CN110981716A - Method for producing levulinic acid by catalyzing starchy raw material with mechanically activated and reinforced metal Lewis acid - Google Patents
Method for producing levulinic acid by catalyzing starchy raw material with mechanically activated and reinforced metal Lewis acid Download PDFInfo
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Abstract
The invention discloses a method for producing levulinic acid by catalyzing starch raw materials by mechanical activation reinforced metal Lewis acid, which is characterized in that the starch raw materials are pretreated by mechanical activation or mechanical activation combined with the metal Lewis acid, so that the crystallization and particle structure of starch can be effectively destroyed, and the catalytic effect of a catalyst during hydrothermal reaction is improved; then the pretreated starch is catalytically converted by taking metal Lewis acid as a catalyst under the hydrothermal condition, and AlCl is used in the method3、CuCl2、FeCl3Or ZnCl2The catalyst is used for catalyzing starch to produce levulinic acid, the catalysis effect is good, and the yield of the levulinic acid is high.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to a method for producing levulinic acid by catalyzing starchy materials with mechanically activated and strengthened metal Lewis acid.
Background
Levulinic Acid Levulinic Acid (LA) [ CAS:123-76-2 ]]Also known as 5-oxopentanoic acid, 4-pentanoic acid, was the simplest gamma-oxocarboxylic acid, found by Mulder in mineral acid degradation products of sucrose in 1840. The name levulinic acid was named by Grote in 1950 and was chosen as a high potential C for the synthesis of high value-added chemicals in the 50 s of the 20 th century5A compound is provided. In 2004, Werpy and Petersen listed levulinic acid as "TOP 12 Large platform chemical". The application of the compound in the industries of pesticide, solvent, medicine, food additive, cosmetics and the like is increasingly wide, and the economic growth is expected to be continuously promoted in the coming years. In 2013, the global market demand for levulinic acid is 2606.2 tons, and 3820 tons is expected to be reached by 2020. The predicted market share of levulinic acid in 2013 is as follows: 23.3% of medicine, 42.8% of agriculture, 13% of cosmetics and 21% of food additive, wherein the price fluctuates between $ 1000 and $ 3000 per ton.
At present, the domestic levulinic acid preparation industry mainly carries out catalytic conversion by inorganic acid, the industrial process has high energy consumption and serious environmental pollution, and does not meet the requirements of the current chemical industry. In addition, a method for producing levulinic acid by using biomass raw materials such as starch and cellulose is also a relatively common method, the biomass raw materials and inorganic acid (hydrochloric acid, sulfuric acid and the like) or salt (cobalt sulfate, ferric sulfate and aluminum sulfate) solution thereof are heated together at a high temperature, the reaction temperature is between 100 and 250 ℃, and then the levulinic acid is obtained by filtering, separating and purifying, wherein the reaction mechanism is as follows: the biomass raw material is hydrolyzed into glucose, the glucose is further decomposed into 5-hydroxymethylfurfural and other side reaction products under the high-temperature condition, and the 5-hydroxymethylfurfural is decomposed into levulinic acid and formic acid under the acidic condition.
The Guangxi is the biggest cassava advantage producing area in China, the cassava planting and the cassava yield are the first in China, and about 80% of cassava starch and cassava powder are provided by the Guangxi every year in China. Meanwhile, Guangxi is a big province of oil and coal shortage, and the industrial development taking cassava ethanol as a characteristic resource can reduce the dependence on fossil fuel, promote the quality of fuel oil to be improved, improve the atmospheric quality, stimulate agriculture and provide more employment opportunities. Therefore, research and development of a new levulinic acid production process are carried out, the concept of green chemical industry is fully exerted by utilizing the advantageous crop cassava in Guangxi, and the method has important significance for fully exerting the advantages of the Guangxi cassava industry.
However, the above conventional methods for preparing levulinic acid from biomass raw materials have the problems of long reaction time, low conversion rate of levulinic acid and the like, and therefore, a better method for producing levulinic acid from biomass raw materials cassava needs to be explored.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for producing levulinic acid by catalyzing starch raw materials by using mechanical activation reinforced metal Lewis acid.
The technical scheme of the invention is as follows:
a method for producing levulinic acid by catalyzing starchy materials with mechanically activated and strengthened metal Lewis acid comprises the following steps: pretreating the starchy raw material by mechanical activation to obtain pretreated starch, and then carrying out catalytic conversion on the pretreated starch by taking metal Lewis acid as a catalyst under a hydrothermal condition to obtain levulinic acid.
Preferably, the method comprises the following steps:
(1) pretreatment of starch: adding starch into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50-55 ℃ and the reaction time at 30-60min, and then sieving to obtain pretreated starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, then adding a metal Lewis acid catalyst for hydrothermal reaction at the temperature of 120 ℃ and 240 ℃ for 2-2.5h, and then cooling the obtained reaction solution and then coating the reaction solution to obtain the levulinic acid.
Preferably, when the starchy raw material is pretreated, metal Lewis acid is also added into the raw material, and the metal Lewis acid comprises AlCl3、CuCl2、FeCl3、ZnCl2The amount of the metal Lewis acid added to each gram of starch is 0.05-0.3 mmol.
As further optimization of the technical scheme, the metal Lewis acid is AlCl3Adding AlCl into each gram of starch3The amount of (B) is 0.05-0.15 mmol.
Preferably, the starchy raw materials comprise cassava, corn, rice, potatoes, wheat and barley.
Preferably, the metal Lewis acid catalyst is AlCl3、CuCl2、FeCl3Or ZnCl2The amount of the metal Lewis acid catalyst added in per gram of starch is 0.05-0.3 mmol.
As further optimization of the technical scheme, the metal Lewis acid catalyst is AlCl3Adding AlCl into each gram of starch3The amount of (B) is 0.05-0.1 mmol.
Preferably, in the step (2), the mass ratio of the pretreated starch to the metal Lewis acid catalyst is 1: 40-50.
Preferably, the pore size of the membrane is 0.20 to 0.25 μm.
Preferably, the yield of the levulinic acid is 30-55%.
The principle of the invention is as follows:
the method comprises the steps of pretreating a starch raw material by using mechanical activation or mechanical activation combined with metal Lewis acid, then carrying out hydrothermal reaction on the pretreated starch and a metal Lewis acid catalyst, wherein the crystal structure and the particle structure of the starch are obviously destroyed by the mechanical activation of the pretreated starch raw material, so that the contact reaction sites of the starch and the metal Lewis acid catalyst are increased, and meanwhile, the diffusion resistance of the metal Lewis acid catalyst is reduced by pretreated starch paste liquid, so that the metal Lewis acid catalyst is more easily diffused into the molecules of the starch to hydrolyze the starch, thereby enhancing the catalytic reaction; when the starch is pretreated by the cooperation of mechanical activation and metal Lewis acid, the metal Lewis acid catalyst can enter the starch granules smoothly during hydrothermal reaction, the direct action of metal Lewis acid ions and the hydroxyl of the starch is promoted, and the catalytic effect is improved.
The invention has the beneficial effects that:
(1) the method uses mechanical activation or mechanical activation combined with metal Lewis acid to pretreat the starchy raw material, can effectively destroy the crystallization and the particle structure of the starch, smoothly inserts the metal Lewis acid into the starch, promotes the direct action of metal Lewis acid ions and the hydroxyl of the starch, has good catalytic effect, can greatly reduce the dosage of a catalyst in hydrothermal reaction, and compared with untreated starch, the starch subjected to mechanical activation pretreatment can reduce the dosage of the catalyst by 33.3-50 percent and has higher levulinic acid yield under the same reaction time.
(2) The invention uses AlCl3、CuCl2、FeCl3Or ZnCl2The catalyst is used for catalyzing starch to produce levulinic acid, the starch can be better catalyzed and converted into the levulinic acid, the yield of the levulinic acid is 30-55 percent, and particularly AlCl is selected3When the catalyst is used, the yield of the levulinic acid is highest and can reach 55 percent.
(3) The invention embodies the atom economy in green chemistry while avoiding the use of external H+The energy consumption of equipment and the loss of facilities in the conversion process are reduced to the maximum extent. The method of the invention not only can be used for catalytically converting the cassava starch to produce the levulinic acid, but also can be used for catalytically converting other starchy raw materials such as corn, rice, potato, wheat, barley and the like to produce the levulinic acid, and the raw materials have wide application range and are convenient to popularize and apply.
Drawings
FIG. 1 is a graph comparing the yields of levulinic acid for comparative example 1 and examples 1-2;
FIG. 2 is a graph comparing the yields of glucose for comparative example 1 and examples 1-2;
FIG. 3 is a graph comparing the yields of levulinic acid for comparative example 1 and examples 3-4;
FIG. 4 is a graph comparing the yields of glucose for comparative example 1 and examples 3-4;
FIG. 5 shows crude potato chipsStarch, mechanically activated pretreated cassava starch, mechanical activation and AlCl3Performing FT-IR characterization on pretreated cassava starch;
FIG. 6 shows the mixture of raw potato starch and hand-mixed AlCl3The cassava starch, the cassava starch subjected to mechanical activation pretreatment and the cassava starch subjected to mechanical activation and AlCl3And (3) XRD characterization results of the pretreated cassava starch.
Detailed Description
The invention will be further described in detail with reference to the following detailed description and the accompanying drawings, but the invention is not limited to the scope of protection.
Comparative example 1
40g of Untreated (Untreated) tapioca starch were added to a hydrothermal reaction kettle, followed by 1600ml of LAlCl3Hydrothermal reaction in water solution (adding AlCl according to per gram starch)3The amounts of which are respectively 0.05, 0.075, 0.1, 0.125, 0.15, 0.2, 0.25 and 0.3mmol, are divided into 8 groups), the reaction temperature is 200 ℃, the reaction time is 2 hours, and then the obtained reaction solution is cooled and filtered through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
Example 1 mechanical activation
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: adding 40g of cassava starch into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50 ℃, the rotation speed at 400rpm, and the reaction time at 60min, and then sieving with a 200-mesh sieve to obtain mechanically activated pretreated (MA) starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1600mL of AlCl3Hydrothermal reaction in water solution (adding AlCl according to per gram starch)3The amounts of which are respectively 0.05, 0.075, 0.1, 0.125, 0.15, 0.2, 0.25 and 0.3mmol, are divided into 8 groups), the reaction temperature is 200 ℃, the reaction time is 2 hours, and then the obtained reaction solution is cooled and filtered through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
Example 2 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of cassava starch and 2mmol of AlCl3Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50 deg.C, rotating speed at 400rpm, and reaction time at 60min, and sieving with 200 mesh sieve to obtain mechanical activation and metal Lewis acid pretreatment (MA-AlCl)3) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1600mL of AlCl3Hydrothermal reaction in water solution (adding AlCl according to per gram starch)3The amounts of which are respectively 0.05, 0.075, 0.1, 0.125, 0.15, 0.2, 0.25 and 0.3mmol, are divided into 8 groups), the reaction temperature is 200 ℃, the reaction time is 2 hours, and then the obtained reaction solution is cooled and filtered through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
The yield of levulinic acid (using Y) of comparative example 1 and examples 1-2 was comparedLExpressed) and yield of glucose (in Y)GShown) were compared, respectively, and the results are shown in fig. 1 and 2. As can be seen from FIGS. 1 and 2, AlCl is added per gram of starch3When the amount of the active ingredient is 0.05-0.1mmol, the active ingredient is subjected to mechanical activation pretreatment (MA) and mechanical activation plus metal Lewis acid pretreatment (MA-AlCl)3) The yield of levulinic acid in tapioca starch is at a higher level than in Untreated (unrated) tapioca starch. The cassava powder is pretreated by mechanical activation, so that the crystal structure and the particle structure of the cassava starch are obviously destroyed, and the cassava starch and AlCl are added3The contact reaction sites are simultaneously reduced by the cassava starch paste liquid after mechanical activation pretreatment3Diffusion resistance of (2) to AlCl3The cassava starch is easier to diffuse into the molecules of the cassava starch to hydrolyze the cassava starch, so that the catalytic reaction is enhanced; in addition, mechanical activation works in conjunction with AlCl3The cassava starch is pretreated, and the metal Lewis acid can enter the cassava powder particles more smoothly during the hydrothermal reaction, so that AlCl is added into each gram of starch3When the amount of (b) is 0.075mmol, MA-AlCl3The yield of the levulinic acid of the pretreated cassava starch and the MA pretreated cassava starch is obviously higher than that of the same cassava starchUntreated tapioca starch, MA and MA-AlCl under equal conditions3The levulinic acid yield of the pretreated cassava starch is respectively obtained by adding AlCl into each gram of starch3The amounts of 0.075 and 0.1mmol are maximum, whereas the untreated tapioca starch is charged with AlCl per gram of starch3The maximum levulinic acid yield is reached at 0.15 mmol.
The levulinic acid yield begins to decline gradually after the maximum levulinic acid yield is reached, because the crystal structure and the grain structure of the tapioca starch have been completely destroyed and can be reacted with AlCl3Fully contact reaction, the starch molecules in the amorphous area are fully contacted with AlCl3And converted into glucose, so that AlCl is continuously increased3The amount used has no promoting effect on the catalytic effect. In conclusion, it can be seen that the pretreatment of starch by mechanical activation has the effect of increasing the yield of levulinic acid, and that the mechanical activation and AlCl3The co-pretreatment of starch shows a synergistic effect in increasing the yield of levulinic acid.
Example 3 mechanical activation
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: adding 40g of cassava starch into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50 ℃, the rotation speed at 400rpm, and the reaction time at 60min, and then sieving with a 200-mesh sieve to obtain mechanically activated pretreated (MA) starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1600mL of 0.075mmol AlCl per gram of starch3(optimum amount of catalyst for mechanical activation pretreatment) of AlCl3Carrying out hydrothermal reaction in the aqueous solution at 200 ℃ for 2h (7 groups according to the reaction time of 0.5, 1, 1.5, 2, 3, 4 and 5h respectively), cooling the obtained reaction solution, and filtering the cooled reaction solution through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
Example 4 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of cassava starch and 4mmol of AlCl3Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50 deg.C, rotating speed at 400rpm, and reaction time at 60min, and sieving with 200 mesh sieve to obtain mechanical activation and metal Lewis acid pretreatment (MA-AlCl)3) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1600mL of 0.1mmol of AlCl per gram of starch3(MA-AlCl3Optimum amount of pretreated catalyst) of AlCl3Carrying out hydrothermal reaction in the aqueous solution at 200 ℃ for 2h (7 groups according to the reaction time of 0.5, 1, 1.5, 2, 3, 4 and 5h respectively), cooling the obtained reaction solution, and filtering the cooled reaction solution through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
The yield of levulinic acid (with Y) for comparative example 1 and examples 3 to 4 is comparedLExpressed) and yield of glucose (in Y)GShown) were compared, respectively, and the results are shown in fig. 3 and 4. As can be seen from FIGS. 3 and 4, either the Untreated (Untreated) starch or the mechanical activation pretreatment (MA), the mechanical activation in combination with the AlCl3Pretreatment (MA-AlCl)3) The optimal reaction time for catalytic conversion of the starch is 2 h. The yield of the levulinic acid is increased rapidly within 0.5-2.0 h, and the MA and MA-AlCl are generated because the crystal structure and the particle structure of the cassava flour are obviously damaged by the mechanical activation pretreatment3The levulinic acid yield value of the pretreated starch rises faster, but the highest levulinic acid yield of the three different pretreated cassava starches is achieved within 2 hours, and the levulinic acid yield value is greatly reduced after 2-5 hours, which indicates that the levulinic acid further reacts to generate gamma-valerolactone, so that the optimal reaction time for catalytic conversion of the cassava starch is 2 hours. And when the reaction time is 2-3h, the reaction is carried out by MA and MA-AlCl3The yield of levulinic acid of the pretreated tapioca starch is high compared to the yield of levulinic acid of Untreated (unrated) tapioca starch. In conclusion, it can be seen that the pretreatment of starch by mechanical activation has the effect of increasing the yield of levulinic acid, and that the mechanical activation and AlCl3The co-pretreatment of starch shows a synergistic effect in increasing the yield of levulinic acid.
Example 5 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of barley starch and 6mmol of AlCl3Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 55 ℃, the rotating speed at 400rpm, the reaction time at 60min, and then sieving with a 200-mesh sieve to obtain mechanically activated AlCl3Pretreatment (MA-AlCl)3) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1600mL of 0.15mmol of AlCl per gram of starch3AlCl of3Carrying out hydrothermal reaction in the aqueous solution at the reaction temperature of 200 ℃ for 1.5h, cooling the obtained reaction solution, and then passing the reaction solution through a filter membrane with the pore diameter of 0.22 mu m to obtain the levulinic acid.
The yield of levulinic acid for this example was determined to be 51%.
Example 6 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of corn starch and 8mmol of CuCl2Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 52 ℃, the rotating speed at 400rpm, the reaction time at 50min, and then sieving with a 200-mesh sieve to obtain the mechanical activation + CuCl2Pretreatment (MA-CuCl)2) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, adding 1700mL of CuCl, and adding 0.2mmol of CuCl per gram of starch2CuCl of2Carrying out hydrothermal reaction in the aqueous solution at the temperature of 180 ℃ for 2.5h, cooling the obtained reaction solution, and then passing the cooled reaction solution through a filter membrane with the aperture of 0.25 mu m to obtain the levulinic acid.
The yield of levulinic acid for this example was determined to be 45%.
Example 7 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of potato starch and 4.8mmol of FeCl3Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 53 ℃, the rotating speed at 400rpm, the reaction time at 40min, and then sieving with a 200-mesh sieve to obtain the mechanical activation + FeCl3Pre-treatment (MA-FeCl)3) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 1800mL of FeCl 0.12mmol per gram of starch3FeCl of3Carrying out hydrothermal reaction in the aqueous solution at the reaction temperature of 120 ℃ for 3h, cooling the obtained reaction solution, and then passing the cooled reaction solution through a filter membrane with the pore diameter of 0.20 mu m to obtain the levulinic acid.
The yield of levulinic acid for this example was determined to be 41.7%.
Example 8 mechanical activation + Metal Lewis acid catalyst
A method for producing levulinic acid from a mechanically activated enhanced metal lewis acid catalyzed starchy feedstock, the method comprising the steps of:
(1) pretreatment of starch: 40g of wheat starch and 12mmol of ZnCl2Adding into a ball milling tank for ball milling reaction, controlling the reaction temperature at 55 ℃, the rotating speed at 400rpm, the reaction time at 30min, and then sieving with a 200-mesh sieve to obtain the mechanical activation + ZnCl2Pretreatment (MA-ZnCl)2) Starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, and then adding 2000mL of ZnCl, wherein 0.3mmol of ZnCl is added into each gram of starch2ZnCl of2Carrying out hydrothermal reaction in the aqueous solution at the temperature of 240 ℃ for 2h, cooling the obtained reaction solution, and then passing the cooled reaction solution through a filter membrane with the pore diameter of 0.25 mu m to obtain the levulinic acid.
The yield of levulinic acid for this example was determined to be 40%.
Material characterization
FT-IR characterization
The molecular groups of the pretreated starch obtained in examples 1 and 2 and the untreated tapioca starch obtained in comparative example 1 were characterized by a fourier transform infrared spectrometer, and whether derivatization occurred after pretreatment was judged. Taking potassium bromide as a substrate, under the irradiation of an infrared sample preparation lamp, uniformly mixing and grinding 200mg of dry KBr and 2mg of cassava powder sample, putting the mixture into a die, pressing the mixture into a transparent sheet for detection and analysis, and scanning the transparent sheet with the wave number ranging from 4000 to 500cm-1。
The FT-IR characterization results are shown in FIG. 5, wherein a, b and c are respectively raw potato starch, mechanically activated pretreated tapioca starch, and mechanically activated AlCl3FT-IR diagram of pretreated tapioca starch. The infrared characteristic absorption peaks of the raw potato powder are respectively as follows: 3422cm-1Near a long and wide associated O-H stretching vibration peak, 2928cm-1Nearby C-CH2-C characteristic peak of asymmetric stretching vibration, 1644 cm-1Nearby is H2Characteristic peaks of O bending vibration, 1430 and 1353cm-1The vicinity is a characteristic peak of C-H stretching and bending vibration, 1159cm-1The vicinity is a characteristic peak of C-O-C asymmetric stretching vibration, which is 700-1100 cm-1Is the characteristic peak of C-O stretching vibration of D-glucopyranose and connecting-OH. Comparing the infrared spectra of the raw potato powder, the cassava starch is pretreated by mechanical activation alone or the cassava starch is cooperated with AlCl by mechanical activation3No new absorption peak appears in the infrared spectrogram of the pretreated cassava starch, namely, the cassava powder is mechanically activated or mechanically activated plus AlCl3No new groups are generated in the pretreatment process, and no derivatization reaction occurs in the pretreatment process.
Characterization by XRD
The pretreated starches from examples 1 and 2, the untreated tapioca starch from comparative example 1 and the hand-mixed AlCl3Of tapioca starch (40g of tapioca starch and 2mmol of AlCl)3) The structure of the cassava starch is characterized, and the change of the crystallinity after the pretreatment of the cassava starch is researched. Detection conditions are as follows: the source of the diffraction is Cu target KαSpectral line, Ni plate filtering, 8 °. min-1The scanning frequency is continuously scanned between 5 degrees and more than or equal to 2 degrees and less than or equal to 45 degrees, the tube pressure of 40kV and the tube flow of 30mA are adopted.
The XRD characterization results are shown in FIG. 6, wherein a, b, c and d are respectively raw potato starch and hand-mixed AlCl3The cassava starch, the cassava starch subjected to mechanical activation pretreatment and the cassava starch subjected to mechanical activation and AlCl3XRD pattern of pretreated tapioca starch. As can be seen from the figure, the raw potato starch is mixed with the hand-operated AlCl3The characteristic diffraction of the cassava starch (2 theta is a double peak at 17 degrees and a single peak at 15 degrees and 23 degrees) shows that the crystal structure of the cassava starch cannot be changed by manual mixing, and the mechanical activation, the mechanical activation and the AlCl3The characteristic diffraction of the pretreated cassava starch at 17 degrees, 15 degrees and 23 degrees almost completely disappears, the diffraction peak height is reduced, the dispersibility is enhanced, and the cassava starch becomes a steamed bread peak, which shows that the crystal structure of the cassava starch is completely destroyed and is changed into an amorphous structure, and shows that the mechanical activation obviously reduces the crystallinity of the cassava starch.
Claims (10)
1. A method for producing levulinic acid by catalyzing starchy materials with mechanically activated and strengthened metal Lewis acid is characterized by comprising the following steps: pretreating the starchy raw material by mechanical activation to obtain pretreated starch, and then carrying out catalytic conversion on the pretreated starch by taking metal Lewis acid as a catalyst under a hydrothermal condition to obtain levulinic acid.
2. The process for the production of levulinic acid from a mechanically activated, strengthened metal lewis acid catalyzed starchy feedstock of claim 1, wherein the process comprises the steps of:
(1) pretreatment of starch: adding starch into a ball milling tank for ball milling reaction, controlling the reaction temperature at 50-55 ℃ and the reaction time at 30-60min, and then sieving to obtain pretreated starch;
(2) hydrothermal reaction: adding the pretreated starch into a hydrothermal reaction kettle, then adding a metal Lewis acid catalyst for hydrothermal reaction at the temperature of 120 ℃ and 240 ℃ for 2-2.5h, and then cooling the obtained reaction solution and then coating the reaction solution to obtain the levulinic acid.
3. The method for producing levulinic acid by catalyzing starchy materials with mechanically activated and strengthened metal Lewis acids according to claim 2, wherein metal Lewis acids are also added to the starchy materials when the starchy materials are pretreated, and the metal Lewis acids comprise AlCl3、CuCl2、FeCl3、ZnCl2The amount of the metal Lewis acid added to each gram of starch is 0.05-0.3 mmol.
4. The method for producing levulinic acid from starchy materials catalyzed by mechanically activated enhanced metal Lewis acid as in claim 3, wherein the metal Lewis acid is AlCl3Adding AlCl into each gram of starch3The amount of (B) is 0.05-0.15 mmol.
5. The method of mechanically activating an enhanced metal lewis acid catalyzed starchy feedstock of claim 1 or 2 for the production of levulinic acid, wherein the starchy feedstock comprises tapioca, corn, rice, potato, wheat, barley.
6. The method for producing levulinic acid from starchy materials with mechanically activated enhanced metal lewis acid as in claim 2, wherein the metal lewis acid catalyst is AlCl3、CuCl2、FeCl3Or ZnCl2The amount of the metal Lewis acid catalyst added in per gram of starch is 0.05-0.3 mmol.
7. The method for producing levulinic acid from starchy materials with mechanically activated and strengthened metal lewis acid as in claim 6, wherein the metal lewis acid catalyst is AlCl3Adding AlCl into each gram of starch3The amount of (B) is 0.05-0.1 mmol.
8. The method for producing levulinic acid from a mechanically activated and strengthened metal lewis acid catalyzed starchy material according to claim 2, wherein in step (2), the mass ratio of pretreated starch to metal lewis acid catalyst is 1: 40-50.
9. The method of mechanically activating an enhanced metal lewis acid catalyzed starchy material to produce levulinic acid as in claim 2, wherein the pore size of the membrane is between 0.20 and 0.25 μ ι η.
10. The process for producing levulinic acid from a mechanically activated, strengthened metal lewis acid catalyzed starchy feedstock of claim 2, wherein the yield of levulinic acid is between 30 and 55 percent.
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