CN105348230A - Method for preparing valerolactone - Google Patents
Method for preparing valerolactone Download PDFInfo
- Publication number
- CN105348230A CN105348230A CN201510933837.6A CN201510933837A CN105348230A CN 105348230 A CN105348230 A CN 105348230A CN 201510933837 A CN201510933837 A CN 201510933837A CN 105348230 A CN105348230 A CN 105348230A
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- CN
- China
- Prior art keywords
- palladium
- valerolactone
- aluminium nitride
- levulinic acid
- reaction
- 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.)
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/824—Palladium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing valerolactone. The method comprises the following steps: putting acetylpropionic acid and palladium-loaded aluminum nitride into a reaction device; adding distilled water and introducing hydrogen gas to react at 60 DEG C to 100 DEG C for 1 to 6 hours, wherein the loading amount of palladium is 1 percent to 10 percent, the pressure of the hydrogen gas is 0.5MPa to 2MPa, and the mass ratio of the palladium-loaded aluminum nitride to the acetylpropionic acid is (0.2 to 0.8):1. The method has moderate reaction conditions and has a relatively high valerolactone yield.
Description
Technical field
The present invention relates to a kind of method preparing valerolactone.
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 preparing valerolactone.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Prepare a method for valerolactone, comprise the steps: the aluminium nitride of levulinic acid and supported palladium to be placed in reaction unit, add distilled water, pass into hydrogen, at 60 ~ 100 DEG C, react 1 ~ 6h; The charge capacity of described palladium is 1% ~ 10%; The pressure of described hydrogen is 0.5 ~ 2MPa; The aluminium nitride of described supported palladium and the mass ratio of described levulinic acid are 0.2 ~ 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 palladium effect with load.
Preferably, the charge capacity of described palladium is 5%.
Preferably, the pressure of described hydrogen is 1MPa.
Preferably, described temperature of reaction is 80 DEG C.
Preferably, the aluminium nitride of described supported palladium and the mass ratio of described levulinic acid are 0.5:1.
Preferably, the described reaction times is 4h.
The aluminium nitride of described supported palladium 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 palladium 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 preparing valerolactone, the aluminium nitride of described supported palladium 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 supported palladium:
Be distributed in the distilled water of 10ml by 500mg aluminium nitride, add containing the 70mg potassium palladochloride aqueous solution, 80 DEG C are stirred 1h, then slowly drip sodium borohydride solution (NaBH
4the ratio of the molar weight of/Pd is 5:1), stirring at room temperature 4h, filter, distilled water wash, 80 DEG C of vacuum-dryings, obtain the aluminium nitride (5%Pd/ALN) of load 5% palladium.
Valerolactone prepared by catalysis levulinic acid:
The catalyzer accurately taking 200mg levulinic acid and 100mg 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, 80 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 ~ 9
Be with the difference of embodiment 1, the mass ratio (A) of the charge capacity of temperature of reaction, hydrogen pressure, palladium, the aluminium nitride of supported palladium and levulinic acid and different palladium, 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. prepare a method for valerolactone, it is characterized in that, comprise the steps: the aluminium nitride of levulinic acid and supported palladium to be placed in reaction unit, add distilled water, pass into hydrogen, at 60 ~ 100 DEG C, react 1 ~ 6h; The charge capacity of described palladium is 1% ~ 10%; The pressure of described hydrogen is 0.5 ~ 2MPa; The aluminium nitride of described supported palladium and the mass ratio of described levulinic acid are 0.2 ~ 0.8:1.
2. the method preparing valerolactone according to claim 1, is characterized in that, the charge capacity of described palladium is 5%.
3. the method preparing valerolactone according to claim 1, is characterized in that, the pressure of described hydrogen is 1MPa.
4. the method preparing valerolactone according to claim 1, is characterized in that, described temperature of reaction is 80 DEG C.
5. the method preparing valerolactone according to claim 1, is characterized in that, the aluminium nitride of described supported palladium and the mass ratio of described levulinic acid are 0.5:1.
6. the method preparing valerolactone according to claim 1, is characterized in that, the described reaction times is 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510933837.6A CN105348230A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510933837.6A CN105348230A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105348230A true CN105348230A (en) | 2016-02-24 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510933837.6A Pending CN105348230A (en) | 2015-12-15 | 2015-12-15 | Method for preparing valerolactone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105348230A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866589A (en) * | 2017-01-17 | 2017-06-20 | 浙江大学 | A kind of preparation method of γ valerolactones |
| CN108059594A (en) * | 2017-11-17 | 2018-05-22 | 中山大学 | A kind of green syt Pd catalyst conversion of biomass monomer is the method for clean fuel |
| CN110756213A (en) * | 2019-11-07 | 2020-02-07 | 中国科学院上海高等研究院 | Aluminum nitride-based catalyst, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
| CN103232418A (en) * | 2013-05-06 | 2013-08-07 | 中国科学技术大学 | Homogeneous catalytic preparation method of gamma-valerolactone |
| CN104496943A (en) * | 2014-11-28 | 2015-04-08 | 林康艺 | Method for preparing dihydroxymethyl tetrahydrofuran |
-
2015
- 2015-12-15 CN CN201510933837.6A patent/CN105348230A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
| CN103232418A (en) * | 2013-05-06 | 2013-08-07 | 中国科学技术大学 | Homogeneous catalytic preparation method of gamma-valerolactone |
| CN104496943A (en) * | 2014-11-28 | 2015-04-08 | 林康艺 | Method for preparing dihydroxymethyl tetrahydrofuran |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866589A (en) * | 2017-01-17 | 2017-06-20 | 浙江大学 | A kind of preparation method of γ valerolactones |
| CN106866589B (en) * | 2017-01-17 | 2019-02-26 | 浙江大学 | A kind of preparation method of gamma-valerolactone |
| CN108059594A (en) * | 2017-11-17 | 2018-05-22 | 中山大学 | A kind of green syt Pd catalyst conversion of biomass monomer is the method for clean fuel |
| CN108059594B (en) * | 2017-11-17 | 2021-03-12 | 中山大学 | Method for converting biomass monomer into clean fuel by green synthesis of Pd catalyst |
| CN110756213A (en) * | 2019-11-07 | 2020-02-07 | 中国科学院上海高等研究院 | Aluminum nitride-based catalyst, preparation method and application |
| CN110756213B (en) * | 2019-11-07 | 2022-08-26 | 中国科学院上海高等研究院 | Aluminum nitride-based catalyst, preparation method and application |
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Application publication date: 20160224 |