CN107337598A - It is a kind of to be catalyzed the method that xylose is levulic acid isopropyl ester in isopropanol based on acidic catalyst - Google Patents
It is a kind of to be catalyzed the method that xylose is levulic acid isopropyl ester in isopropanol based on acidic catalyst Download PDFInfo
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- CN107337598A CN107337598A CN201710586263.9A CN201710586263A CN107337598A CN 107337598 A CN107337598 A CN 107337598A CN 201710586263 A CN201710586263 A CN 201710586263A CN 107337598 A CN107337598 A CN 107337598A
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- isopropanol
- acidic catalyst
- xylose
- levulic acid
- catalyzed
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method that xylose is levulic acid isopropyl ester is catalyzed in isopropanol based on acidic catalyst the invention discloses a kind of, is comprised the following steps：By acid macroreticular resin, xylose and isopropanol solvent mixing, air-discharging, heating, cooling, washing, separation and drying.The present invention is using acid macroreticular resin as catalyst, and catalytic efficiency is higher, and cost is low；Using isopropanol as solvent, target product conversion ratio ratio is high in normal propyl alcohol, solves the problems, such as that xylose conversion ratio in normal propyl alcohol solvent is low, operating method is convenient and simple.
Description
Technical field
The present invention relates to a kind of method for transformation of levulic acid isopropyl ester, more particularly to a kind of acidic catalyst that is based on is different
The method that xylose is levulic acid isopropyl ester is catalyzed in propyl alcohol.
Background technology
At present, non-renewable resources increasingly depleted, the energy and environmental problem annoying the mankind.But in nature extensively
Existing lignocellulosic is expected to turn into a kind of environmentally friendly and reproducible alternative energy source.Exactly this raw material is cheap, number
The characteristics of huge is measured, energy problem can be alleviated to a certain extent, so being prepared using discarded renewable crops effective
Chemicals increases its surcharge, and oneself has been subjected to the concern of many laboratories and factory.
Levulic acid isopropyl ester, plays the role of important in chemical field, is many organic compounds of synthesis and synthesis tree
The raw material of fat, can synthesizing fungicide, anticancer antiphlogistic in drug field；Fragrance dressing agent and flavouring can be used as in fragrance industry
Agent；Preservative etc. is also used as in food service industry.Levulic acid isopropyl ester is mainly made by agricultural byproducts high temperature acidolysis at present.
Industrial production levulic acid isopropyl ester mainly utilizes agricultural and sideline crop product, such as bagasse, corncob, wheat straw
Deng.The most important principle of production technology of levulic acid isopropyl ester is exactly that the xylan hydrolysis in lignocellulosic are produced into wood
Sugar, the xylose of generation is then generated into levulic acid isopropyl ester through catalytic dehydration.Xylose levulic acid is different in traditional handicraft
Propyl ester process is numerous and diverse, is particularly in normal propyl alcohol solvent, and conversion ratio is extremely low, and adds inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid
Deng although these inorganic acid catalytic efficiencies are higher, strong acid is to the seriously corroded of reactor, and there is major safety risks；
These acid are miscible with water, after reaction terminates, it is difficult to are separated with product, liquid waste processing difficulty cost is high.
The content of the invention
The present invention is directed to the deficiency of above-mentioned technology, there is provided one kind is catalyzed xylose based on acidic catalyst in isopropanol
For the method for levulic acid isopropyl ester, it is intended to solve prior art by xylose levulic acid isopropyl ester process it is numerous and diverse and turn
The problem of rate is relatively low, using isopropanol as solvent, levulic acid isopropyl ester is prepared by xylose, target product conversion ratio ratio exists
It is high in normal propyl alcohol；Solve the problems, such as that xylose conversion ratio in normal propyl alcohol solvent is low, operating method is convenient and simple.
The present invention is achieved through the following technical solutions, and the present invention provides a kind of acidic catalyst that is based in isopropanol
The method that xylose is levulic acid isopropyl ester is catalyzed, is comprised the following steps：
(1) mix：It is put into autoclave and stirs at room temperature after acidic catalyst, xylose and isopropanol solvent are mixed
Mix uniformly；Acidic catalyst is acid macroreticular resin；(2) air-discharging：Exclude the air in autoclave；(3) heat：By mixture
Heating is stirred in autoclave；(4) cool：Autoclave is down to room temperature；(5) wash, separate, dry：Life to collection
Washed, separated with acidic catalyst into thing, the solids after separation is dried to constant weight.
Isopropanol solvent functions not only as medium dissolving xylose, and it is acetyl to be also used as reactant and participate in xylose
In the reaction of isopropyl propionate；Isopropanol participate in reaction in mechanism be：Isopropanol is a hydrogen supply dissolvent, it may occur that dehydrogenation
Reaction generation acetone, the hydrogen of removing is furfuryl alcohol furfural in-situ reducing, and acidolysis is levulinate to furfuryl alcohol again.It is from isopropanol
Solvent, reaction medium can be stablized, promote the formation of levulic acid isopropyl ester, can slow down acetyl with the extension in reaction time
The decomposition of isopropyl propionate.Using isopropanol as solvent, target product conversion ratio ratio is high in normal propyl alcohol, solves xylose just
The problem of conversion ratio is low in propanol solvent, operating method are convenient and simple.Using acid macroreticular resin as catalyst, catalytic efficiency
Higher, cost is relatively low, free from environmental pollution.
Preferably, in step (1), the particle diameter of the acid macroreticular resin is 0.121~0.989mm.This particle diameter is catalyzed
The catalytic efficiency of agent is higher.
Preferably, in step (1), it is 5~10g to add acidic catalyst quality, and xylose quality is 5~10g, isopropanol
The volume of solvent is 50~100mL.
Preferably, in step (1), mixing speed is 400~700rpm, and mixing time is 10~20min.Stirring be for
Accelerate dissolving.
Preferably, in step (2), the air in autoclave is excluded using High Purity Nitrogen.
Preferably, in step (3), mixture is heated to 175 DEG C in autoclave, and firing rate is 10 DEG C/min.
Preferably, in step (5), product and acidic catalyst are subjected to washing 3-5 times by acetone soln, washed
Product after washing is separated by vacuum filtration.Acidic catalyst enters in acetone soln during washing, and catalyst is with acetone
Solution filters out, the catalyst acetone soln that vacuum filtration separation is not filtered out.
Preferably, in step (5), the solids after separation dries 4~6h to constant weight at 105 DEG C.The product of drying
That is levulic acid isopropyl ester.
Beneficial effects of the present invention are：
(1) it is provided by the invention to prepare the convenient and simple of levulic acid isopropyl ester, suitable for industrial production；Made with isopropanol
For solvent, levulic acid isopropyl ester is prepared by xylose, target product conversion ratio ratio is high in normal propyl alcohol, solves xylose just
The problem of conversion ratio is low in propanol solvent.
(2) for the present invention using acid macroreticular resin as catalyst, catalytic efficiency is higher, and cost is relatively low, free from environmental pollution,
Prior art is overcome using strong acid as catalyst, waste liquid is difficult to the defects of environment is polluted in processing.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is that the present invention is catalyzed the reaction equation that xylose prepares levulic acid isopropyl ester in isopropanol solvent；
Fig. 2 is the present invention and the conversion rate curve of contrast experiment's xylose under the differential responses time；
Fig. 3 is the gaschromatographic mass spectrometry figure of the product of contrast test；
Fig. 4 is the gaschromatographic mass spectrometry figure of the product of the present invention；
Fig. 5 present invention and the yield curve of contrast experiment's levulic acid propyl ester under the differential responses time.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1, the present invention are that a kind of xylose is catalyzed in isopropanol based on acidic catalyst is that levulic acid is different
The method of propyl ester, comprises the following steps：
(1) mix：It is 5g by acid macroreticular resin quality, xylose quality is 10g and the volume of isopropanol solvent is
It is put into autoclave and stirs at room temperature after 50mL mixing, mixing speed 700rpm, mixing time 20min；
(2) air-discharging：After mixture is added to reactor, the air in autoclave is excluded using High Purity Nitrogen；
(3) heat：Mixture in autoclave reactor is heated to 175 DEG C under conditions of stirring, firing rate is
10℃/min；
(4) sample：Sample after heating is continued into the insulation reaction at 175 DEG C, and taken in the process every 20min
Sample once, tests conversion ratio of the xylose in isopropanol, as shown in Figure 2；React 90min, the conversion ratio of xylose turns 100%
The accessory substance of change is less；
(5) cool：High pressure reactor reaction device is cooled to room temperature；
(6) wash, separate, dry：Product and catalyst are subjected to washing 3 times, upper strata after filtering by acetone soln
After clear liquid, product is separated by being filtered by vacuum, and separation product is positioned in baking oven 4~6h is dried at 105 DEG C to constant weight；Knot
Fruit be illustrated in figure 3 the present invention can not under the reaction time levulic acid isopropyl ester richness block diagram.
Isopropanol solvent functions not only as medium dissolving xylose, and it is acetyl to be also used as reactant and participate in xylose
In the reaction of isopropyl propionate；The mechanism that isopropanol is participated in reaction is that it is a hydrogen supply dissolvent, it may occur that dehydrogenation reaction
Acetone is generated, the hydrogen of removing is furfuryl alcohol furfural in-situ reducing, and acidolysis is levulinate to furfuryl alcohol again.Its reaction equation is as schemed
Shown in 1.It is solvent from isopropanol, reaction medium can be stablized, promotes the formation of levulic acid isopropyl ester, with the reaction time
Extension can slow down the decomposition of levulic acid isopropyl ester.It is inexpensively easy as catalyst, macroreticular resin using acid macroreticular resin
, there is good pore structure, big specific surface area, catalytic efficiency is higher, free from environmental pollution, have excellent mechanical strength with
Chemical stability, energy high temperature resistant, is a kind of good solid acid catalyst of application prospect.
Contrast experiment：It is a kind of to be catalyzed the side that xylose is levulic acid n-propyl in normal propyl alcohol based on acidic catalyst
Method, comprise the following steps：
(1) mix：It is 5g by acid macroreticular resin quality, xylose quality is 10g and the volume of normal propyl alcohol solvent is
It is put into autoclave and stirs at room temperature after 50mL mixing, mixing speed 700rpm, mixing time 20min；
(2) air-discharging：After mixture is added to reactor, the air in autoclave is excluded using High Purity Nitrogen；
(3) heat：Mixture in autoclave reactor is heated to 175 DEG C under conditions of stirring, firing rate is
10℃/min；
(4) sample：Sample after heating is continued into the insulation reaction at 175 DEG C, and taken in the process every 20min
Sample once, tests conversion ratio of the xylose in normal propyl alcohol, as shown in Figure 2；React 90min, the conversion ratio of normal propyl alcohol 100%,
But the accessory substance of conversion is more；
(5) cool：High pressure reactor reaction device is cooled to room temperature；
(6) drying is washed：Product and catalyst are subjected to washing 3 times by acetone soln, after filtering after supernatant liquor,
Product is separated by being filtered by vacuum, and separation product is positioned in baking oven 4~6h is dried at 105 DEG C to constant weight；As a result as schemed
3 show the richness block diagram of contrast test levulic acid n-propyl under the differential responses time.
Experimental result：Table 1 is the xylose rate of the invention measured with contrast experiment after 90min is reacted, levulic acid
The data of the yield of propyl ester richness and levulic acid propyl ester；Fig. 2 is the present invention and contrast experiment under the differential responses time
The conversion rate curve of xylose；For the present invention when the reaction time is 90min, the conversion ratio of xylose is 100%, Fig. 5 in isopropanol
Shown, the accessory substance in isopropanol after xylose is few, generates 93% levulic acid isopropyl ester；Contrast experiment is reacting
During 90min, although xylose rate is also 100% in normal propyl alcohol, as shown in figure 5, the accessory substance after xylose compared with
It is more, only generate 35% levulic acid n-propyl；Fig. 3 is the gaschromatographic mass spectrometry figure of the product of contrast test, can from Fig. 3
Using the product obtained by drawing as levulic acid n-propyl；Fig. 4 is the gaschromatographic mass spectrometry figure of the product of the present invention, from Fig. 4
The product that gained can be drawn is levulic acid isopropyl ester；Fig. 5 is the present invention and contrast experiment's acetyl under the differential responses time
The yield curve of propyl propionate；The yield of levulic acid isopropyl ester is significantly larger than levulic acid n-propyl yield.
Table 1
Under conditions of acid macroreticular resin catalyst, solvent is made to xylose as levulic acid isopropyl ester using isopropanol
Conversion ratio be greater than the conversion ratio for making solvent xylose with normal propyl alcohol.
Certainly, described above is also not limited to the example above, the technical characteristic of the invention without description can by or
Realized, will not be repeated here using prior art；Above example and accompanying drawing are merely to illustrate technical scheme
It is limitation of the present invention, the present invention is described in detail with reference to preferred embodiment, the ordinary skill people of this area
Member is it should be appreciated that change, remodeling, the addition that those skilled in the art are made in the essential scope of the present invention
Or replace the claims that without departure from spirit of the invention, should also belong to the present invention.
Claims (8)
1. a kind of be catalyzed the method that xylose is levulic acid isopropyl ester based on acidic catalyst in isopropanol, including following
Step：
(1) mix：It is put into autoclave and stirs at room temperature after acidic catalyst, xylose and isopropanol solvent are mixed
It is even；Acidic catalyst is acid macroreticular resin；(2) air-discharging：Exclude the air in autoclave；(3) heat：By mixture in height
Heating is stirred in pressure kettle；(4) cool：Autoclave is down to room temperature；(5) wash, separate, dry：To the product of collection
Washed, separated with acidic catalyst, the solids after separation is dried to constant weight.
It is that levulic acid is different that 2. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (1), the particle diameter of the acid macroreticular resin is 0.121~0.989mm.
It is that levulic acid is different that 3. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (1), it is 5~10g to add acidic catalyst quality, and xylose quality is 5~10g,
The volume of isopropanol solvent is 50~100mL.
It is that levulic acid is different that 4. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (1), mixing speed is 400~700rpm, and mixing time is 10~20min.
It is that levulic acid is different that 5. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (2), the air in autoclave is excluded using High Purity Nitrogen.
It is that levulic acid is different that 6. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (3), mixture is heated to 175 DEG C in autoclave, and firing rate is 10 DEG C/
min。
It is that levulic acid is different that 7. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (5), product and acidic catalyst are subjected to washing 3-5 by acetone soln
Secondary, the product after washing is separated by vacuum filtration.
It is that levulic acid is different that 8. one kind according to claim 1 is catalyzed xylose based on acidic catalyst in isopropanol
The method of propyl ester, it is characterised in that：In step (5), the solids after separation dries 4~6h to constant weight at 105 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710586263.9A CN107337598A (en) | 2017-07-18 | 2017-07-18 | It is a kind of to be catalyzed the method that xylose is levulic acid isopropyl ester in isopropanol based on acidic catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710586263.9A CN107337598A (en) | 2017-07-18 | 2017-07-18 | It is a kind of to be catalyzed the method that xylose is levulic acid isopropyl ester in isopropanol based on acidic catalyst |
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| CN107337598A true CN107337598A (en) | 2017-11-10 |
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| CN201710586263.9A Pending CN107337598A (en) | 2017-07-18 | 2017-07-18 | It is a kind of to be catalyzed the method that xylose is levulic acid isopropyl ester in isopropanol based on acidic catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409559A (en) * | 2018-03-29 | 2018-08-17 | 济南大学 | A kind of method that furfural prepares ethyl levulinate |
| CN108911985A (en) * | 2018-07-09 | 2018-11-30 | 集美大学 | The method and its application of p-Coumaric Acid ethyl ester are isolated and purified from camellia pollen |
-
2017
- 2017-07-18 CN CN201710586263.9A patent/CN107337598A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| LENNTECH: "Amberlyst 70", 《GOOGLE》 * |
| XUN HU等: "Acid-Catalyzed Conversion of Xylose in 20 Solvents: Insight into Interactions of the Solvents with Xylose , Furfural, and the Acid Catalyst", 《ACS SUSTAINABLE CHEM. ENG.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409559A (en) * | 2018-03-29 | 2018-08-17 | 济南大学 | A kind of method that furfural prepares ethyl levulinate |
| CN108911985A (en) * | 2018-07-09 | 2018-11-30 | 集美大学 | The method and its application of p-Coumaric Acid ethyl ester are isolated and purified from camellia pollen |
| CN108911985B (en) * | 2018-07-09 | 2021-07-27 | 集美大学 | Method for separating and purifying ethyl p-hydroxycinnamate from camellia pollen and application of ethyl p-hydroxycinnamate |
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Application publication date: 20171110 |