CN105384711A - Method for preparing valerolactone by acetylpropionic acid catalysis - Google Patents
Method for preparing valerolactone by acetylpropionic acid catalysis Download PDFInfo
- Publication number
- CN105384711A CN105384711A CN201510934027.2A CN201510934027A CN105384711A CN 105384711 A CN105384711 A CN 105384711A CN 201510934027 A CN201510934027 A CN 201510934027A CN 105384711 A CN105384711 A CN 105384711A
- Authority
- CN
- China
- Prior art keywords
- levulinic acid
- ruthenium
- valerolactone
- catalysis
- aluminium nitride
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing valerolactone by acetylpropionic acid catalysis. The method comprises putting levulinic acid and ruthenium-loaded aluminum nitride into a reactor, feeding distilled water and hydrogen into the reactor, and carrying out a reaction process at a temperature of 60-120 DEG C for 1-6h, wherein a ruthenium loading amount is in a range of 3-10%, hydrogen pressure is in a range of 0.5-2MPa and a mass ratio of ruthenium-loaded aluminum nitride to acetylpropionic acid is 0.4-0.8: 1. The method has mild reaction conditions and a high valerolactone yield.
Description
Technical field
The present invention relates to a kind of method that valerolactone prepared by catalysis levulinic acid.
Background technology
Hydrogenation reaction is that inverting biological raw material prepares one of important reaction of fuel and fine chemicals.The levulinic acid coming from biomass material is outstanding platform chemicals, can prepare other important fine chemicals by hydrogenation reaction.Levulinic acid can selective hydrogenation be valerolactone, and wherein valerolactone is the valuable chemical of a kind of tool, can be used as the intermediate of resin solvent and various allied compound.Also lubricant, softening agent, the jelling agent of nonionic surface active agent, the lactone additive of leaded up gasoline is used as, for the dyeing of cellulose ester and synthon.Valerolactone has vanillin food grade,1000.000000ine mesh and coconut aroma.China GB2760-86 is defined as the flavouring agent allowing to use.Main in order to prepare the type essence such as peach, coconut, vanilla.Also being used as solvent, the organic synthesis intermediate of insoluble resin, is a kind of platform chemicals that can be used in producing polymkeric substance and special fine chemicals.But in the middle of prior art, need higher reaction conditions as temperature of reaction or reaction pressure from levulinic acid selective hydrogenation to valerolactone.In order to prepare valerolactone under gentleer reaction conditions, people need to develop the catalyzer having more activity.
Summary of the invention
The present invention is the defect overcoming above-mentioned prior art, provides a kind of method that valerolactone prepared by catalysis levulinic acid.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A method for valerolactone prepared by catalysis levulinic acid, comprises the steps: the aluminium nitride of levulinic acid and load ruthenium to be placed in reaction unit, adds distilled water, passes into hydrogen, at 60 ~ 120 DEG C, react 1 ~ 6h; The charge capacity of described ruthenium is 3% ~ 10%; The pressure of described hydrogen is 0.5 ~ 2MPa; The aluminium nitride of described load ruthenium and the mass ratio of described levulinic acid are 0.4 ~ 0.8:1.
Described aluminium nitride has nitrogen-atoms, and total is rich in electronics, is conducive to levulinic acid hydrogenation.The nitrogen element interaction of described levulinic acid and described aluminium nitride, is fixed in the plane of aluminium nitride, is more conducive to the ruthenium effect with load.
Preferably, the charge capacity of described ruthenium is 5%.
Preferably, the pressure of described hydrogen is 1MPa.
Preferably, described temperature of reaction is 100 DEG C.
Preferably, the aluminium nitride of described load ruthenium and the mass ratio of described levulinic acid are 0.6:1.
Preferably, the described reaction times is 4h.
The aluminium nitride of described load ruthenium can adopt existing method to prepare, and preferably adopts and prepares with the following method: be distributed to by aluminium nitride in distilled water, add ruthenium salts solution, mixing, then slowly drips sodium borohydride solution, reaction 4h, filter, distilled water wash, vacuum-drying.
Compared with prior art, the invention has the beneficial effects as follows:
The invention discloses a kind of method that valerolactone prepared by catalysis levulinic acid, the aluminium nitride of described load ruthenium can effective catalysis levulinic acid valerolactone, and required reaction conditions is gentle, has higher valerolactone productive rate.
Embodiment
Below in conjunction with embodiment, invention is further described.These embodiments are only describe typical case of the present invention, but the present invention is not limited thereto.Test method used in following embodiment if no special instructions, is ordinary method, the raw material used, reagent etc., and if no special instructions, being can from raw material that commercial sources obtains and the reagent such as routine is commercial.
embodiment 1
The preparation of the aluminium nitride of load ruthenium:
Be distributed in the distilled water of 10ml by 500mg aluminium nitride, add containing 67mg ruthenium chloride aqueous solution, 100 DEG C are stirred 1h, then slowly drip sodium borohydride solution (NaBH
4the ratio of the molar weight of/Ru is 5:1), stirring at room temperature 4h, filter, distilled water wash, 100 DEG C of vacuum-dryings, obtain the aluminium nitride (5%Ru/ALN) of load 5% ruthenium.
Valerolactone prepared by catalysis levulinic acid:
The catalyzer accurately taking 200mg levulinic acid and 120mg joins in the liner of autoclave, adds the water of 3ml.After packaged stainless autoclave, take a breath 3 times with hydrogen, then at room temperature pour 1MPa hydrogen.Oil bath pan is preheating to the temperature of requirement, puts into autoclave, 100 DEG C of reaction 4h, stopped reaction, is cooled to room temperature.
After reacted, by filtering product and catalyst separating, after processing filtrate, utilize high performance liquid chromatography (HPLC) to analyze product and reactant, the productive rate calculating valerolactone is 95%
embodiment 2 ~ 11
Be with the difference of embodiment 1, the mass ratio (A) of the charge capacity of temperature of reaction, hydrogen pressure, ruthenium, the aluminium nitride of load ruthenium and levulinic acid and different ruthenium, it the results are shown in as table 1.
table 1
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (6)
1. a method for valerolactone prepared by catalysis levulinic acid, it is characterized in that, comprises the steps: the aluminium nitride of levulinic acid and load ruthenium to be placed in reaction unit, adds distilled water, passes into hydrogen, at 60 ~ 120 DEG C, react 1 ~ 6h; The charge capacity of described ruthenium is 3% ~ 10%; The pressure of described hydrogen is 0.5 ~ 2MPa; The aluminium nitride of described load ruthenium and the mass ratio of described levulinic acid are 0.4 ~ 0.8:1.
2. the method for valerolactone prepared by catalysis levulinic acid according to claim 1, it is characterized in that, the charge capacity of described ruthenium is 5%.
3. the method for valerolactone prepared by catalysis levulinic acid according to claim 1, it is characterized in that, the pressure of described hydrogen is 1MPa.
4. the method for valerolactone prepared by catalysis levulinic acid according to claim 1, it is characterized in that, described temperature of reaction is 100 DEG C.
5. the method for valerolactone prepared by catalysis levulinic acid according to claim 1, it is characterized in that, the aluminium nitride of described load ruthenium and the mass ratio of described levulinic acid are 0.6:1.
6. the method for valerolactone prepared by catalysis levulinic acid according to claim 1, it is characterized in that, the described reaction times is 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510934027.2A CN105384711A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone by acetylpropionic acid catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510934027.2A CN105384711A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone by acetylpropionic acid catalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105384711A true CN105384711A (en) | 2016-03-09 |
Family
ID=55417536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510934027.2A Pending CN105384711A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone by acetylpropionic acid catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384711A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114716A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | The catalyst of one kind gamma-valerolactone and preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496945A (en) * | 2015-01-08 | 2015-04-08 | 山西大学 | Preparation method of gamma-valerolactone |
-
2015
- 2015-12-15 CN CN201510934027.2A patent/CN105384711A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496945A (en) * | 2015-01-08 | 2015-04-08 | 山西大学 | Preparation method of gamma-valerolactone |
Non-Patent Citations (2)
| Title |
|---|
| 姚义俊, 刘 斌，苏 静，蒋晓龙: "高氮/低氧混合气氛下热处理对氮化铝粉末抗水解性能的研究", 《中国陶瓷》 * |
| 姜珩: "氮化铝粉末的制备研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114716A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | The catalyst of one kind gamma-valerolactone and preparation and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496943A (en) | Method for preparing dihydroxymethyl tetrahydrofuran | |
| CN105237371B (en) | Method for preparing vanillin by catalytic oxidative degradation of lignin | |
| Caetano et al. | One-pot synthesis of amines from biomass resources catalyzed by HReO 4 | |
| CN107304367A (en) | A kind of preparation method of branched paraffin in gasoline, aviation kerosine or diesel range | |
| CN101864324B (en) | Method for synthesizing liquid hydrocarbon | |
| CN103275096A (en) | Method for preparing isosorbide based on cellulose | |
| CN105348230A (en) | Method for preparing valerolactone | |
| CN105713642A (en) | Novel method for synthesizing high density aviation fuel from lignocellulose | |
| CN102895974B (en) | Method for synthesizing N-methyl piperidine and supported catalyst used by the method | |
| CN105384711A (en) | Method for preparing valerolactone by acetylpropionic acid catalysis | |
| CN105400540B (en) | A kind of method of fatty alcohol production aviation fuel | |
| CN110372516A (en) | A method of preparing cyclohexylamine | |
| CN105348234A (en) | Method for converting furfural into furfuryl alcohol by catalysis | |
| CN104496775A (en) | Method for preparing benzaldehyde by catalyzing benzyl alcohol | |
| CN108129426B (en) | Method for synthesizing 2, 5-dimethylamino furan by catalytic hydrogenation of 2, 5-dicyanofuran | |
| CN104788408B (en) | A kind of method that γ valerolactones are produced by hemicellulose | |
| CN108250165A (en) | A kind of method for preparing N- (5- methyl furfuryl group) aniline and derivative using biomass carbohydrates | |
| CN111135831A (en) | Preparation method of catalyst for preparing 2-methyltetrahydrofuran by gas-phase hydrogenation of 2-methylfuran | |
| CN105860059A (en) | Method for preparing polyurea from CO2 and diamine in presence of ionic liquid catalyst | |
| CN104059097B (en) | A kind of disproportionation is prepared the method for dimethyldichlorosilane | |
| CN105348229A (en) | Method for catalyzing levulinic acid for conversion | |
| CN111072477A (en) | Method for preparing p-hydroxycinnamate by carrying out copper-catalyzed depolymerization on lignin | |
| CN105348235A (en) | Method for preparing furfuryl alcohol by catalyzing furfural | |
| CN105418551A (en) | Method for preparing furfuryl alcohol by catalyzing furfural | |
| CN104130210B (en) | The preparation method of N-methylmorpholine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160309 |
|
| WD01 | Invention patent application deemed withdrawn after publication |