CN110483268A - A kind of method that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid - Google Patents
A kind of method that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid Download PDFInfo
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- CN110483268A CN110483268A CN201910829768.2A CN201910829768A CN110483268A CN 110483268 A CN110483268 A CN 110483268A CN 201910829768 A CN201910829768 A CN 201910829768A CN 110483268 A CN110483268 A CN 110483268A
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- microcrystalline cellulose
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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Abstract
The invention discloses a kind of methods that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid, belong to biomass chemical field.The present invention uses gamma-valerolactone-water mixed solution for reaction medium using microcrystalline cellulose as raw material, carries out catalysis reaction using heteropoly acid, is separated by solid-liquid separation after purification, obtains product levulic acid.The method raw material sources are extensive and cheap, and catalyst activity is strong and property is stablized, and entire reaction process is more mild, and reaction process process is simple, and easy to implement, efficiency of pcr product is high, and industrializationization has a extensive future.
Description
Technical field
The invention belongs to biomass chemical field, it is related to the side that a kind of heteropoly acid catalysis microcrystalline cellulose prepares levulic acid
Method.
Background technique
Levulic acid is a kind of important platform chemicals, the property with carboxylic acid and ketone, therefore has goodization
Reactivity is learned, the reactions such as chlorination, esterification plus hydrogen, substitution, polymerization, redox is able to carry out, is widely used in resin, medicine
The compounds such as product, rubber and plastic additive, fuel additive, herbicide, flavouring agent, surfactant and novel high polymer close
At.Currently, levulic acid production main technique is hydrolysis of biomass, the principle of the method is the In using biomass as raw material
It is monosaccharide using acid or base catalysis biomass by hydrolyzation under hot conditions, monosaccharide is dehydrated to form 5 hydroxymethyl furfural, and it is raw to continue decarboxylation
At levulic acid.The advantages of method is that raw material sources are wide and price is low, and process flow is simple, easily operated, but there are still acid
The problems such as pollution, reaction temperature height and low yield.
Heteropoly acid is that a kind of have acid, oxidation-reduction quality and thermal stability by what oxygen atom bridges metallic atom was formed
Green metal oxygen cluster function catalyst.Microcrystalline cellulose is one of biomass resource important form, and gamma-valerolactone is applied in life
Substance is converted into the reaction process of platform chemicals ideal sustainable petroleum derived solvents substitute.Research is with crystallite fibre
Dimension element is raw material, in gamma-valerolactone-water mixed solution, is reacted using heteropoly acid catalysis and generates levulic acid, be can reduce anti-
Temperature is answered, efficiency of pcr product is improved, is reduced to environmental disruption, environmental-friendly and production cost is low, is easy to industrialization promotion implementation, symbol
Close current green chemical industry developing direction.
Summary of the invention
To solve the problems, such as that environmental pollution and energy consumption of reaction are high, the present invention provides a kind of heteropoly acid catalysis microcrystalline celluloses
The method for preparing levulic acid, it is therefore intended that make full use of agricultural stalk microcrystalline cellulose biomass resource, reduce energy consumption, subtract
Of low pollution improves yield and save the cost, increases economic benefit, ecological benefits and social benefit.
To achieve the goals above, the present invention is achieved by the following technical programs:
A kind of method that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid, comprising the following steps:
(1) microcrystalline cellulose and heteropoly acid are added in reaction kettle according to mass ratio 1: 5~10: 1；
(2) gamma-valerolactone-water mixed solution of 10~100 times of microcrystalline celluloses is added into reaction kettle, then will fill
The reaction kettle of reactant is placed in 110 DEG C~180 DEG C 1~8h of reaction under stiring；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation and purify can be obtained product levulic acid.
According to technique described above scheme, step (1) microcrystalline cellulose is corn stover microcrystalline cellulose, rice
One of stalk microcrystalline cellulose, wheat stalk microcrystalline cellulose and producing fibre from cotton stalk element are a variety of.
According to technique described above scheme, step (1) heteropoly acid be support type phosphomolybdic acid, carried phospho-tungstic acid and
One of load type silicotungstic acid is a variety of.Wherein load carriers are Titania-Zirconia metal composite oxide.
According to technique described above scheme, step (2) gamma-valerolactone-water mixed solution is according to volume ratio 1: 10
~25: 1 configuration.
According to technique described above scheme, step (2) stirring rate is 300~450 revs/min.
According to technique described above scheme, step (3) described separation method is high speed centrifugation or is filtered under diminished pressure.
According to technique described above scheme, step (3) described purification process is that the solution after separation is carried out decompression steaming
It evaporates to obtain levulic acid.
Compared with prior art, remarkable advantage of the invention is:
The carried heteropoly acid catalyst and reaction dissolvent gamma-valerolactone that the present invention selects are green chemical, to ring
Border pollution destroys small.It is raw material that stalk microcrystalline cellulose is utilized in the present invention, improves agricultural waste straw added value, is enhanced
Economic benefit and social benefit.The technological process of production is simple in the present invention, can moral conduct it is strong, easy to implement, reaction is mild, acetyl
Propionic acid yield is high, and product application is wide, with good application prospect.
Specific embodiment
It will come that the present invention is described in further detail with specific embodiment below, but protection scope of the present invention is not
It is confined to these specific examples.
Embodiment 1:
(1) corn stover microcrystalline cellulose and carried titanium dioxide-zirconium dioxide metal composite oxide phosphomolybdic acid are pressed
It is added in reaction kettle according to mass ratio 1: 1；
(2) 25 times of corn stover microcrystalline cellulose gamma-valerolactone-water mixed solutions are added into reaction kettle, wherein γ-penta
Lactone and water volume ratio are 1: 10, and the reaction kettle for filling reactant is then placed in 150 DEG C of reaction 4h under 300 revs/min of stirrings；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation with supercentrifugal process, solution carries out decompression steaming after separation
Purifying is evaporated, levulic acid efficiency of pcr product is 62%.
Embodiment 2:
(1) wheat stalk microcrystalline cellulose and carried titanium dioxide-zirconium dioxide metal composite oxide phosphomolybdic acid are pressed
It is added in reaction kettle according to mass ratio 2: 1；
(2) 15 times of corn stover microcrystalline cellulose gamma-valerolactone-water mixed solutions are added into reaction kettle, wherein γ-penta
Lactone and water volume ratio are 5: 1, and the reaction kettle for filling reactant is then placed in 180 DEG C of reaction 2h under 400 revs/min of stirrings；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation with supercentrifugal process, solution carries out decompression steaming after separation
Purifying is evaporated, levulic acid efficiency of pcr product is 72%.
Embodiment 3:
(1) rice straw microcrystalline cellulose and carried titanium dioxide-zirconium dioxide metal composite oxide phosphomolybdic acid are pressed
It is added in reaction kettle according to mass ratio 5: 1；
(2) 50 times of corn stover microcrystalline cellulose gamma-valerolactone-water mixed solutions are added into reaction kettle, wherein γ-penta
Lactone and water volume ratio are 10: 1, and the reaction kettle for filling reactant is then placed in 175 DEG C of reaction 4h under 400 revs/min of stirrings；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation with the method that is filtered under diminished pressure, solution carries out decompression steaming after separation
Purifying is evaporated, levulic acid efficiency of pcr product is 67%.
Embodiment 4:
(1) cotton stalk microcrystalline cellulose and carried titanium dioxide-zirconium dioxide metal composite oxide phosphomolybdic acid are pressed
It is added in reaction kettle according to mass ratio 8: 1；
(2) 75 times of corn stover microcrystalline cellulose gamma-valerolactone-water mixed solutions are added into reaction kettle, wherein γ-penta
Lactone and water volume ratio are 5: 1, and the reaction kettle for filling reactant is then placed in 135 DEG C of reaction 6h under 450 revs/min of stirrings；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation with the method that is filtered under diminished pressure, solution carries out decompression steaming after separation
Purifying is evaporated, levulic acid efficiency of pcr product is 68%.
Claims (5)
1. a kind of method that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid, it is characterised in that the following steps are included:
(1) microcrystalline cellulose and heteropoly acid are added in reaction kettle according to mass ratio 1: 5~10: 1；
(2) gamma-valerolactone-water mixed solution of 10~100 times of microcrystalline celluloses is added into reaction kettle, then will fill reaction
The reaction kettle of object is placed in 110 DEG C~180 DEG C 1~8h of reaction under stiring；
(3) after reaction, 20 DEG C are cooled to, will be separated by solid-liquid separation and purify can be obtained product levulic acid.
2. the method that heteropoly acid catalysis microcrystalline cellulose according to claim 1 prepares levulic acid, it is characterised in that: step
Suddenly (1) described microcrystalline cellulose is corn stover microcrystalline cellulose, rice straw microcrystalline cellulose, wheat stalk microcrystalline cellulose
With one of producing fibre from cotton stalk element or a variety of.
3. the method that heteropoly acid catalysis microcrystalline cellulose according to claim 1 prepares levulic acid, it is characterised in that: step
Suddenly (1) described heteropoly acid is one of support type phosphomolybdic acid, carried phospho-tungstic acid and load type silicotungstic acid or a variety of.
4. the method that heteropoly acid catalysis microcrystalline cellulose according to claim 1 prepares levulic acid, it is characterised in that: step
Suddenly (2) described gamma-valerolactone-water mixed solution is configured according to volume ratio 1: 10~25: 1.
5. the method that heteropoly acid catalysis microcrystalline cellulose according to claim 1 prepares levulic acid, it is characterised in that: step
Suddenly (3) described separation method is high speed centrifugation or is filtered under diminished pressure.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149822A (en) * | 2021-01-15 | 2021-07-23 | 太原工业学院 | Method for efficiently producing levulinic acid from cellulose resources |
| CN113185394A (en) * | 2021-04-15 | 2021-07-30 | 华南农业大学 | Method for preparing levulinic acid by using Dowson configuration tungsten-phosphorus heteropoly acid for catalyzing and hydrolyzing cellulose |
| CN115108903A (en) * | 2022-06-07 | 2022-09-27 | 安徽秸家生物科技开发有限公司 | Method for preparing acetic acid by treating alkalized straw based on one-pot two-step method |
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| CN102671712A (en) * | 2012-04-18 | 2012-09-19 | 广西工学院 | Preparation method of novel solid superacid catalyst and application thereof in catalysis of microcrystalline cellulose for synthesis of levulinic acid |
| CN103435577A (en) * | 2013-06-25 | 2013-12-11 | 天津大学 | Method for preparing levulinic acid and co-producing gamma-valerolactone from biomass |
| CN106755611A (en) * | 2017-03-01 | 2017-05-31 | 中国科学技术大学 | A kind of method of heteropoly acid catalysis lignocellulosic hydrolysis |
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Patent Citations (3)
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| CN102671712A (en) * | 2012-04-18 | 2012-09-19 | 广西工学院 | Preparation method of novel solid superacid catalyst and application thereof in catalysis of microcrystalline cellulose for synthesis of levulinic acid |
| CN103435577A (en) * | 2013-06-25 | 2013-12-11 | 天津大学 | Method for preparing levulinic acid and co-producing gamma-valerolactone from biomass |
| CN106755611A (en) * | 2017-03-01 | 2017-05-31 | 中国科学技术大学 | A kind of method of heteropoly acid catalysis lignocellulosic hydrolysis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149822A (en) * | 2021-01-15 | 2021-07-23 | 太原工业学院 | Method for efficiently producing levulinic acid from cellulose resources |
| CN113149822B (en) * | 2021-01-15 | 2023-10-24 | 太原工业学院 | Method for efficiently producing levulinic acid from cellulose resources |
| CN113185394A (en) * | 2021-04-15 | 2021-07-30 | 华南农业大学 | Method for preparing levulinic acid by using Dowson configuration tungsten-phosphorus heteropoly acid for catalyzing and hydrolyzing cellulose |
| CN115108903A (en) * | 2022-06-07 | 2022-09-27 | 安徽秸家生物科技开发有限公司 | Method for preparing acetic acid by treating alkalized straw based on one-pot two-step method |
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