CN115725116B - Method for producing epoxy plasticizer by taking lignocellulose biomass as raw material - Google Patents
Method for producing epoxy plasticizer by taking lignocellulose biomass as raw material Download PDFInfo
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- CN115725116B CN115725116B CN202111001814.3A CN202111001814A CN115725116B CN 115725116 B CN115725116 B CN 115725116B CN 202111001814 A CN202111001814 A CN 202111001814A CN 115725116 B CN115725116 B CN 115725116B
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- acid
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- microbial oil
- hydrolysis
- epoxy
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
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Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for producing an epoxy plasticizer by taking lignocellulose biomass as a raw material, which comprises the following steps: pretreating lignocellulose biomass to obtain a liquid-solid mixture; hydrolyzing the liquid-solid mixture to obtain fermentable sugar solution; fermenting the fermentable sugar solution to obtain cells containing microbial oil; extracting and refining the grease from the cells to obtain microbial grease; epoxidizing the microbial oil to obtain epoxy microbial oil; and removing impurities from the epoxy microbial oil, washing and drying to obtain the epoxy plasticizer. The method provided by the invention can convert the lignocellulose biomass into the grease-based epoxy plasticizer, can realize solid waste treatment of the lignocellulose biomass, can change waste into valuable to obtain a high-value product, and has remarkable environmental and social benefits.
Description
Technical Field
The invention relates to the field of biochemical industry, in particular to a method for producing an epoxy plasticizer by taking lignocellulose biomass as a raw material, for example, a method for preparing the epoxy plasticizer by utilizing lignocellulose biomass raw materials such as agricultural waste straws, forestry waste and the like.
Background
Polyvinyl chloride (PVC) is the second most versatile plastic used worldwide. However, the interaction force between PVC molecular chains is strong, the temperature required for softening and melting the pure PVC resin is high, and the processing is very inconvenient. The plasticizer is an additive with the largest dosage in the PVC product, and the addition of the plasticizer is favorable for reducing the interaction force among PVC molecules to enhance the plasticity, thereby improving the fluidity of the PVC resin during molding processing to enable the PVC resin to be easier to process, and improving the flexibility of the product. The phthalate plasticizer has the advantages of good compatibility, high plasticizing efficiency and the like, and is always the product with the largest dosage in the plasticizer for a long time. In recent years, along with the progress of research on plasticizer toxicity and the like, phthalate plasticizers are found to pollute the environment and have potential carcinogenic and teratogenic effects on human bodies. Thus, considerable national and organizational legislation or related policies are being adopted to limit the use of phthalate plasticizers. Therefore, the development of nontoxic environment-friendly plasticizers is one of the key problems to be solved urgently in the PVC industry.
The existing environment-friendly plasticizer mainly comprises citric acid esters, aliphatic dibasic acid esters, polyalcohols, polyesters, epoxy and other varieties. Epoxy plasticizers refer to compounds containing epoxy groups in the molecular structure. In the processing process of the PVC resin, the epoxy plasticizer not only has plasticizing effect on the PVC, but also can absorb hydrogen chloride generated by the degradation of the PVC resin, thereby inhibiting the continuous catalytic decomposition of the PVC, and playing a role in stabilizing PVC products and prolonging the service life. In the preparation process of the PVC product, the characteristics of photo-thermal stability are utilized to improve the weather resistance of the product. Compared with the o-phenyl ester plasticizer, the epoxy plasticizer is almost nontoxic, has the advantages of heat resistance, light resistance, low price and the like, and is approved to be applied to packaging materials of medicines and foods in many countries and regions. According to the difference of raw materials, the epoxy plasticizer can be mainly divided into epoxy neutral grease obtained by epoxidation by taking unsaturated vegetable grease as a raw material and epoxy fatty acid methyl ester obtained by epoxidation by taking unsaturated fatty acid methyl ester as a raw material. The epoxidized soybean oil is the most widely used polyvinyl chloride plasticizer and stabilizer at present, has the advantages of excellent heat resistance and light resistance, good compatibility with resin, low volatility, difficult extraction, good electrical property, better low flexibility, no toxicity and the like. But epoxidized soybean oil is prepared from edible soybean oil. The soybean oil consumed by China per year exceeds 1600 ten thousand tons, so that more than 1 hundred million tons of soybean are required to be imported per year. Therefore, from the industrial application point of view, the epoxy plasticizer can be prepared by taking inedible grease as a raw material, so that an important way of 'competing with people for grains and competing with the grains for land' is avoided.
Lignocellulosic biomass, such as agricultural waste straw, forestry waste, is the most abundant renewable biomass in nature. The annual crop straw yield in China is close to 10 hundred million tons, the conversion and the utilization of the crop straw have remarkable environmental benefits, and waste can be changed into valuable, so that a high-value product is obtained. However, the main components of lignocellulose are cellulose, hemicellulose and lignin, and the multi-layered structure of the plant cell wall makes bioconversion of lignocellulose an extremely challenging topic. On the other hand, the chemical structure of lignocellulose components and the vegetable oil-based epoxy plasticizer have great difference, and the lignocellulose components and the vegetable oil-based epoxy plasticizer can be realized through multiple steps by adopting various methods such as coupling biology, chemistry, thermochemical and the like. The present invention therefore aims to provide a process for the preparation of a grease-based epoxy plasticizer from lignocellulosic biomass feedstock, such as straw, in particular to convert lignocellulose into fermentable sugars, further into microbial grease having a fatty acid composition similar to soybean oil, and then obtaining an epoxidized microbial grease plasticizer by epoxidation reaction.
Disclosure of Invention
The invention aims to provide a method for preparing an oil-based epoxy plasticizer by taking lignocellulose biomass such as straw and the like as a raw material, which converts agricultural and forestry waste into an environment-friendly epoxy plasticizer and realizes the high-value and resource utilization of the waste biomass raw material.
The inventors have found by analysis that the first step in the preparation of oil-based epoxy plasticizers from lignocellulosic biomass is to obtain a lipid feedstock having a similar unsaturation and fatty acid composition as soybean oil for epoxidation, while some microorganisms can convert sugars to microbial lipids that accumulate in their cells, but these microorganisms need to first convert the glycans of the lignocellulosic biomass, including cellulose and hemicellulose, to fermentable sugars, in order to achieve efficient conversion of straw glycans to lipids, so that pretreatment and hydrolysis of the feedstock such as straw is required while controlling inhibitor formation. Therefore, to achieve the preparation of the grease-based epoxy plasticizer from the lignocellulosic biomass feedstock, multiple steps of pretreatment, hydrolysis, fermentation, extraction, epoxidation, and the like are coupled, and suitability regulation and parameter optimization are performed.
To this end, the invention provides a process for producing epoxy plasticizers from lignocellulosic biomass, characterized in that it comprises the following steps:
step (1): pretreating lignocellulose biomass to obtain a liquid-solid mixture;
step (2): hydrolyzing the liquid-solid mixture in the step (1) to obtain fermentable sugar solution;
step (3): fermenting the fermentable sugar solution obtained in the step (2) to obtain cells containing microbial oil;
step (4): extracting and refining the grease from the cells obtained in the step (3) to obtain microbial grease;
step (5): epoxidizing the microbial oil obtained in the step (4) to obtain epoxy microbial oil;
step (6): and (3) removing impurities, washing and drying the epoxy microbial oil obtained in the step (5) to obtain the epoxy plasticizer.
According to an embodiment of the invention, the pretreatment in step (1) is a steam pretreatment, preferably based on dilute acid hydrolysis, i.e. the pretreatment is carried out by introducing steam after the raw material is pre-impregnated with a dilute acid solution; optionally, the pretreatment conditions are: the liquid-solid ratio (L/kg) is 1:1-10:1, the sulfuric acid consumption based on the dry weight of the raw materials is 0.01-10%, and the pretreatment temperature is 130-180 ℃. The main purpose of the pretreatment is to increase accessibility of cellulose and simultaneously convert hemicellulose into fermentable sugars such as xylose, so that steam pretreatment based on dilute acid hydrolysis is preferable, and the accessibility of cellulose is remarkably increased and fermentable sugars such as xylose are obtained by hydrolyzing hemicellulose, destroying the structure of cell walls and increasing porosity. However, monosaccharide degradation and lignin depolymerization are inevitably caused in the pretreatment process, and inhibitors with negative effects on subsequent enzymolysis and fermentation are generated, so that factors such as the hydrolysis rate of polysaccharide, the sugar yield, the concentration of inhibitors and the like are required to be comprehensively considered, and the reaction conditions of pretreatment are controlled.
According to an embodiment of the present invention, the step (2) of hydrolyzing the pretreated liquid-solid mixture preferably uses cellulase; optionally, the pH of the liquid-solid mixture is adjusted to 3-6 with a base before hydrolysis; optionally, adding a nonionic surfactant in the hydrolysis process, wherein the nonionic surfactant is selected from one of Tween 20, tween 80, sodium lignin sulfonate, span 20, span 80, triton X-100 and triton X-114; optionally, the hydrolysis temperature is 30 to 60 ℃.
Preferably, the hydrolysis process in the step (2) is a non-isothermal process, i.e. the hydrolysis temperature is periodically changed at 30-60 ℃; optionally, the hydrolysis temperature is periodically switched between a first temperature range of 50-55 ℃ and a second temperature range of 40-45 ℃ every 12 hours, and the total hydrolysis time is 72-120 hours. The solids in the pretreated liquid-solid mixture need to be further hydrolyzed and saccharified to obtain glucose for further fermentation. The preferred hydrolysis methods include acid hydrolysis and enzyme hydrolysis, since acid hydrolysis needs to be carried out at a higher temperature, which causes higher sugar loss, enzyme hydrolysis is preferred in the present invention, but enzyme hydrolysis needs to consider ineffective adsorption of lignocellulose to cellulase, so in the preferred embodiment of the present invention, nonionic surfactant is added in the enzymolysis process to reduce ineffective adsorption of cellulase, but surfactant selection needs to consider the influence of the nonionic surfactant on subsequent fermentation, too high an amount causes strong inhibition of strain growth, and therefore, in the preferred embodiment of the present invention, the hydrolysis process is carried out under non-isothermal conditions to adjust adsorption of enzyme on substrate and lignocellulose through temperature change operation, thereby obtaining better enzymolysis efficiency at lower surfactant usage.
According to an embodiment of the present invention, the oleaginous microorganism for fermenting the fermentable sugar solution in the step (3) is preferably one of rhodosporidium toruloides, rhodotorula glutinis, oleaginous stoniae and candida picolinae; optionally, the fermentation conditions are: the temperature is 25-60 ℃, the pH is 4.5-8.0, and the carbon nitrogen ratio of the culture medium is 5:1-1000:1; further, the fermentation is to adopt the same strain to perform two-step fermentation reaction, wherein the first-step fermentation reaction controls the carbon-nitrogen ratio to be 5:1-20:1, and the second-step fermentation reaction controls the carbon-nitrogen ratio to be 200:1-1000:1. The grease microorganism refers to a microorganism which converts fermentable sugar into grease, and comprises yeast, mould, bacteria, algae and the like, wherein eukaryotic yeast, mould and algae can synthesize triglyceride with similar composition as vegetable oil. The preferred grease microorganism of the invention is yeast, because the yeast has the advantages of fast growth rate, wide carbon source and the like. The grease microorganism disclosed by the invention is preferably yeast subjected to normal temperature plasma (ARTP) mutagenesis or hydrolysis liquid inhibitor tolerance domestication treatment so as to improve the tolerance of the strain to inhibitors such as organic acid, furan aldehyde and phenolic compounds. On the other hand, grease accumulation is carried out under the condition of far excessive carbon source, namely, little nitrogen source, but the little nitrogen source is unfavorable for the growth of strains, thereby affecting the grease yield. Therefore, in the embodiment provided by the invention, the culture and the oil production of the grease microorganism are preferably carried out by adopting a two-step method, the nitrogen source of the first-step fermentation reaction is relatively sufficient, the biomass accumulation process is carried out, and the carbon source in the second-step fermentation reaction is far excessive, so that the grease accumulation process is carried out.
According to an embodiment of the present invention, the extraction of the oil from the cells in step (4) is preferably performed by solvent extraction; optionally, the solvent is selected from one or more of dichloromethane, chloroform, ethylene oxide, petroleum ether, ethyl acetate, acetone, methanol and diethyl ether; optionally, the cells are subjected to centrifugation or filtration dehydration, steam or acid treatment steps prior to solvent extraction to extract the oil. Since microbial oil accumulates in cells, it is necessary to destroy the cell wall structure of the cells in order to extract the oil efficiently. In the technical scheme disclosed by the invention, steam or acid treatment is preferred to degrade cell walls and improve the oil yield.
According to an embodiment of the present invention, the epoxidation of the microbial oil in step (5) is performed under lipase catalysis; optionally, the lipase is selected from the group consisting of immobilized lipases; optionally, the epoxidation reaction is carried out in an organic solvent system, wherein the organic solvent is selected from one of tertiary butanol, ethyl acetate, toluene, cyclohexane and petroleum ether; optionally, an oxygen carrier is employed in the epoxidation reaction, the oxygen carrier being selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid.
According to an embodiment of the present invention, wherein the epoxidation reaction of the microbial oil in step (5) is performed under the following conditions: the oxygen carrier is 5-25% based on the weight of the microbial oil, the hydrogen peroxide is 5-20% based on the weight of the microbial oil, the lipase is 1.5-20% based on the weight of the microbial oil, the organic solvent is 1-6 times based on the weight of the microbial oil, the reaction temperature is 30-50 ℃, the stirring speed is 100-500rpm, and the reaction time is 2-24 hours.
According to an embodiment of the present invention, hydrogen peroxide is added to the reaction system in a stepwise manner during the epoxidation of the microbial oil in step (5), preferably in a stepwise manner, the hydrogen peroxide is added within the first 100 minutes of the reaction, each time at a time interval of 5 to 10 minutes, and each time in an amount of 1/20 to 1/10 of the total amount.
The grease can be used for preparing the epoxy grease plasticizer through epoxidation. Conventional epoxidation processes use hydrogen peroxide as the oxygen donor, an organic acid such as formic acid or acetic acid as the oxygen carrier, and sulfuric acid as the catalyst. Hydrogen peroxide and organic acid generate peroxy organic acid under the catalysis of sulfuric acid, and the peroxy organic acid is subjected to epoxidation reaction with unsaturated double bonds of grease at an oil-water interface. According to the embodiment of the invention, lipase, especially immobilized lipase, is preferably used as a catalyst, so that the production of peroxy organic acid can be catalyzed under mild conditions, and further microbial grease is epoxidized, and the problems that the ring-opening side reaction is serious, the catalyst cannot be recycled, acid-containing wastewater is generated and the like in the traditional sulfuric acid catalysis process are avoided. Hydrogen peroxide, however, has a significant toxic effect on lipases and the usual formic acid or acetic acid oxygen carriers also have a significant inhibitory effect on lipases, so that it is necessary to re-screen the oxygen carriers and to strictly control the reaction conditions. On the other hand, the hydrogen peroxide used in the epoxidation process is usually 30% hydrogen peroxide aqueous solution, a large amount of hydrogen peroxide solution is added into the system to inevitably change the system into heterogeneous phase, and in order to avoid the problem of immobilized lipase protein shedding caused by heterogeneous phase reaction, an organic solvent system can be adopted to obtain a homogeneous system. According to a specific embodiment of the present invention, the oxygen carrier used in the epoxidation reaction is selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid; further preferably, the oxygen carrier is a medium-long chain fatty acid selected from one of heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid, so as to avoid the negative effects caused by the use of low chain fatty acid acidity. According to the embodiment of the invention, the organic solvent is one of toluene, tertiary butanol, ethyl acetate, cyclohexane and petroleum ether, so that a good homogeneous reaction system is obtained, and meanwhile, negative influence on lipase is avoided. Furthermore, epoxidation reaction conditions are key controlling factors affecting enzyme stability and activity and epoxidation efficiency. According to the specific embodiment provided by the invention, the oxygen carrier is 5-25% based on the weight of the microbial oil, the hydrogen peroxide is 5-20% based on the weight of the microbial oil, the lipase is 1.5-20% based on the weight of the microbial oil, the organic solvent is 1-6 times based on the weight of the microbial oil, the temperature is 30-50 ℃, and the stirring speed is 100-500rpm; higher epoxide numbers can be obtained with reaction times of 2 to 24 hours. On the other hand, according to the embodiment of the invention, 30% of hydrogen peroxide is added to the reaction system in a stepwise addition manner, preferably in such a manner that the hydrogen peroxide is added within the first 100 minutes of the reaction, each time at a time interval of 5 to 15 minutes, and each time at an amount of 1/20 to 1/10 of the total amount, so as to avoid deactivation of the lipase caused by an excessively high hydrogen peroxide concentration.
According to an embodiment of the present invention, the conditions for removing impurities, washing and drying the epoxy microbial oil in the step (6) are as follows: the oil phase is distilled at 40-60 ℃ and 5-10kpa absolute pressure for 30-120 minutes, then is washed for 1-3 times at 30-60 ℃ by adopting sodium bicarbonate solution with the mass fraction of 3-5%, and is distilled at 40-60 ℃ and 5-10kpa absolute pressure for 30-120 minutes. The purpose of the treatment process is to remove the residual organic acid and water in the reaction system to obtain purified epoxy microbial oil, namely the epoxy plasticizer.
In conclusion, the method provided by the invention can convert lignocellulose biomass into the grease-based epoxy plasticizer, can realize solid waste treatment of lignocellulose biomass, can change waste into valuable to obtain high-value products, and has remarkable environmental and social benefits.
Drawings
The invention will be further described with reference to the drawings and examples.
Fig. 1 is a technical flow of preparing an epoxy plasticizer from a lignocellulosic biomass feedstock in accordance with the present invention.
The reference numerals in the figures illustrate:
1. pretreatment of lignocellulose; 2. catalytic hydrolysis by cellulase; 3. liquid-solid separation; 4. microbial oil production; 5. liquid-solid separation; 6. extracting and purifying grease; 7. epoxidation of grease; 8. purifying and removing impurities from the product.
Detailed Description
The present invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1: lignocellulose dilute acid hydrolysis pretreatment and inhibitor formation
The lignocellulose raw material is wheat straw, and the origin is Shandong province. The wheat straw is cut into 1-2cm length for standby. The wheat straw used was subjected to a principal component analysis according to the lignocellulosic component determination method of the renewable energy laboratory in the united states, with the determination result: moisture 5.1%, dextran (cellulose) 33.40%, xylan 22.26%, arabinan 3.10%, lignin 20.08%, acetyl 2.01%, ash 6.48%, other soluble solids 7.57%. The straw biomass is subjected to dilute acid hydrolysis treatment in a 5L stainless steel high-pressure reaction kettle at a solid-to-liquid ratio (kg/L) of 1:10 at different temperatures and sulfuric acid concentrations, and the concentrations of different sugars and inhibitors in the water phase are measured as shown in the following table:
TABLE 1 acid hydrolysis pretreatment of wheat straw liquid phase at different temperatures and sulfuric acid concentrations
It is known that the concentration of xylose in the liquid phase tends to increase with increasing temperature and increasing sulfuric acid concentration, but higher temperature and acid concentration conversely decrease xylose concentration, while the corresponding concentration of inhibitors such as furfural increases.
Example 2: cellulase hydrolysis and total fermentable sugar yield of pretreated solids
The lignocellulose raw material is hydrolyzed for 120 hours under the conditions of 15FPU/g solid cellulase dosage, 5% solid content and pH 4.8 after the wheat straw is subjected to dilute acid hydrolysis pretreatment as described in example 1, and meanwhile, the influence of 5g/L Tween 80 or Tween 20 added and not added on the cellulase hydrolysis conversion rate is compared, and the cellulase hydrolysis conversion rate can be improved by 8-10% by adding 5g/L Tween 80 and 6-8% by adding Tween 20. By combining the xylose yields in the dilute acid hydrolysis pretreatment, the total fermentable sugar yields under different conditions can be obtained as shown in the following table:
TABLE 2 Total fermentable sugar yield of pretreated wheat straw at different temperatures and sulfuric acid concentrations
It is known that higher temperatures and sulfuric acid concentrations are beneficial to increasing the yield of fermentation sugars for cellulase conversion, but higher temperatures and acid concentrations result in more xylose loss, thereby reducing the overall sugar yield. For the wheat straw biomass raw material, the preferable condition is 140 ℃ and the sulfuric acid concentration is 0.5-0.6%, and the condition can obtain the highest total sugar yield.
Further, the hydrolysis reaction in example 2 was studied for hydrolysis temperature procedure as follows:
hydrolyzing wheat straw pretreated by 0.6% sulfuric acid at 140 ℃ for 120 hours under the conditions of 15FPU/g solid cellulase dosage, 5% solid content and pH 4.8, and simultaneously comparing the influence of isothermal process operation and non-isothermal process operation on enzymolysis, wherein the isothermal process is that the enzymolysis temperature is always kept at 50 ℃, the enzymolysis temperature is controlled to be 50 ℃ in the non-isothermal process in the 0 th to 12 th, 24 th to 36 th, 48 th to 60 th, 72 th to 84 th, 96 th to 108 th hours, the enzymolysis temperature is controlled to be 45 ℃ in the 12 th to 24 th, 60 th to 72 th, 108 th to 120 th hours, the enzymolysis temperature is controlled to be 55 ℃ in the 36 th to 48 th and 84 th to 96 th hours, and the temperature change period is 12 hours. After 120 hours of reaction, the zymosan conversion rate in the reactants prepared by the isothermal process and the non-isothermal process is detected, and the zymosan conversion rate obtained by the isothermal process is measured to be 64% and the zymosan conversion rate obtained by the non-isothermal process is measured to be 68.5%.
Example 3: microbial oil produced by fermenting straw hydrolysis sugar in one step by using oil microorganism
The grease microorganism is rhodosporidium toruloides Rhodosporidium toruloides subjected to mutagenesis by using a constant temperature plasma (ARTP), and compared with a wild strain, the mutagenized strain has obviously enhanced tolerance to organic acids, furfural and phenolic compounds in dilute acid hydrolysate. Fermenting and producing oil in a 250ml triangular flask, regulating the pH of the straw hydrolysate obtained in the example 2 to 5.5 by adopting calcium hydroxide, sterilizing for 15min at 115 ℃, inoculating yeast seed liquid cultured in a YEPD culture medium into the sterilized straw hydrolysate culture medium with 10% of volume inoculation amount, and culturing at 30 ℃ and 200 r/min. Along with the fermentation process, the strain continuously consumes carbon sources and nitrogen sources, the carbon-nitrogen ratio in the fermentation liquor is changed within the range of 50:1-500:1, and the biomass dry weight of the thalli is 17.6g/L after 7 days. And collecting thalli, and extracting and analyzing the grease by adopting an acid heating method to obtain the thalli with the grease content of 30.3 percent. The fatty acid composition of the microbial oil obtained by gas chromatography was found to contain 1.19% myristic acid, 24.3% palmitic acid, 0.73% palmitoleic acid, 9.99% stearic acid, 52.9% oleic acid, 9.16% linoleic acid, 0.97% linolenic acid, 0.46% arachidic acid and 0.29% behenic acid. The fatty acid composition is similar to soybean oil except that the palmitic acid content is higher than that of soybean oil, and the linoleic acid content is lower.
Example 4: microbial oil produced by fermenting straw hydrolysis sugar in two steps by using oil microorganism
The grease microorganism strain used was the same as in example 3. The straw hydrolysate obtained in example 2 was subjected to oleaginous fermentation in a 5L fermenter, pH was adjusted to 5.5 with calcium hydroxide, concentrated by rotary evaporation to a total sugar concentration of 150-200g/L and sterilized at 115℃for 15min. Inoculating yeast seed solution cultured in a YEPD culture medium into a sterilized straw hydrolysate culture medium with the volume inoculation amount of 10%, supplementing 20-30g/L ammonium sulfate as a nitrogen source, and culturing for 5 days under the conditions of 32 ℃ and 300r/min and ventilation of 1.5vvm with the biomass dry weight of the bacterial cells of 35g/L, wherein the carbon-nitrogen ratio is 5:1-10:1. And (3) feeding sterilized sugar solution from the fifth day, keeping the total sugar concentration in the fermentation liquor at a level of 20-30g/L, and continuously culturing for 10 days to obtain the biomass of the bacterial cells of 50g/L. After the grease is extracted and analyzed by the acid heating method, the grease content of the thalli is 50.3 percent. The fatty acid composition of the microbial oil obtained by gas chromatography analysis was found to be similar to that of oil cultured in shake flasks, and it was found that the oil contained 1.2% myristic acid, 29.3% palmitic acid, 0.7% palmitoleic acid, 9.38% stearic acid, 46.3% oleic acid, 9.92% linoleic acid, 2.66% linolenic acid, 0.35% arachidic acid and 0.12% behenic acid.
Example 5: lipase-catalyzed microbial oil epoxidation
The microbial oil obtained in example 4 was used as a raw material, and an oil-based epoxidized plasticizer was prepared by catalytic epoxidation with immobilized lipase (Novozyme 435). Epoxidation was carried out under the following conditions: tertiary butanol which is 5 times of the weight of the grease is taken as a solvent, lauric acid which is 5% of the weight of the grease is taken as an oxygen carrier, hydrogen peroxide which is 30wt% is taken as 0.5 times of the weight of the grease, lipase is taken as 2% of the weight of the grease, and hydrogen peroxide is added into a reactor in a stepwise manner under the conditions of the temperature of 45 ℃ and the rotating speed of 150rpm, namely, all hydrogen peroxide is added within 140min every 10min after 1/14 of the total amount is added. After reacting for 12 hours under the above conditions, the immobilized lipase was separated by filtration, the solvent was removed by evaporation under reduced pressure, and the epoxy microbial oil was obtained after washing with water and further evaporation under reduced pressure, and the epoxy value thereof was found to be 4.05%.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the technical means and technical contents disclosed above without departing from the scope of the technical solution of the present invention. Therefore, all equivalent changes according to the shape, structure and principle of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A method for producing an epoxy plasticizer from lignocellulosic biomass, comprising the steps of:
step (1): pretreating lignocellulose biomass to obtain a liquid-solid mixture;
step (2): hydrolyzing the liquid-solid mixture in the step (1) to obtain fermentable sugar solution;
step (3): fermenting the fermentable sugar solution obtained in the step (2) to obtain cells containing microbial oil;
step (4): extracting and refining the grease from the cells obtained in the step (3) to obtain microbial grease;
step (5): epoxidizing the microbial oil obtained in the step (4) to obtain epoxy microbial oil;
step (6): removing impurities, washing and drying the epoxy microbial oil obtained in the step (5) to obtain an epoxy plasticizer;
wherein, the epoxidation of the microbial oil in the step (5) is carried out under the catalysis of lipase;
optionally, the lipase is selected from the group consisting of immobilized lipases;
optionally, the epoxidation reaction is carried out in an organic solvent system selected from one of t-butanol, ethyl acetate, toluene, cyclohexane, petroleum ether.
2. The method for producing epoxy plasticizers from lignocellulosic biomass according to claim 1, characterized in that the pretreatment in step (1) is a steam pretreatment based on dilute acid hydrolysis;
optionally, the pretreatment conditions are: the liquid-solid ratio L/kg is 1:1-10:1, the sulfuric acid dosage based on the dry weight of the raw materials is 0.01-10%, and the pretreatment temperature is 130-180 ℃.
3. The method of producing epoxy plasticizers from lignocellulosic biomass as claimed in claim 1, wherein the hydrolysis of the liquid-solid mixture in step (2) is performed under cellulase catalysis;
optionally, before hydrolysis, the pH of the liquid-solid mixture is adjusted to 3-6;
optionally, during the hydrolysis process, adding a nonionic surfactant;
optionally, the nonionic surfactant is selected from one of tween 20, tween 80, sodium lignin sulfonate, span 20, span 80, triton X-100, and triton X-114;
optionally, the hydrolysis temperature is 30 to 60 ℃.
4. The method for producing epoxy plasticizer by using lignocellulose biomass as raw material according to claim 3, wherein the hydrolysis process in step (2) is a non-isothermal process, and the hydrolysis temperature is periodically changed at 30-60 ℃;
optionally, the hydrolysis temperature is periodically switched between a first temperature range of 50-55 ℃ and a second temperature range of 40-45 ℃ every 12 hours, and the total hydrolysis time is 72-120 hours.
5. The method for producing epoxy plasticizer by using lignocellulose biomass as raw material according to claim 1, characterized in that, in the step (3), the fermentation of the fermentable sugar solution is performed under the conditions of 25-60 ℃ and pH 4.5-8.0, and the carbon-nitrogen ratio of the culture medium is 5:1-1000:1;
optionally, the fermentation is a two-step fermentation reaction, wherein the carbon-nitrogen ratio is controlled to be 5:1-20:1 in the first step of fermentation reaction, and the carbon-nitrogen ratio is controlled to be 200:1-1000:1 in the second step of fermentation reaction;
optionally, the lipid microorganism for fermentation is selected from one of rhodosporidium toruloides, rhodotorula glutinis, oleaginous stonus and candida Pityrosporum.
6. The method for producing epoxy plasticizer by using lignocellulose biomass as raw material according to claim 1, wherein the oil extraction of the cells in step (4) is a solvent extraction method;
optionally, the solvent is selected from one or more of dichloromethane, chloroform, ethylene oxide, petroleum ether, ethyl acetate, acetone, methanol and diethyl ether;
optionally, the cells are subjected to centrifugation or filtration dehydration, steam or acid treatment prior to solvent extraction of the cells to extract the oil.
7. The method for producing an epoxy plasticizer using lignocellulosic biomass as a feedstock according to claim 1, wherein an oxygen carrier is used in the epoxidation reaction, the oxygen carrier being selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid.
8. The method for producing epoxy plasticizers from lignocellulosic biomass as claimed in claim 7, wherein the epoxidation reaction conditions in step (5) are: the oxygen carrier is 5-25% based on the weight of the microbial oil, the hydrogen peroxide is 5-20% based on the weight of the microbial oil, the lipase is 1.5-20% based on the weight of the microbial oil, the organic solvent is 1-6 times based on the weight of the microbial oil, the reaction temperature is 30-50 ℃, the stirring speed is 100-500rpm, and the reaction time is 2-24 hours.
9. The method for producing epoxy plasticizer by using lignocellulose biomass as raw material according to claim 8, characterized in that hydrogen peroxide in step (5) is added into the reaction system by way of stepwise addition;
optionally, the step-by-step addition is carried out by adding hydrogen peroxide within the first 100 minutes of reaction, wherein the time interval of each addition is 5-10min, and the total dosage of each addition is 1/20-1/10.
10. The method for producing epoxy plasticizer by using lignocellulose biomass as raw material according to claim 1, wherein the conditions of the impurity removal, washing and drying treatment of the epoxy microbial oil in the step (6) are as follows: the oil phase is distilled at 40-60 ℃ and 5-10kPa absolute pressure for 30-120 minutes, then is washed for 1-3 times at 30-60 ℃ by adopting sodium bicarbonate solution with mass fraction of 3-5%, and is distilled at 40-60 ℃ and 5-10kPa absolute pressure for 30-120 minutes.
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| CN102703224A (en) * | 2012-06-06 | 2012-10-03 | 北京林氏精化新材料有限公司 | Method for preparing substance containing epoxyfatty acid low carbon alcohol ester plasticizer by palm oil |
| CN104356097A (en) * | 2014-10-20 | 2015-02-18 | 中国科学院广州能源研究所 | Preparation method of microbial oil-based epoxide |
| CN112708643A (en) * | 2021-02-05 | 2021-04-27 | 武汉科技大学 | Method for preparing microbial oil by using straw resources |
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| CN102703224A (en) * | 2012-06-06 | 2012-10-03 | 北京林氏精化新材料有限公司 | Method for preparing substance containing epoxyfatty acid low carbon alcohol ester plasticizer by palm oil |
| CN104356097A (en) * | 2014-10-20 | 2015-02-18 | 中国科学院广州能源研究所 | Preparation method of microbial oil-based epoxide |
| CN112708643A (en) * | 2021-02-05 | 2021-04-27 | 武汉科技大学 | Method for preparing microbial oil by using straw resources |
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