CN107162899A - A kind of microwave radiation technology phosphotungstic acid or and its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl propionic ester method - Google Patents
A kind of microwave radiation technology phosphotungstic acid or and its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl propionic ester method Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a kind of microwave radiation technology phosphotungstic acid or and its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl propionic ester method.The preparation method comprises the following steps：Under conditions of microwave radiation technology and catalyst are present, biomass carbohydrates carry out reaction with alcohol and produce the levulinate；The catalyst is phosphotungstic acid or phosphotungstate；The phosphotungstate is any in aluminium phosphotungstic acid, phosphotungstic acid iron, phosphotungstic acid indium and phosphotungstic acid chromium；The consumption of the catalyst is alcohol described in 0.1~0.5mmol/15g.The present invention using microwave radiation technology phosphotungstic acid or its salt catalysis biomass is carbohydrate-modifying prepares levulinate, its technique is simple, and reaction condition is gentle, and the reaction time is short, it is possible to reduce energy consumption, and levulinate yield is high；Used catalyst prepares simple, reaction raw materials is applicable wide, reusable and catalytic activity is without being decreased obviously.
Description
Technical field
The present invention relates to a kind of microwave radiation technology phosphotungstic acid or its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl third
The method of acid esters, belongs to the synthetically prepared field of levulinate.
Background technology
At present, the increasingly depleted of the non-renewable fossil resource such as traditional oil, natural gas and coal and its consumption are brought
Environmental problem turned into two hang-ups that have grown continuously and fast of restriction human society.Biomass is a kind of rich reserves, distribution
Extensively, renewable resource that is cheap and possessing carbon fixation function, HC fuel and chemical industry are produced with fossil resource is replaced
The potential of product.In recent years, Efficient Conversion has obtained more and more extensive concern using biomass resource.Research finds wooden fibre
The biomass such as dimension are mainly made up of cellulose, hemicellulose and lignin, and cellulose and glucose can be obtained by pretreatment
Etc. carbohydrate raw material, these raw materials can be for production high valuable chemicals and bio oil.
Levulinate is (such as：Methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate etc.) it is the important change of a class
Learn intermediate and new green energy compound, can be fired as spices, flavor enhancement, plasticizer, gasoline additive and biofluid
Material etc. is widely used in the industries such as food, rubber, medicine, coating, agricultural chemicals and transport, with good response characteristic and wide
Industrial application value.Industrial levulic acid esters are obtained by industrial chemicals organic synthesis at present, but expensive original
Material cost limits its large-scale application.Using the biomass such as the reproducible cellulose of rich reserves or hexasaccharide carbohydrate as
Raw material, levulinate is obtained by direct alcoholysis, advantageously reduces the production cost of levulinate, for development circulation warp
Ji, environmental protection builds conservation-minded society's tool and is of great significance.
Conventional mode of heating is that reactant is heated by modes such as heat transfer, convection current and radiation, these sides
Formula is limited by convection current and the heat conductivility of reaction medium and container, and not only firing rate is slow, temperature of reaction system it is uneven and
Substantial amounts of energy loss is had in heat transfer process.
The catalyst for preparing levulinate currently used for biomass carbohydrates alcoholysis mainly has (inorganic or organic)
Liquid acid, solid acid and ionic liquid etc..The shortcomings of wherein ionic liquid preparation process is complicated, synthesis cost is high limit its
Industrial application；Liquid acid is although cheap, and reactivity is high, but also has side reaction more, serious to equipment corrosion,
And be not easily recycled, the shortcomings of causing environmental pollution with discharging of waste liquid；Solid acid catalyst has reaction condition gentle, environment friend
It is good and the advantages of be easily recycled, but there is also reactivity it is low, it is poor to reaction raw materials universality the problems such as.
Chinese patent CN 104402724A disclose a kind of sulfonic functional heteropoly acid catalysis cellulose alcoholysis for acetyl
The method of propionic ester.This method prepares levulic acid in autoclave using sulfonic functional heteropoly acid catalysis cellulose
Ester, it is recyclable with catalyst, the advantages of small to equipment corrosion.But there is activity reduction after catalyst recovery in this method,
Temperature is high needed for reaction, and the time is long, the problems such as methyl ester levulinate yield is relatively low.For example 1h, levulic acid first are reacted at 190 DEG C
The conversion ratio of ester is 36mol%, and in low temperature (≤170 DEG C) even if under the conditions of react 3h, methyl ester levulinate yield is also only
11mol%~13mol%.
Chinese patent CN 104693023A disclose a kind of method that biomass sugar prepares levulinate, with biomass
Sugar is raw material, and magnetic basic zirconium phosphate solid is catalyst, and alcoholysis produces levulinate in autoclave.Urged used in the invention
Agent synthesis is with low cost, low in the pollution of the environment to equipment corrosion very little, it is easy to separate, and activity height is reused, with industry
The potentiality of upper large-scale application.But its severe reaction conditions, it is necessary to reaction temperature be 190~210 DEG C, the reaction time be 3~
6h, adds production cost.
Chinese patent CN 103724201A disclose the side that a kind of directly alcoholysis of catalysis biomass sugar prepares levulinate
Method, utilizes a series of cheap Al3+Salt is catalyzed carbohydrate synthesis levulinate.This method reaction condition is gentle, high conversion rate, second
Acyl propionic ester maximum output is up to 67mol%.2.5h, the conversion of aluminum sulfate as catalyst glucose are reacted at 160 DEG C using this method
Be 64mol% for the yield of methyl ester levulinate, however when reacted between shorten to 0.5~1.5h, the production of methyl ester levulinate
Rate just only has 32~52mol%.And replace glucose to make raw material with cellulose and 5h, levulic acid are reacted at a temperature of 160 DEG C
The yield of methyl esters is only 23mol%, is warming up to 180 DEG C, methyl ester levulinate yield just rises to 44mol%.Illustrate this method
There is also the required reaction time is long, the problems such as catalytic effect is undesirable such as cellulose to high glycan, and catalyst can not have
Imitate recycling.
Therefore, exploitation is efficient, catalytic activity is high, environment-friendly, raw material is applicable wide levulinate preparation method, right
Efficient Conversion is very necessary using biomass resource.
The content of the invention
Closed it is an object of the invention to provide a kind of microwave radiation technology phosphotungstic acid or its salt catalysis biomass carbohydrate alcoholysis
Into the method for levulinate, this method have efficiently, quick, reaction condition is gentle, raw material is applicable wide, environment-friendly and yield
High the advantages of, and the recyclable reuse of catalyst.
The preparation method of levulinate provided by the present invention, comprises the following steps：
Under conditions of microwave radiation technology and catalyst are present, biomass carbohydrates carry out reaction with alcohol and produce the second
Acyl propionic ester；
The catalyst is phosphotungstic acid or phosphotungstate.
The reaction is preferably carried out under an inert atmosphere, in such as argon gas atmosphere.
Selection polytetrafluoro pipe is used as reaction vessel.
Before the reaction, magnetic stirrer reactant (biomass carbohydrates, the alcohol and institute are utilized
State the mixture of catalyst) it is well mixed, completed such as in 1min.
In above-mentioned preparation method, the temperature of the reaction can be 120~190 DEG C, concretely 140~190 DEG C, 140
~160 DEG C, 160~190 DEG C, 140 DEG C, 160 DEG C or 190 DEG C, the time can be 5~60min, concretely 30~60min, 40~
60min, 30~40min, 30min, 40min or 60min.
In above-mentioned preparation method, under conditions of microwave power can be 400~800W (setting value), in 1~2min
The system of the reaction is heated to the temperature of the reaction, such as under conditions of microwave power is 600W, heated up in 2min
To the temperature of the reaction.
In above-mentioned preparation method, carried out under conditions of microwave power can be 300~600W under the reaction, i.e. constant temperature
The reaction is carried out, and is carried out in the case where at the uniform velocity stirring.
In above-mentioned preparation method, the phosphotungstate can be aluminium phosphotungstic acid, phosphotungstic acid iron, phosphotungstic acid indium and phosphotungstic acid chromium
In it is any；
The consumption of the catalyst can be alcohol described in 0.1~0.5mmol/15g, concretely alcohol described in 0.1mmol/15g,
Alcohol described in 0.3mmol/15g, alcohol described in 0.4mmol/15g or alcohol described in 0.5mmol/15g；
The phosphotungstic acid is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, using it is preposition in vacuum drying chamber in 100
DEG C vacuum drying 4~6h, be then placed in drier standby；
The phosphotungstate can be according to document (Filek et al.Structural stability and bronsted
acidity of thermally treated AlPW12O40in comparision with H3PW12O40) the subdivision of report
It is prepared by solution：By phosphotungstic acid and metal salt solution mixed in equal amounts, 2h is stirred at room temperature, then heating, which is evaporated, produces；
The metal salt can be the nitrate or chlorate of respective metal；
By taking aluminium phosphotungstic acid as an example, concrete operation method is：2mmol phosphotungstic acid is gone with 6ml respectively with 2mmol aluminum nitrates
Ionized water dissolving is made into the aqueous solution, aluminum nitrate aqueous solution is slowly added in phosphotungstic acid aqueous solution with 1ml/min speed, simultaneously
A few drop 1mol/L salpeter solutions are added into solution, 2h is then stirred at room temperature, solution is finally placed in 100 DEG C of bakings in baking oven
It is dry, gained solid be can obtain into aluminium phosphotungstic acid by grinding.
In above-mentioned preparation method, the biomass carbohydrates can be glucose, fructose, sucrose and cellulose in extremely
Few one kind.
In above-mentioned preparation method, the alcohol can be at least one of methanol, ethanol, isopropanol and n-butanol；
The mass ratio (liquid-solid ratio) of the alcohol and the biomass carbohydrates can be 1~20：1, concretely 7.5~
20：1st, 7.5~15：1st, 7.5~10：1、7.5：1、10：1、15：1 or 20：1.
In above-mentioned preparation method, after the reaction terminates, methods described also includes the regeneration step of the catalyst.
In above-mentioned preparation method, the regeneration step is as follows：
1) system after the reaction terminates is filtered after centrifugation, obtains filter residue and filtrate；
2) extracted again after the concentrating filter liquor, obtain extract and raffinate；The levulinate is extracted
Get in extract；It can be extracted using dichloromethane；
3) aqueous solution of nitric acid (>=1mol/L) is added into the raffinate, solid is obtained after being evaporated, it is namely regenerated to urge
Agent, so far realizes the regeneration of the catalyst；
Step 1) in first filter residue (filter residue being filtrated to get) is repeatedly rinsed using methanol and deionized water (5ml)
Step.
Through the regeneration step, the catalyst reusable edible, and catalytic activity is without being decreased obviously, such as through present invention tool
Body embodiment verifies that the methyl ester levulinate yield after circulating 1 time is 62mol%, the methyl ester levulinate production after circulating 2 times
Rate is 59mol%, and the methyl ester levulinate yield after circulating 3 times is 61mol%, the methyl ester levulinate yield after circulating 4 times
For 61mol%, the methyl ester levulinate yield after circulating 5 times is 58mol%.
The present invention compared with prior art, has the following advantages that：
The present invention using microwave radiation technology phosphotungstic acid or its salt catalysis biomass is carbohydrate-modifying prepares levulinate,
Its technique is simple, and reaction condition is gentle, and the reaction time is short, it is possible to reduce energy consumption, and levulinate yield is high；Used catalyst system
It is standby simple, reaction raw materials are applicable wide, reusable and catalytic activity is without being decreased obviously.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
The phosphotungstic acid used in following embodiments is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, using preposition dry in vacuum
4~6h is dried in vacuo in 100 DEG C in dry case, drier is then placed in standby.
The phosphotungstate used in following embodiments is according to document (Filek et al.Structural stability
and bronsted acidity of thermally treated AlPW12O40in comparision with
H3PW12O40) prepared by the double decomposition of report：By phosphotungstic acid and metal salt solution mixed in equal amounts, 2h is stirred at room temperature,
Then heating, which is evaporated, produces.
The metal salt can be the nitrate or chlorate of respective metal；
Specifically, it is as follows with the preparation method of aluminium phosphotungstic acid：2mmol phosphotungstic acid and 2mmol aluminum nitrates are used into 6ml respectively
Deionized water dissolving is made into the aqueous solution, aluminum nitrate aqueous solution is slowly added in phosphotungstic acid aqueous solution with 1ml/min speed, together
When a few drop 1mol/L salpeter solutions are added into solution, 2h is then stirred at room temperature, solution is finally placed in baking oven 100 DEG C
Drying, aluminium phosphotungstic acid is obtained by gained solid by grinding.
The preparation method of phosphotungstic acid iron, the preparation method of phosphotungstic acid indium and phosphotungstic acid chromium and aluminium phosphotungstic acid is essentially identical.
In following embodiments, the condition of gas chromatographic analysis is as follows：
Chromatographic column：DB-5 (30m × 0.250mm, 0.25 μm)；Flame ionization ditector (FID)；Heating schedule：Just
Beginning temperature 60 C, keeps 3min；180 DEG C are risen to 6 DEG C/min, 3min is kept；270 DEG C, holding are risen to 10 DEG C/min again
15min；250 DEG C of injector temperature；270 DEG C of detector temperature；Sample size is 1 μ L；Carrier gas is nitrogen；Using external standard method by standard
Curve calculates the yield of methyl ester levulinate.
Embodiment 1：
2g glucose, 15g methanol (liquid-solid ratio 7.5 are added into polytetrafluoro pipe:1g/g) and 0.4mmol aluminium phosphotungstic acids,
Stirrer is added, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant
It is well mixed；Microwave power 600W is set, 160 DEG C are warming up in 2min.The temperature is kept under 500W microwave powers
30min, is reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly using ice-water bath after room temperature and takes out reaction mixing
Thing.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate is 64mol%.
Embodiment 2：
1g sucrose, 15g ethanol (liquid-solid ratio 15 are added into polytetrafluoro pipe:1g/g) and 0.3mmol phosphotungstic acids, addition is stirred
Son is mixed, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant mixing equal
It is even；Microwave power 600W is set, 190 DEG C are warming up in 2min.Temperature 30min is kept under 500W microwave powers, in perseverance
Speed stirring is lower to be reacted；After reaction terminates, it is cooled to using ice-water bath after room temperature rapidly and takes out reactant mixture.Negating to mix
Liquid is closed, the yield that gas chromatographic analysis calculates ethyl levulinate is 45mol%.
Embodiment 3：
0.75g fructose, 15g methanol (liquid-solid ratio 20 are added into polytetrafluoro pipe:1g/g) and 0.1mmol phosphotungstic acid iron,
Stirrer is added, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant
It is well mixed；Microwave power 600W is set, 120 DEG C are warming up in 2min.The temperature is kept under 500W microwave powers
60min, is reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly using ice-water bath after room temperature and takes out reaction mixing
Thing.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate is 48mol%.
Embodiment 4：
1g glucose, 15g methanol (liquid-solid ratio 15 are added into polytetrafluoro pipe:1g/g) and 0.4mmol phosphotungstic acid indiums, plus
Enter stirrer, be passed through after argon gas is installed and be put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus mixes reactant
Close uniform；Microwave power 600W is set, 160 DEG C are warming up in 2min.Temperature 40min is kept under 500W microwave powers,
Reacted under constant speed stirring；After reaction terminates, it is cooled to using ice-water bath after room temperature rapidly and takes out reactant mixture.Negate
Mixed liquor is answered, the yield that gas chromatographic analysis calculates methyl ester levulinate is 50mol%.
Embodiment 5：
1g fructose, 15g methanol (liquid-solid ratio 15 are added into polytetrafluoro pipe:1g/g) and 0.4mmol phosphotungstic acid chromium, add
Stirrer, is passed through after argon gas is installed and is put into microwave reaction chamber, and stirring 1min in advance using magnetic stirring apparatus mixes reactant
Uniformly；Microwave power 600W is set, 140 DEG C are warming up in 2min.Temperature 40min is kept under 500W microwave powers,
Constant speed stirring is lower to be reacted；After reaction terminates, it is cooled to using ice-water bath after room temperature rapidly and takes out reactant mixture.Negating should
Mixed liquor, the yield that gas chromatographic analysis calculates methyl ester levulinate is 60mol%.
Embodiment 6：
1.5g celluloses, 15g methanol (liquid-solid ratio 10 are added into polytetrafluoro pipe:1g/g) and 0.4mmol aluminium phosphotungstic acids,
Stirrer is added, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant
It is well mixed；Microwave power 600W is set, 160 DEG C are warming up in 2min.The temperature is kept under 500W microwave powers
60min, is reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly using ice-water bath after room temperature and takes out reaction mixing
Thing.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate is 49mol%.
Embodiment 7：
1g glucose, 15g methanol (liquid-solid ratio 10 are added into polytetrafluoro pipe:1g/g) and 0.5mmol aluminium phosphotungstic acids, plus
Enter stirrer, be passed through after argon gas is installed and be put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus mixes reactant
Close uniform；Microwave power 600W is set, 160 DEG C are warming up in 2min.Temperature 40min is kept under 500W microwave powers,
Reacted under constant speed stirring；After reaction terminates, it is cooled to using ice-water bath after room temperature rapidly and takes out reactant mixture.Negate
Mixed liquor is answered, the yield that gas chromatographic analysis calculates methyl ester levulinate is 53mol%.
Embodiment 8
In addition to the reaction time is 5min, other conditions and step are same as Example 1, and gas chromatographic analysis calculates levulinic
The yield 37mol% of sour methyl esters.
Embodiment 9：
Except glucose addition is 3g (liquid-solid ratioes 5:1g/g), the reaction time is other conditions and step and reality outside 40min
Apply that example 1 is identical, gas chromatographic analysis calculates the yield 56mol% of methyl ester levulinate.
Embodiment 10：
In addition to alcohol used is isopropanol, other conditions and step are same as Example 1, and gas chromatographic analysis calculates levulinic
The yield 19mol% of isopropyl propionate.
Embodiment 11：
In addition to alcohol used is n-butanol, other conditions and step are same as Example 1, and gas chromatographic analysis calculates levulinic
The yield 35mol% of acid butyl ester.
Embodiment 12-16：
In addition to used catalyst is recovery catalyst and cycle-index difference, other conditions and step are same as Example 1,
The yield that gas chromatographic analysis calculates methyl ester levulinate is as shown in table 1.
Specific catalyst recovery step is as follows：
After reaction terminates, taking-up polytetrafluoro pipe, which is placed in ice-water bath, from microwave digestion device is cooled to room temperature；Will reaction
Solution centrifugal is filtered afterwards, obtains filter residue and filtrate, and filtrate is concentrated by being evaporated under reduced pressure, then adds dichloromethane into concentration filtrate
Alkane, levulinate is to be extracted to dichloromethane layer；Into raffinate, (standard of " appropriate " is can to make solution in right amount for addition
It is changed into the state close to clarification, a small amount of (once adding 1ml) multiple adding method is taken during practical operation) 1mol/L nitric acid
The aqueous solution, heats on electric hot plate and boils, until solution is finally evaporated close to clarification, and gained solid is namely regenerated after drying to urge
Agent, is recycled.
Methyl ester levulinate yield during the difference cycle-index of table 1
It is reusable after catalyst regeneration in data in table 1, the inventive method, and catalytic activity is without bright
It is aobvious to decline.
Embodiment 17, the consumption on catalyst
1g glucose, 15g methanol (liquid-solid ratio 15 are added into polytetrafluoro pipe：1g/g) and it is a certain amount of (0.05mmol~
0.6mmol) aluminium phosphotungstic acid, adds stirrer, is passed through after argon gas is installed and is put into microwave reaction chamber, pre- using magnetic stirring apparatus
Stirring 1min is well mixed reactant；Microwave power 600W is set, 160 DEG C are warming up in 2min.In 500W microwave powers
Lower holding temperature 40min, is reacted under constant speed stirring；After reaction terminates, it is cooled to using ice-water bath after room temperature rapidly
Take out reactant mixture.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate specifically see the table below：
Methyl ester levulinate yield during 2 different catalysts addition of table
| Catalyst loading (mmol) | Methyl ester levulinate yield |
| 0.05 | 18mol% |
| 0.1 | 28mol% |
| 0.2 | 47mol% |
| 0.3 | 54mol% |
| 0.4 | 58mol% |
| 0.5 | 52mol% |
| 0.6 | 44mol% |
Catalyst loading is too low it can be seen from the data in table 2, and reaction efficiency is substantially reduced, catalyst loading
Methyl ester levulinate yield during methyl ester levulinate productivity ratio 0.05mmol during for 0.1mmol improves 55%；Catalyst
Adding too much, can promote side reaction, reduce methyl ester levulinate yield, while production cost is added, it is thus determined that catalysis
The addition of agent is 0.1mmol~0.5mmol/15g alcohol.
Embodiment 18, on liquid-solid ratio
A certain amount of glucose and methanol (liquid-solid ratio 3~25 are added into polytetrafluoro pipe：1g/g) and 0.4mmol phosphotungstic acids
Aluminium, adds stirrer, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reaction
Thing is well mixed；Microwave power 600W is set, 160 DEG C are warming up in 2min.The temperature is kept under 500W microwave powers
40min, is reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly using ice-water bath after room temperature and takes out reaction mixing
Thing.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate specifically see the table below：
The methyl ester levulinate yield of the different liquid-solid ratioes of table 3
Liquid-solid ratio is less than 5 it can be seen from the data in table 3：It when 1, can not be sufficiently mixed, drop between reactant and solvent
Low reaction efficiency；Liquid-solid ratio is too high to cause the increase of later stage separating difficulty, increase production cost, and yield declines, it is thus determined that
Liquid-solid ratio is 5~20：1.
Embodiment 19, on reaction temperature
2g glucose, 15g methanol (liquid-solid ratio 7.5 are added into polytetrafluoro pipe:1g/g) and 0.4mmol aluminium phosphotungstic acids,
Stirrer is added, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant
It is well mixed；Microwave power 600W is set, certain temperature (140~190 DEG C) is warming up in 2min.Under 500W microwave powers
Temperature 40min is kept, is reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly after room temperature and is taken using ice-water bath
Go out reactant mixture.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate specifically see the table below：
The methyl ester levulinate yield of the different temperatures of table 4
| Temperature (DEG C) | Methyl ester levulinate yield |
| 140 | 42mol% |
| 150 | 51mol% |
| 160 | 64mol% |
| 170 | 62mol% |
| 180 | 57mol% |
| 190 | 43mol% |
The second of higher yields can be obtained under 140~190 DEG C of reaction temperature it can be seen from the data in table 4
Acyl methyl propionate.
Embodiment 20, on the reaction time
2g glucose, 15g methanol (liquid-solid ratio 7.5 are added into polytetrafluoro pipe:1g/g) and 0.4mmol aluminium phosphotungstic acids,
Stirrer is added, is passed through after argon gas is installed and is put into microwave reaction chamber, stirring 1min in advance using magnetic stirring apparatus makes reactant
It is well mixed；Microwave power 600W is set, 160 DEG C are warming up in 2min.Keep the temperature certain under 500W microwave powers
Time (0~60min), reacted under constant speed stirring；After reaction terminates, it is cooled to rapidly after room temperature and is taken out using ice-water bath
Reactant mixture.Reaction mixture is taken, the yield that gas chromatographic analysis calculates methyl ester levulinate specifically see the table below：
The methyl ester levulinate yield of the different time of table 5
The reaction time is zero to refer to that being raised to assigned temperature just cools in table 5, because temperature-rise period needs 2min, in this section
Partial Conversion is had inside time.
It can be seen from the data in table 5 reaction be less than 5min when, yield is too low, and yield during 60min compared to
Yield during 50min decreases, it is seen then that the reaction time is long to cause the decline of yield, therefore will be defined as 5 in the reaction time
~60min.
Comparative example 1：
Except conventional heating is carried out using autoclave (being furnished with electric heating cover), 160 DEG C are heated to by 30min, other
Condition and step are same as Example 1, and gas chromatographic analysis calculates the yield 61mol% of methyl ester levulinate.Illustrate microwave pair
The DeGrain that reaction yield is improved.But compared to traditional heating, microwave firing rate is fast (to reach reaction temperature in 2min
Degree), the time required to substantially reducing whole reaction process.Microwave directly acts on reaction system simultaneously, it is to avoid traditional heating
The energy loss brought in mode heat transfer process, it is possible to reduce energy expenditure, is a kind of mode of heating of clean and effective.
Comparative example 2~4：
According to (catalyst amount is 0.4mmol/15g methanol) is carried out the step of embodiment 16, simply catalyst is distinguished
Replace with aluminum sulfate, aluminium chloride and aluminum nitrate, the yield that gas chromatographic analysis calculates methyl ester levulinate be respectively 29mol%,
7mol% and 2mol%, it is seen then that be substantially less than the yield 58mol% of aluminium phosphotungstic acid catalysis, illustrates used catalyst tool of the present invention
There is efficient catalytic.
Shown by above-described embodiment：The present invention is a kind of method that utilization renewable resource prepares levulinate, with
Biomass carbohydrates are raw material, using phosphotungstic acid and its salt as catalyst, using microwave radiation technology in temperate condition by biomass
A kind of method of the carbohydrate Efficient Conversion into levulinate.
The present invention reacts 30min and 60min, methyl ester levulinate production at 160 DEG C respectively using glucose, cellulose as raw material
Rate can respectively reach 64mol% (embodiment 1) and 49mol% (embodiment 6).Compared with published related invention, this hair
Bright reaction condition is gentle, and required temperature is low, the time is short, and levulinate yield is high, and catalyst is reusable, and this is efficient
Scientific basis and technical support are provided using renewable resource.
Claims (9)
1. a kind of preparation method of levulinate, comprises the following steps：
Under conditions of microwave radiation technology and catalyst are present, biomass carbohydrates carry out reaction with alcohol and produce the levulinic
Acid esters；
The catalyst is phosphotungstic acid or phosphotungstate.
2. preparation method according to claim 1, it is characterised in that：The temperature of the reaction is 120~190 DEG C, time
For 5~60min.
3. preparation method according to claim 1 or 2, it is characterised in that：In the condition that microwave power is 400~800W
Under, in the temperature that the system of the reaction is heated to the reaction in 1~2min.
4. the preparation method according to any one of claim 1-3, it is characterised in that：It is 300~600W in microwave power
Under conditions of carry out the reaction.
5. the preparation method according to any one of claim 1-4, it is characterised in that：The phosphotungstate is phosphotungstic acid
It is any in aluminium, phosphotungstic acid iron, phosphotungstic acid indium and phosphotungstic acid chromium；
The consumption of the catalyst is alcohol described in 0.1~0.5mmol/15g.
6. the preparation method according to any one of claim 1-5, it is characterised in that：The biomass carbohydrates are
At least one of glucose, fructose, sucrose and cellulose.
7. the preparation method according to any one of claim 1-6, it is characterised in that：The alcohol is methanol, ethanol, isopropyl
At least one of alcohol and n-butanol；
The mass ratio of the alcohol and the biomass carbohydrates is 5~20：1.
8. the preparation method according to any one of claim 1-7, it is characterised in that：After the reaction terminates, the side
Method also includes the regeneration step of the catalyst.
9. preparation method according to claim 8, it is characterised in that：The regeneration step is as follows：
1) system after the reaction terminates is filtered after centrifugation, obtains filter residue and filtrate；
2) extracted again after the concentrating filter liquor, obtain extract and raffinate；
3) aqueous solution of nitric acid is added into the raffinate, solid is obtained after being evaporated, namely regenerated catalyst is so far realized
The regeneration of the catalyst.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993616A (en) * | 2018-07-20 | 2018-12-14 | 江苏扬农化工集团有限公司 | A kind of regeneration method of phosphorus molybdenum/heteropoly tungstic acid quaternary ammonium salt catalyst |
| CN109173962A (en) * | 2018-09-26 | 2019-01-11 | 郑州睿科生化科技有限公司 | The device of phosphotungstate catalyzed conversion glucose synthesis levulic acid |
| CN109913593A (en) * | 2019-04-01 | 2019-06-21 | 长春工业大学 | A kind of magnetic nanometer composite material and preparation method thereof based on polyacid |
| CN111548582A (en) * | 2020-06-11 | 2020-08-18 | 安徽奥凯材料股份有限公司 | Ferric phosphotungstate flame-retardant smoke-suppression semi-rigid PVC (polyvinyl chloride) sheet and preparation method thereof |
| CN112473736A (en) * | 2020-12-04 | 2021-03-12 | 北华大学 | Novel supported polyacid catalyst and application thereof in preparation of levulinate |
| CN113845419A (en) * | 2021-10-21 | 2021-12-28 | 中国科学技术大学 | Preparation method of levulinate |
| CN113896699A (en) * | 2021-10-21 | 2022-01-07 | 中国科学技术大学 | Preparation method of gamma-valerolactone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
| JP2015098454A (en) * | 2013-11-19 | 2015-05-28 | 国立研究開発法人産業技術総合研究所 | Manufacturing method of levulinic acid |
| CN105728042A (en) * | 2016-03-07 | 2016-07-06 | 中国科学院山西煤炭化学研究所 | Catalyst for producing levulinate through furfural and preparation method and application of catalyst |
-
2017
- 2017-05-22 CN CN201710363145.1A patent/CN107162899B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015098454A (en) * | 2013-11-19 | 2015-05-28 | 国立研究開発法人産業技術総合研究所 | Manufacturing method of levulinic acid |
| CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
| CN105728042A (en) * | 2016-03-07 | 2016-07-06 | 中国科学院山西煤炭化学研究所 | Catalyst for producing levulinate through furfural and preparation method and application of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 曾珊珊等: "磷钨酸盐催化转化葡萄糖合成乙酰丙酸", 《化工学报》 * |
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| CN108993616A (en) * | 2018-07-20 | 2018-12-14 | 江苏扬农化工集团有限公司 | A kind of regeneration method of phosphorus molybdenum/heteropoly tungstic acid quaternary ammonium salt catalyst |
| CN108993616B (en) * | 2018-07-20 | 2021-06-29 | 江苏扬农化工集团有限公司 | Regeneration method of phosphomolybdic/tungstic heteropoly acid quaternary ammonium salt catalyst |
| CN109173962A (en) * | 2018-09-26 | 2019-01-11 | 郑州睿科生化科技有限公司 | The device of phosphotungstate catalyzed conversion glucose synthesis levulic acid |
| CN109913593A (en) * | 2019-04-01 | 2019-06-21 | 长春工业大学 | A kind of magnetic nanometer composite material and preparation method thereof based on polyacid |
| CN111548582A (en) * | 2020-06-11 | 2020-08-18 | 安徽奥凯材料股份有限公司 | Ferric phosphotungstate flame-retardant smoke-suppression semi-rigid PVC (polyvinyl chloride) sheet and preparation method thereof |
| CN112473736A (en) * | 2020-12-04 | 2021-03-12 | 北华大学 | Novel supported polyacid catalyst and application thereof in preparation of levulinate |
| CN112473736B (en) * | 2020-12-04 | 2023-07-07 | 北华大学 | Supported polyacid catalyst and application thereof in preparation of levulinate |
| CN113845419A (en) * | 2021-10-21 | 2021-12-28 | 中国科学技术大学 | Preparation method of levulinate |
| CN113896699A (en) * | 2021-10-21 | 2022-01-07 | 中国科学技术大学 | Preparation method of gamma-valerolactone |
| CN113896699B (en) * | 2021-10-21 | 2023-03-10 | 中国科学技术大学 | Preparation method of gamma-valerolactone |
| CN113845419B (en) * | 2021-10-21 | 2023-10-20 | 中国科学技术大学 | Preparation method of levulinate |
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