 A CN 102558108A
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Abstract
The invention relates to a process for preparing gamma-valerolactone by utilizing an iridium-pincer ligand complex catalyst, particularly to the process for preparing the gamma-valerolactone by catalyzing levulinic acid for hydrogenation reduction and and lactonization. The process for preparing the gamma-valerolactone by utilizing the iridium-pincer ligand complex catalyst is characterized in that 1-5 MPa hydrogen is used as a reducing agent at a temperature between 50 DEG C and 100 DEG C, the gamma-valerolactone is prepared by catalyzing the levulinic acid for hydrogenation reduction and lactonization under the action of iridium catalyst which accounts for 0.01 to 0.1 mol% of quantity of levulinic acid. The process for preparing the gamma-valerolactone by utilizing the iridium-pincer ligand complex catalyst eliminates the disadvantage that a high temperature and high pressure reaction condition is required for gamma-valerolactone production so that economy and security of the production system are improved. Dosage of the catalyst is small, productivity is high and selectivity is good.
Description
Technical field
The present invention relates to a kind ofly prepare the method for γ-Wu Neizhi with iridium-pincer ligand complex compound catalyst, is the method for preparing γ-Wu Neizhi with iridium-pincer ligand complex compound catalyst catalysis levulinic acid hydrogenation reduction and lactonization reaction specifically.
Background technology
At present human society is depended on the required energy and chemical for existence and development mainly from traditional fossil feedstock; Like coal, oil, Sweet natural gas etc.; Coal still can be exploited 100 years, oil 30～40 years, Sweet natural gas 50～60 years; Along with the consumption gradually of these fossil feedstock, people begin to seek new alternate resources.In numerous renewable resourcess such as wind energy, sun power, morning and evening tides, biomass both can be used as the energy, and the source that also can be used as organic carbon produces chemical and material, therefore were considered to have the new resources of most possible replacement 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 chemical of the source of organic carbon in order to synthetic high added value again.γ-Wu Neizhi is a renewable resources, and storage security is convenient, can use in a large number in the world.The 10v/v% γ-Wu Neizhi mixed with the 95-octane gasoline of 90v/v% with 10v/v% ethanol have similar character with the propellant combination of the 95-octane gasoline mixing gained of 90v/v%; And because γ-Wu Neizhi and water can not form azeotropic mixture, so the rectifying energy consumption of γ-Wu Neizhi is lower.In sum, γ-Wu Neizhi is the novel biomass resource with important application prospect.
The preparation of γ-Wu Neizhi is a raw material with biomass plateform molecules levulinic acid mainly, through heterogeneous catalyst (Ru/C etc.) or homogeneous catalyst hydrogenating reduction and the acquisition that lactonizes.Patent WO 02074760 and US20030055270 show levulinic acid under the loaded noble metal catalyst effect when temperature of reaction is 215 ℃ and the hydrogen reaction of 700～800psi can obtain γ-Wu Neizhi with 97% productive rate.Patent US20040254384 points out that levulinic acid can obtain γ-Wu Neizhi with the productive rate more than 99% with the loaded noble metal catalyst catalytic hydrogenation when temperature of reaction is 151 ℃ in supercritical fluid carbon dioxide.Patent CN 101805316A discloses a kind of method for preparing γ-Wu Neizhi with supported iridium catalyst; In temperature of reaction is 25～200 ℃; Can obtain γ-Wu Neizhi with the productive rate more than 99% when hydrogen pressure is 0.1～5MPa, but Preparation of catalysts needs hot conditions.Use heterogeneous catalyst can produce a spot of 2-methyltetrahydrofuran (be prone to generate superoxide, have hidden peril of explosion).Patent CN 101376650 reported with formic acid be hydrogen source when temperature of reaction is 100～200 ℃, catalytic hydrogenation prepares γ-Wu Neizhi under the ruthenium-based catalyst effect of 0.1～0.2mol% of levulinic acid amount of substance, productive rate is the highest can to reach 99%.In a word, exist severe reaction conditions (high temperature, high pressure), problem that catalyst levels is bigger when preparing γ-Wu Neizhi, cause production cost high, be difficult to large-scale production with current technology.
Summary of the invention
The objective of the invention is to propose a kind ofly prepare the method for γ-Wu Neizhi, can overcome the drawback of prior art with iridium-pincer ligand complex compound catalyst.It is little that the present invention has a catalyst levels, and product yield is high, and reaction conditions is gentle relatively, meets the characteristics of the requirement of Green Chemistry, and wide prospect in industrial application is arranged.
Catalyzer used in the present invention is on-the-spot complex compound that generates of pincer ligand shown in general formula I or the general formula I I and iridium precursor or the iridium that the prepares in advance-pincer ligand complex compound shown in the general formula III, and the iridium precursor is [Ir (coe)
2Cl]
2Or [Ir (cod) Cl]
2
General formula I or II, wherein L
1And L
2Respectively doing for oneself contains the coordinating group of phosphine ligating atom or nitrogen ligating atom, and X is CH
2, O, Y is CH, N.
Coordinating group L
1, L
2Respectively doing for oneself contains the coordinating group of phosphine, and the group that this type contains phosphine preferably has general formula R
1R
2P, wherein R
1And R
2Can be independently selected from C
1-C
6Alkyl, C
5-C
6Naphthenic base, any substituted aryl.
Work as R
1And/or R
2Be C
1-C
6During alkyl, said C
1-C
6Alkyl can be the straight or branched alkyl.Aptly, said C
1-C
6Alkyl is methyl, ethyl, sec.-propyl or the tertiary butyl.
Aptly, R
1And R
2Identical.Like this, L
1, L
2Can independently be selected from PMe
2, PEt
2, P
iPr
2, p
tBu
2
Work as R
1And/or R
2During for any substituted aryl, said aryl is preferably any substituted phenyl.Aptly, L
1And/or L
2Can be PPh
2
Perhaps, coordinating group L
1, L
2The nitrogenous coordinating group of respectively doing for oneself, the nitrogenous group of this type preferably has general formula R
1R
2N, wherein R
1And R
2Definition above R
1R
2P.
Coordinating group L
1, L
2Can be identical or different.
General formula III, wherein Z is H or other complex anion such as halogen, OCOR, OCOCF
3, OSO
2R, OSO
2CF
3, CN, OR, NR
2, SR, R is H, alkyl, naphthenic base, aryl, alkylaryl, heterocyclic radical, aromatic heterocyclic.L
1, L
2Definition above general formula I or II.
Suitable pincer ligand comprises shown in the following structural formula:
Suitable iridium-pincer ligand complex compound comprises shown in the following structural formula:
Pincer ligand can be buied from market or be synthetic according to method well known in the art.In particular, pincer ligand can be according to Organometallics, and 2001,20,1960-1964 and Angew.Chem., Int.Ed.2008,47,8661-8664 and similarly method is synthetic with it.
The present invention is characterised in that by the method for iridium-pincer ligand complex compound catalyst catalysis levulinic acid hydrogenation preparing γ-Wu Neizhi: in autoclave, add solvent and a certain amount of reactant levulinic bronsted lowry acids and bases bronsted lowry; The iridium catalyst that adds 0.001～0.1mol% of levulinic acid amount of substance then; After mixing,, fill the hydrogen of 1～5MPa with the autoclave sealing; Control reaction temperature is 50～100 ℃; Reacted 15～80 hours, adding hydrochloric acid regulation system pH value is 3～4, promptly obtains the title product γ-Wu Neizhi.Product is analyzed through GC-MS.
The used solvent of the present invention is an organic solvent commonly used such as methyl alcohol, ethanol, Virahol, THF, toluene, also can be the mixed solvent of THF and water.
The used alkali of the present invention is mineral alkalis such as Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, salt of wormwood, also can be organic basess such as triethylamine.
The present invention has following advantage:
1) activity of such catalysts is high, good reaction selectivity, and productive rate is high.
2) reaction conditions is gentle, and temperature of reaction and pressure have improved the economy of production system far below other homogeneous phases or heterogeneous catalysis system.
Embodiment
Describe the present invention through embodiment below, but content of the present invention is not limited thereto.
Embodiment 1
The preparation of catalyzer 7
In the 10mL of dried and clean Schlenk pipe, add
tBu-PNp (compound 1) (119mg, 302 μ mol) and [Ir (coe)
2Cl]
2(90mg; 100 μ mol), system is replaced into the THF (5.5mL) that adds the degassing behind the argon atmosphere, stirring and dissolving is transferred to this solution in the high-pressure hydrogenation still of argon shield after evenly; The displacement argon gas is three times fast; Regulating hydrogen pressure behind the displacement hydrogen five times is 2.5MPa, and oil bath is heated to 90 ℃, stirring reaction 12 hours.Be chilled to room temperature, under argon shield, system be transferred in the 10mL Schlenk pipe of another clean dried, vacuum precipitation to residual volume is about 0.5mL; Add the normal hexane (5mL) of the degassing, separate out white precipitate, argon shield is filtered down; Filter cake is again with the normal hexane that outgases (2 * 5mL) washings; Vacuum-drying gets white solid product 7 (100mg, 80%).
1H?NMR(400MHz，CDCl
3)δ7.53(t，J＝7.7Hz，1H)，7.24(d，J＝7.7Hz，2H)，4.00-3.41(m，4H)，1.53-1.12(m，36H)，-19.47(br，s，1H)，-23.59(br，s，1H).
31PNMR(162MHz，CDCl
3)δ58.12(s).
Embodiment 2
The preparation of catalyzer 8
In the 10mL of dried and clean Schlenk pipe, add (
tBu-PNP) IrH
2Cl (7) (125mg, 200 μ mol), sodium hydride (500mg, 20mmol), system is replaced into argon atmosphere after; Add the THF (6mL) of the degassing, oil bath was heated to 50 ℃ of stirring reactions 16 hours, filtered down in argon shield after being chilled to room temperature; Filtrating is transferred in the 10mL Schlenk pipe of another dried and clean, and vacuum precipitation to system volume is about 0.5mL, adds the normal hexane (5mL) of the degassing; Have brown solid to separate out, argon shield is filtered down, and filter cake is again with the normal hexane that outgases (2 * 5mL) washings; Vacuum-drying gets khaki color solid product 8 (50mg, 42%).
1H?NMR(400MHz，C
6D
6)δ6.82(t，J＝7.7Hz，1H)，6.50(d，J＝7.7Hz，2H)，3.13(s，4H)，1.42(t，J＝6.4Hz，36H)，-10.12(td，J＝15.3，5.2Hz，2H)，-19.78(tt，J＝14.8，4.8Hz，1H).
31P?NMR(162MHz，C
6D
6)δ88.03(s).
1H?NMR(400MHz，CD
2Cl
2)δ7.36(t，J＝7.6Hz，1H)，7.08(d，J＝7.6Hz，2H)，3.41(s，4H)，1.32(t，J＝6.4Hz，36H)，-10.87(td，J＝15.0，5.0Hz，2H)，-21.01(tt，J＝14.0，4.8Hz，1H).
13C?NMR(101MHz，CD
2Cl
2)δ163.53(t，J＝3.6Hz)，133.42(s)，118.55(t，J＝4.2Hz)，42.80(t，J＝9.9Hz)，33.80(t，J＝11.4Hz)，29.80(t，J＝2.9Hz).
31P?NMR(162MHz，CD
2Cl
2)δ72.88(s).HRMS(MALDI)calcd?for?C
23H
43IrNP
2 +([M-3H]
+)：588.2494；Found：588.2489.
Embodiment 3～8:
In glove box, take by weighing [Ir (coe)
2Cl]
2(1.3mg; 1.5 μ mol) and Bu-PNP (compound 1) (1.8mg; 4.5 μ mol) in the 10mL of dried and clean Schlenk pipe, system is replaced into the corresponding solvent (2mL) that adds the degassing behind the argon atmosphere, heating in water bath to 50 ℃; Stir complexing 30 minutes, be replaced into atmosphere of hydrogen (hydrogen balloon) subsequently and continue to stir complexing 15 minutes.With the levulinic acid of preparation in advance (348.3mg, the solution that 3mmol) is dissolved in corresponding solvent (2mL) joins in the above-mentioned catalyst solution, after stirring system being joined the weighing that is replaced into argon atmosphere has 1.2 Equivalent Hydrogen potassium oxides (85% purity) (230mg; 3.5mmol) the high-pressure hydrogenation still in, replace argon gas three times fast after, replace hydrogen fast five times; The adjusting hydrogen pressure is 5Mpa, and oil bath is heated to 100 ℃, and stirring reaction (1250rpm) is after 15 hours; System is chilled to room temperature, adds the hydrochloric acid regulation system, stir after 20 minutes for acid (pH is about 3～4); Sampling is with the productive rate of GC detection γ-Wu Neizhi.Concrete reaction solvent and detected result are listed in the table 1, and sequence number is 1～6.
Embodiment 9～12:
In glove box, take by weighing [Ir (coe)
2Cl]
2(1.3mg, 1.5 μ mol) and
tBu-PNP (compound 1) (1.8mg; 4.5 μ mol) in the 10mL of dried and clean Schlenk pipe, system is replaced into the ethanol (2mL) that adds the degassing behind the argon atmosphere, heating in water bath to 50 ℃; Stir complexing 30 minutes, be replaced into atmosphere of hydrogen (hydrogen balloon) subsequently and continue to stir complexing 15 minutes.(348.3mg 3mmol) joins in the above-mentioned catalyst solution with the ethanolic soln (2mL) of the corresponding alkali of 1.2 equivalents (3.5mmol), after stirring system is joined in the high-pressure hydrogenation still that is replaced into argon atmosphere with the levulinic acid of preparation in advance; Behind the quick displacement argon gas three times, replace hydrogen fast five times, the adjusting hydrogen pressure is 5Mpa; Oil bath is heated to 100 ℃, and stirring reaction (1250rpm) was chilled to room temperature with system after 15 hours; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Concrete alkali and detected result are listed in the table 1, and sequence number is 7～10.
Embodiment 13～16:
In glove box, take by weighing [Ir (coe)
2Cl]
2(1.3mg, 1.5 μ mol) and
tBu-PNP (compound 1) (1.8mg; 4.5 μ mol) in the 10mL of dried and clean Schlenk pipe, system is replaced into the ethanol (2mL) that adds the degassing behind the argon atmosphere, heating in water bath to 50 ℃; Stir complexing 30 minutes, be replaced into atmosphere of hydrogen (hydrogen balloon) subsequently and continue to stir complexing 15 minutes.With in advance the preparation levulinic acid (348.3mg, 3mmol) with 1.2 Equivalent Hydrogen potassium oxides (85% purity) (230mg, 3.5mmol) ethanolic soln (2mL) joins in the above-mentioned catalyst solution; After stirring system is joined in the high-pressure hydrogenation still that is replaced into argon atmosphere, replace argon gas three times fast after, replace hydrogen fast five times; Conditioned reaction pressure and temperature of reaction behind stirring reaction (1250rpm) required time, are chilled to room temperature with system; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Concrete reaction pressure, temperature of reaction, reaction times and detected result are listed in the table 1, and sequence number is 11～14.
Embodiment 17:
In glove box, take by weighing [Ir (coe)
2Cl]
2(1.3mg, 1.5 μ mol) and
tBu-PNp (compound 1) (1.8mg; 4.5 μ mol) in the 10mL of dried and clean Schlenk pipe, system is replaced into the ethanol (2mL) that adds the degassing behind the argon atmosphere, heating in water bath to 50 ℃; Stir complexing 30 minutes, be replaced into atmosphere of hydrogen (hydrogen balloon) subsequently and continue to stir complexing 15 minutes.With in advance the preparation levulinic acid (3.5g, 30mmol) (2.3g, ethanolic soln 35mmol) (20mL) and above-mentioned catalyst solution join respectively in the high-pressure hydrogenation still that is replaced into argon atmosphere with 1.2 normal Pottasium Hydroxide (85% purity); Behind the quick displacement argon gas three times, replace hydrogen fast five times, the adjusting hydrogen pressure is 5Mpa; Oil bath is heated to 100 ℃, and stirring reaction (1250rpm) was chilled to room temperature with system after 80 hours; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Detected result is listed in the table 1, and sequence number is 15.
Embodiment 18:
In glove box, take by weighing (
tBu-PNP) IrH
2Cl (compound 7) (1.8mg, 3 μ mol) is replaced into the ethanol (2mL) that adds the degassing behind the argon atmosphere with system in the 10mLSchlenk of dried and clean pipe, stirring and dissolving is even.With in advance the preparation levulinic acid (3.5g, 30mmol) (2.3g, ethanolic soln 35mmol) (20mL) and above-mentioned catalyst solution join respectively in the high-pressure hydrogenation still that is replaced into argon atmosphere with 1.2 normal Pottasium Hydroxide (85% purity); Behind the quick displacement argon gas three times, replace hydrogen fast five times, the adjusting hydrogen pressure is 5Mpa; Oil bath is heated to 100 ℃, and stirring reaction (1250rpm) was chilled to room temperature with system after 80 hours; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Detected result is listed in the table 1, and sequence number is 16.
Embodiment 19:
In glove box, take by weighing (
tBu-PNP) IrH
3(compound 8) (1.7mg, 3 μ mol) are replaced into the ethanol (2mL) that adds the degassing behind the argon atmosphere with system in the 10mL of dried and clean Schlenk pipe, stirring and dissolving is even.With in advance the preparation levulinic acid (3.483g, 30mmol) (2.3g, ethanolic soln 35mmol) (20mL) and above-mentioned catalyst solution join respectively in the high-pressure hydrogenation still that is replaced into argon atmosphere with 1.2 normal Pottasium Hydroxide (85% purity); Behind the quick displacement argon gas three times, replace hydrogen fast five times, the adjusting hydrogen pressure is 5Mpa; Oil bath is heated to 100 ℃, and stirring reaction (1250rpm) was chilled to room temperature with system after 24 hours; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Detected result is listed in the table 1, and sequence number is 17.
Embodiment 20:
In glove box, take by weighing (
tBu-PNp) IrH
3(compound 8) (1.7mg, 3 μ mol) are replaced into the ethanol (3mL) that adds the degassing behind the argon atmosphere with system in the 10mL of dried and clean Schlenk pipe, stirring and dissolving evenly back is taken out 1mL solution to another Schlenk pipe.With in advance the preparation levulinic acid (11.0g, 94.7mmol) (9.0g, ethanolic soln 136.6mmol) (20mL) and above-mentioned catalyst solution join respectively in the high-pressure hydrogenation still that is replaced into argon atmosphere with 1.4 normal Pottasium Hydroxide (85% purity); Behind the quick displacement argon gas three times, replace hydrogen fast five times, the adjusting hydrogen pressure is 10Mpa; Oil bath is heated to 100 ℃, and stirring reaction (1250rpm) was chilled to room temperature with system after 48 hours; Add the hydrochloric acid regulation system and be acid (pH is about 3～4); Stir after 20 minutes, sampling is with the productive rate of GC detection γ-Wu Neizhi.Detected result is listed in the table 1, and sequence number is 18.
In all embodiment of the present invention, the productive rate of γ-Wu Neizhi all detects through GC-MS.Carry out qualitatively through the RT of mass spectrum and pure sample article, carry out quantitatively through marker method.All results and detailed reaction conditions are listed in the table 1.
Detected result relatively among each embodiment of table 1
a
aReaction conditions: 3mmol levulinic acid, 0.1mol% [Ir (coe)
2Cl]
2, 0.15mol% ligand 1,4.0mL solvent solvent, 1.2eq. alkali.
bGas spectrum productive rate. only observe γ-Wu Neizhi and unreacted levulinic acid in each reaction.
cVolume ratio 1: 1.
dS/C=10,000.
eCatalyzer 7.
fCatalyzer 8.
gS/C=100,000.
Proved that through above-mentioned experiment iridium-pincer ligand complex compound catalyst shows excellent catalysis characteristics in the hydrogenation reduction of levulinic acid; The optimum response solvent is a green solvent ethanol; Optimal reaction temperature is 100 ℃, and catalyst levels is little, and the selectivity of reaction is good; Reduce the catalyzer cost of production process, demonstrated very high industrial application value.
Claims (10)
1. one kind prepares the method for γ-Wu Neizhi with iridium-pincer ligand complex compound catalyst, and it is to be raw material with the levulinic acid, through catalysis levulinic acid hydrogenating reduction with lactonize; It is characterized in that it is in autoclave, to react; The basic soln of the organic solvent of levulinic acid feeds hydrogen in the presence of iridium-pincer ligand complex compound catalyst, reacting by heating, and reaction system is chilled to room temperature; Use sour conditioned reaction system to be acidity, stir and obtain γ-Wu Neizhi;
Described iridium-pincer ligand complex compound catalyst is on-the-spot complex compound that generates of pincer ligand shown in general formula I or the general formula I I and iridium precursor or the iridium that the prepares in advance-pincer ligand complex compound shown in the general formula III, and the iridium precursor is [Ir (coe)
2Cl]
2, [Ir (cod) Cl]
2
Said coordinating group L
1And L
2Respectively doing for oneself contains phosphine or nitrogen coordinating group, and X is CH
2, O, Y is CH, N; Coordinating group L
1, L
2Can be identical or different; Z is H or other complex anion: halogen, OCOR, OCOCF
3, OSO
2R, OSO
2CF
3, CN, OR, NR
2, SR, R is H, alkyl, naphthenic base, aryl, alkylaryl, heterocyclic radical, aromatic heterocyclic.
2. method according to claim 1 is characterized in that: the pincer ligand of described iridium-pincer ligand complex compound is:
Described iridium-pincer ligand complex compound is a compound shown in the following structural formula:
3. method according to claim 1 is characterized in that: the add-on of described iridium-pincer ligand complex compound catalyst is 0.001～0.1mol% of levulinic acid amount of substance.
4. method according to claim 1 is characterized in that: described reaction conditions is: in autoclave, fill the hydrogen of 1～5MPa, control reaction temperature is 50～100 ℃, reacts 15～80 hours; It is described that to use sour conditioned reaction system acidity be 3～4 as the pH value; Described levulinic acid is 1: 1.2 with the ratio of the amount of substance of alkali.
5. method according to claim 1 is characterized in that L
1, L
2Has general formula R separately
1R
2P or R
1R
2N, wherein R
1And R
2Can be independently selected from C
1-C
6Alkyl, C
5-C
6Naphthenic base, any substituted aryl.
6. method according to claim 5 is characterized in that said C
1-C
6Alkyl is methyl, ethyl, sec.-propyl or the tertiary butyl.
7. method according to claim 5 is characterized in that said aryl is any substituted phenyl.
8. method according to claim 5 is characterized in that L
1, L
2Can independently be selected from PMe
2, PEt
2, P
iPr
2, P
tBu
2, PPh
2, PCy
2, NEt
2, N
iPr
2
9. method according to claim 1 is characterized in that described organic solvent is the mixed solvent of methyl alcohol, ethanol, Virahol, THF, toluene or THF and water.
10. method according to claim 1 is characterized in that described alkali is Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, salt of wormwood or triethylamine.
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| CN103232418A (en) * | 2013-05-06 | 2013-08-07 | 中国科学技术大学 | Homogeneous catalytic preparation method of gamma-valerolactone |
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| WO2016056030A1 (en) | 2014-10-08 | 2016-04-14 | Council Of Scientific & Industrial Research | A process for the preparation of gamma-valerolactone by catalytic hydrogenation of levulinic acid using ru-based catalysts |
| CN109575086A (en) * | 2018-12-11 | 2019-04-05 | 中国科学院理化技术研究所 | A kind of pincer Phosphine ligands iridium eka-gold metal catalyst and its preparation method and application |
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| CN103232418A (en) * | 2013-05-06 | 2013-08-07 | 中国科学技术大学 | Homogeneous catalytic preparation method of gamma-valerolactone |
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| CN105289592B (en) * | 2015-11-19 | 2017-11-28 | 中科合成油技术有限公司 | It is catalyzed method of the levulic acid Hydrogenation for γ valerolactones |
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| CN109575086B (en) * | 2018-12-11 | 2021-07-27 | 中国科学院理化技术研究所 | Forcipated phosphine ligand iridium metal catalyst and preparation method and application thereof |
| CN112898244A (en) * | 2019-12-03 | 2021-06-04 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN112898244B (en) * | 2019-12-03 | 2022-12-13 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN111285753A (en) * | 2020-03-16 | 2020-06-16 | 天津绿菱气体有限公司 | Hexafluoro-1,3-butadiene isomerization rearrangement control and purification method |
| CN111285753B (en) * | 2020-03-16 | 2022-04-22 | 天津绿菱气体有限公司 | Hexafluoro-1,3-butadiene isomerization rearrangement control and purification method |
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