CN109136293B - Rape straw recycling full-utilization method - Google Patents
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Abstract
The invention belongs to the field of xylose blasting extraction and ethanol fermentation preparation, and particularly relates to a rape straw recycling full utilization method. The method comprises the steps of pretreating raw materials, then adopting screw extrusion blasting, xylose extraction, hydrolysis impurity removal, enzymolysis fermentation process, preparing compound fertilizer from fermentation residues, treating and recycling wastewater and the like, so that the resource full utilization of rape straws is realized, the production cost of fermentation ethanol is reduced, and the environment-friendly production process is formed.
Description
Technical Field
The invention belongs to the field of xylose blasting extraction and ethanol fermentation preparation, and particularly relates to a rape straw recycling full utilization method.
Background
With the development of biomass energy utilization technology, crop straws have become important biomass energy resources. China is the second rape planting country in the world, and the rape planting area and the rape seed yield account for about 20 percent of the total amount of the world. In 2013, the rape planting area of China is about 750 kilohm 2, and the yield of rapeseeds is more than 1400 kilotons. The rape is planted, a large amount of rape straws can be generated while rapeseeds are obtained, and therefore, the rape straw resources in China are very rich. The cellulose content in the rape straws is higher than that in the rice straws and the wheat straws,
the composition of rape straw, rice straw and wheat straw is shown in the following table:
as can be seen from the analysis results in the table, the component content of different kinds of straws has larger difference. The cellulose content of rape straws in the 3 straws is the highest, the content of the straws in the rod part is as high as 52.99 percent, and the lignin content is also greatly different: the lignin content difference between the rape straws and the wheat straws is small, which also indicates that the rape straws contain more cellulose and can be used for preparing ethanol by fermentation or papermaking; wherein the content of hemicellulose is still about 20%, and can be used for preparing xylose. The outer surface of the rape straw is compact and smooth and contains weak medium layers such as fat, wax and the like; the overall volume weight is 0.3068 g/cm-3. The main chemical components (cellulose, hemicellulose and lignin) of the composite are close to two common gramineae plants of corn stalks and reeds and poplar broad-leaved wood. Taking 2013 as an example, the collectable amount of rape straw resource amount which is only in Sichuan province is 828 ten thousand t. At present, most of rape stalks are abandoned or randomly burned except a small amount of rape stalks serving as coarse fodder, so that the environment is seriously polluted, and huge resource waste is caused. If the method is used for recycling and energy utilization, the industrial development is realized, and the win-win effect can be achieved.
Application No. 201110244212.0 "a method for preparing rape stalk pulp" discloses a method for preparing rape stalk pulp, which comprises using rape stalk, water, steam and cooking liquor as raw materials, producing rape stalk pulp by dry-wet method stock preparation and horizontal pipe continuous steaming technology, and preparing the finished product by the procedures of rape stalk → cutting machine → hydraulic grass chopper → inclined screw dehydrator → pin drum gauge → presteaming screw → T-shaped pipe → cooking pipe → discharger → jet-blow pan extraction, etc., the method has the advantages that: the method has the advantages of utilizing general papermaking equipment, having less equipment investment, simple process, good economic benefit, little environmental pollution, high pulp whiteness and good stability, changing the rape stalks into valuable, benefiting the nation and the people, and producing the rape stalk pulp which is a good raw material for papermaking. The methods for extracting xylose from rape straws and preparing ethanol by fermentation have not been reported.
The rape straw is a functional super molecular body which is formed by mutually interweaving cellulose, hemicellulose, lignin and the like and has a complex structure. However, many studies on cellulosic ethanol currently take into account how to convert the cellulose part in the raw material into ethanol efficiently, so as to maximize the yield of the ethanol, and less consider the efficient utilization of components such as lignin. As the target product is single, the cellulose ethanol industry is difficult to break through the technical economic clearance, and large-scale industrialized production cannot be realized. In addition, other components in the raw materials cannot be fully utilized, so that the environmental pollution is caused and the production cost is increased while the resources are seriously wasted, so that the cost for preparing the ethanol by fermenting the straws is too high, and the large-scale industrial production cannot be realized.
Disclosure of Invention
The invention aims to provide a rape straw resource full utilization method aiming at the problems. The method adopts the technologies of screw extrusion blasting, xylose extraction, hydrolysis impurity removal, enzymolysis fermentation process, preparation of compound fertilizer from fermentation residues, wastewater treatment and recycling and the like, solves the problem of recycling full utilization of rape straws, reduces the production cost of fermented ethanol, and is green and environment-friendly.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a rape straw recycling full-quality utilization method takes rape straws as raw materials, and obtains the recycling full-quality utilization of xylose, ethanol and compound fertilizer rape straws by the following steps:
(1) pretreatment of
Cutting rape straws to 1-3cm by a hammer mill, and removing impurities and clay with people by a dust remover; the dedusted rape straws enter a hot water washer, and residual soil, water-soluble pigments and other substances are washed off and softened at the temperature of 80-100 ℃; and conveying the pretreated rape straws to a squeezing machine to enable the water content of the materials to reach 40-60 wt%.
Rape straws are crushed by a hammer crusher, the core working devices of the hammer crusher are a hammer sheet and a sieve plate, when the hammer crusher works, the hammer sheet starts to do high-speed rotation motion and continuously hits straws, so that the structure of the straws is damaged, the rape straws meeting the requirement of 1-3cm are discharged through sieve plate holes, the hammer sheet still continuously hits the straws which do not meet the requirement, when the straws are crushed to meet the requirement, the straws are discharged from the sieve holes, dust is removed, and impurities and dust are removed; the dedusted rape straws still carry partial soil and other impurities, and in order to remove the impurities and soften the rape straws for facilitating blasting, hot water with the temperature of 80-100 ℃ is used for carrying out countercurrent washing in a spiral grass washer, the grass washer is an inclined spiral, water enters from the lower part, the rape straws enter from the upper part, and the temperature is maintained by introducing steam from a jacket outside the grass washer. The rape straws washed by hot water are squeezed by a single-screw squeezing machine to ensure that the materials contain 40 to 60 percent of water; the washing water is reused for washing raw materials after being processed.
(2) Screw extrusion spray blasting
Feeding the material obtained in the step (1) into a screw extrusion flash explosion spraying device, kneading and extruding the material by using a screw extruder, pushing the material to move forwards under the pushing of the screw extruder, and spraying flash explosion from an outlet; controlling the temperature at 140 ℃ and 220 ℃, the pressure at 1.4-3.0MPa and the retention time at 80-150 s; and (4) realizing the spray explosion process to obtain the spray explosion material containing xylose.
The extruded materials are sent into a screw extrusion spray blaster, and the residence time of the materials in the body is adjusted by controlling the rotating speed of the screw to be 80-150 s; the screw rod spray blasting machine utilizes the rotation of the screw rod to push the material to advance, and realizes the sealing, pressurization and temperature rise of the material by means of the friction between the plant fiber and the screw rod. The temperature is controlled at 190 ℃ and the pressure is controlled at 1.6-2.0MPa, when the material reaches the outlet, the material is compacted, and the temperature is increased to a certain degree due to frictional heat. Because the material contains a certain amount of water, when the material is continuously discharged from the slit die, high-temperature and high-pressure water in the material is instantaneously discharged to generate huge explosive force, so that the fasciculate tissue structure of plant fibers is damaged, the dissociation of plant fiber cells is realized, the hemicellulose is degraded into xylose, and the spray-exploded material containing the xylose and a small amount of organic acid (acetic acid) is obtained; the washing water is recycled after being treated.
(3) Extraction of xylose
Preparing the spray blasting material into slurry with the mass concentration of 15-25% by using water, pumping the slurry into a high-concentration mill by using a pump to carry out high-concentration milling, and milling fibers to fully dissolve xylose; and (3) performing countercurrent extraction on the ground pulp in an extractor by using hot water at the temperature of 60-90 ℃, extracting xylose and other impurities, controlling the pH to be 6-7, and extruding until the water content is 80-90%. Simultaneously pressing and drying the fiber slurry to reach the water content of 50-60 percent; the extracting solution is processed by a membrane to recover xylose.
Preferably, the organic acid in the countercurrent extraction solution is neutralized to pH7 with NaOH, and then desalted by electrodialysis to facilitate purification of xylose.
And (3) obtaining a refined xylose liquid with the mass percentage of 25% by adopting a microfiltration membrane and a nanofiltration membrane as the counter-current extracting solution and a reverse osmosis membrane.
(4) Acid hydrolysis
Preparing 20-30% fiber pulp from fiber material with water content of 50-60%, and hydrolyzing with 1-2% dilute sulfuric acid at 110-130 deg.C for 30-100 min. Carrying out filter pressing on the hydrolyzed material, and washing filter residues with clear water to a pH value of 5; and (4) combining the press filtrate with the extracting solution in the step (3) to extract xylose.
Preparing 20-10% fiber pulp from fiber material with water content of 80-90%, and hydrolyzing with 1-2% dilute sulfuric acid to fully hydrolyze hemicellulose in the raw material, which is beneficial to subsequent hydrolysis fermentation; the hydrolysis temperature is 110 ℃ and 130 ℃, and the time is 30-100 min. Carrying out filter pressing on the hydrolyzed material, and washing filter residues with clear water to a pH value of 5; and (4) mixing the press filtrate and the extract liquid in the step (3) to extract xylose.
(5) Fermentation for preparing ethanol
Synchronous saccharification and fermentation are adopted, namely enzymolysis of lignocellulose and fermentation of glucose are carried out simultaneously. The cellulose concentration is 10-20%, the cellulose dosage is 7.5IU/g (calculated by absolute dry raw materials), the pichia stipitis is 30-40IU/g (calculated by absolute dry raw materials) and the production period is 90-130h, and synchronous diastatic fermentation (SSF) is carried out to obtain the ethanol fermentation liquor.
Adjusting the pH value of a material containing 10-20% of fibers after xylose extraction to 4-5, adding cellulase and yeast, wherein the addition amounts are respectively 7.5IU/g (calculated by absolute dry raw materials) of the cellulase and 30-40IU/g (calculated by absolute dry raw materials) of tree trunk pichia stipitis, and the production period is 50-60h, and carrying out synchronous saccharification and fermentation to obtain the ethanol fermentation liquor.
(6) And (4) centrifugally filtering the fermentation liquid, and refining the filtrate to obtain the finished product ethanol.
And (3) carrying out solid-liquid separation on the ethanol fermentation liquor by using a horizontal centrifuge, and rectifying the separated liquid to obtain the finished product ethanol.
(7) The filter residue is the fermentation residue after ethanol is extracted and is used for producing the organic compound fertilizer.
The solid rape stalk fermentation residue separated by the centrifuge is mainly composed of lignin, potassium, iron, phosphorus, urea and the like, and is prepared into the slow-release compound fertilizer by a conventional method.
(8) The fermentation wastewater is recycled after being treated by a membrane. Generally, 10-15 tons of ethanol waste liquid is generated every 1 ton of ethanol is prepared, and in order to avoid environmental pollution, the ethanol waste liquid is recycled after being treated by adopting a membrane technology.
The steam explosion method is to saturate the lignocellulosic feedstock with steam under high pressure, and after a period of time, the pressure is suddenly released to atmospheric pressure, so that the feedstock explodes and decomposes itself. During the blasting process, the parent structure of lignocellulose is destroyed due to self expansion, so that the non-crystalline cellulose is converted into crystalline cellulose, the crystallinity of the cellulose is increased, and a plurality of single celluloses are separated out. Hemicellulose is easily degraded into xylose during the steam explosion pretreatment process. At present, most of steam explosion treatment equipment is of a pot type, and the continuity of steam explosion cannot be realized. A continuous steam explosion machine is adopted, a screw rod rotates to push materials to advance, and the materials are conveyed, sealed, pressurized and heated by means of friction between plant fibers and the screw rod. When the material reaches the outlet, it is compacted and the temperature rises to a certain extent due to frictional heating. Because the material contains a certain amount of water, when the material is continuously discharged from the slit outlet, the high-temperature and high-pressure water in the material is instantaneously released to generate huge explosive force, so that the fasciculate tissue structure of the plant fiber is damaged, and the dissociation of plant fiber cells is realized.
In order to fully hydrolyze hemicellulose into xylose, most of the hemicellulose of the rape straws is degraded into xylose after explosion, and a series of substances which have an inhibiting effect on subsequent fermentation are generated at the same time, wherein the substances mainly comprise degradation products such as formic acid, acetic acid and the like. Xylose and organic acid salt are extracted by neutralization and water washing. The fermentation production of ethanol by using hexose is already a well-established technology, and the fermentation production of ethanol by using pentose (such as xylose) is relatively lagged behind. And the conversion rate of ethanol in the fermentation process of xylose is very low, and the utilization rate of pentose is correspondingly low, which is one of the reasons for high cost of ethanol preparation by straw fermentation. Therefore, the invention adds a dilute acid hydrolysis process after washing the explosive materials, and further hydrolyzes the undegraded hemicellulose into xylose for removal.
In the invention, because five-carbon sugar is removed, the enzyme dosage is reduced, the enzymatic hydrolysis process of cellulose and the ethanol fermentation of sugar are synchronously saccharified and fermented in the same container, and the yeast for alcohol fermentation is inoculated while the cellulase is added, so that the generated glucose can be immediately fermented into alcohol by the yeast; the product inhibition is removed, the continuous saccharification of the cellulose can not be hindered, and the alcohol yield can be obviously improved. The method is the so-called synchronous saccharification and fermentation technology, and has the advantages that the glucose of the enzymatic hydrolysate is continuously fermented into ethanol, so that the feedback inhibition of the glucose on the cellulase is eliminated, the enzymatic hydrolysis reaction is favorably carried out, and the saccharification and fermentation efficiency is improved; the process adopts a one-step fermentation method, thereby simplifying the process, reducing the equipment investment and reducing the energy consumption in production.
The invention can prepare the fermentation residues into the compound organic fertilizer, thereby fully utilizing the raw materials, increasing the benefit and reducing the cost of fermenting the ethanol. Most of the fermentation residues are lignin, and lignin molecules have excellent adsorbability and slow release performance and can be used as a slow release carrier of the fertilizer. And then the self-adsorption is utilized to prepare the slow release fertilizer. Meanwhile, as the rape straws are rich in protein (5-6 percent) and are not damaged in the fermentation process, the rape straws can also be used for producing feed.
When the rape straws are fermented to prepare the ethanol, a large amount of wastewater is generated, 10-15 tons of wastewater is generated when 1 ton of ethanol is produced, the organic wastewater mainly comprises organic acid, lignin, aldehydes, saccharides, proteins and other substances, and if the organic wastewater is directly discharged, the environment is polluted, and huge waste is also caused. The waste liquid is first solid-liquid separated, the solid part may be compounded to produce composite fertilizer or to produce coarse fodder for animal culture, the liquid part is treated with film and water is reused in production, and the concentrated liquid is used in producing composite fertilizer or fodder.
The invention mainly aims to provide a rape straw recycling full utilization method, which can reduce the cost of preparing ethanol by cellulose fermentation and is a process technology for green and environment-friendly industrial production.
The positive effects of the invention are as follows:
in the process of straw synchronous saccharification and fermentation, because glucose generated after cellulase hydrolysis is synchronously fermented, the feedback inhibition influence of the glucose on the reaction rate of the cellulase is eliminated, the hydrolysis efficiency is enhanced, the input amount of enzyme is reduced, and the production cost is reduced. Compared with the traditional step enzymolysis fermentation process, the synchronous enzymolysis fermentation process can improve the yield by 20-30 percent and reduce the water consumption by 30 percent.
And secondly, the full and effective utilization of rape stalk resources can be realized, and after the rape stalks are pulped by adopting a green blasting method and xylose is extracted, the ethanol is prepared by fermentation, so that the industrialization cost of the cellulosic ethanol is reduced, the resources are fully utilized, and the pollution to the environment is reduced.
Drawings
FIG. 1 is a process flow chart of the rape straw resource full utilization method of the invention.
Detailed Description
In order that the present disclosure may be more readily understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
In the present document,% means, unless otherwise specified, its mass% content, i.e., wt%.
Example 1:
(1) rape straws are crushed by a hammer crusher, the core working devices of the hammer crusher are a hammer sheet and a sieve plate, when the hammer crusher works, the hammer sheet starts to do high-speed rotation motion and continuously hits straws, so that the structure of the straws is damaged, the rape straws meeting the requirement of 1-3cm are discharged through sieve plate holes, the hammer sheet still continuously hits the straws which do not meet the requirement, when the straws are crushed to meet the requirement, the straws are discharged from the sieve holes, dust is removed, and impurities and dust are removed; the dedusted rape straws still carry partial soil and other impurities, and in order to remove the impurities and soften the rape straws for facilitating blasting, hot water with the temperature of 85 ℃ is used for carrying out countercurrent washing in a spiral grass washer, the grass washer is an inclined spiral, water enters from the lower part, the rape straws enter from the upper part, and the temperature is maintained by introducing steam from a jacket outside the grass washer. The rape straws washed by hot water are squeezed by a single-screw squeezing machine to ensure that the materials contain 50 percent of water; the washing water is treated and then recycled as the washing raw material.
(2) The squeezed materials are sent into a screw extrusion spray blaster, and the retention time of the materials in the body is adjusted for 150s by controlling the rotating speed of the screw; the screw rod spray blasting machine utilizes the rotation of the screw rod to push the material to advance, and realizes the sealing, pressurization and temperature rise of the material by means of the friction between the plant fiber and the screw rod. The temperature is controlled at 170 ℃ and the pressure is controlled at 1.7MPa, when the material reaches the outlet, the material is compacted, and the temperature is raised to a certain extent due to frictional heat. Because the material contains a certain amount of water, when the material is continuously discharged from the slit die, high-temperature and high-pressure water in the material is instantaneously discharged to generate huge explosive force, so that the fasciculate tissue structure of plant fibers is damaged, the dissociation of plant fiber cells is realized, the hemicellulose is degraded into xylose, and the jet-exploded material containing the xylose is obtained; the washing water is recycled after being treated.
(3) The spray blasting material containing xylose is prepared into slurry with the concentration of 20% by water, the slurry is evenly stirred and pumped into a high-concentration mill by a pump to be ground into slurry, and the fiber is ground into fine powder to ensure that the xylose is more fully dissolved out. And (3) feeding the ground pulp into a xylose extractor, performing countercurrent extraction by using hot water at the temperature of 80 ℃, extracting xylose and other harmful substances such as acetic acid and the like which inhibit hydrolytic fermentation, and simultaneously washing and extruding the fiber after xylose extraction by using the extractor until the water content is 80%. The organic acid in the countercurrent extract was neutralized to pH6 with NaOH and then desalted by electrodialysis to facilitate xylose purification. And (3) obtaining a refined xylose liquid with the content of 25% by adopting a microfiltration membrane, a nanofiltration membrane and a reverse osmosis membrane as a countercurrent extracting solution.
(4) Preparing 15% fiber pulp from fiber materials with water content of 80%, and hydrolyzing with 1.2% dilute sulfuric acid to fully hydrolyze hemicellulose in the raw materials, which is beneficial to the subsequent hydrolysis fermentation; the hydrolysis temperature is 120 deg.C, and the hydrolysis time is 45 min. Carrying out filter pressing on the hydrolyzed material, and washing filter residues with clear water to a pH value of 5; the press filtrate is combined with the former extract to extract xylose.
(5) Adjusting the pH value of a material containing 15% of fibers after extracting xylose to 4.8, adding cellulase and yeast, wherein the adding amounts are respectively as follows: the dosage of the cellulase is 7.5IU/g (calculated by absolute dry raw materials), the dosage of the tree trunk pichia stipitis is 35IU/g (calculated by absolute dry raw materials), and the production period is 55h, and the ethanol fermentation liquor is obtained by synchronous diastatic fermentation. And (3) carrying out solid-liquid separation on the ethanol fermentation liquor by using a horizontal centrifuge, and rectifying the separated liquid to obtain the finished product ethanol. The ethanol yield was 50%. The solid rape stalk fermentation residue separated by the centrifuge is mainly composed of lignin, potassium, iron, phosphorus, urea and the like, and is prepared into the slow-release compound fertilizer by a conventional method.
Every 1 ton of ethanol is prepared, about 12 tons of ethanol waste liquid is generated, and in order to avoid environmental pollution, the ethanol waste liquid is recycled after being treated by adopting a membrane technology.
Example 2:
rape straws are crushed by a hammer crusher, the core working devices of the hammer crusher are a hammer sheet and a sieve plate, when the hammer crusher works, the hammer sheet starts to do high-speed rotation motion and continuously hits straws, so that the structure of the straws is damaged, the rape straws meeting the requirement of 1-3cm are discharged through sieve plate holes, the hammer sheet still continuously hits the straws which do not meet the requirement, when the straws are crushed to meet the requirement, the straws are discharged from the sieve holes, dust is removed, and impurities and dust are removed; the dedusted rape straws still carry partial soil and other impurities, and in order to remove the impurities and soften the rape straws for facilitating blasting, hot water with the temperature of 85 ℃ is used for carrying out countercurrent washing in a spiral grass washer, the grass washer is an inclined spiral, water enters from the lower part, the rape straws enter from the upper part, and the temperature is maintained by introducing steam from a jacket outside the grass washer. The rape straws washed by hot water are squeezed by a single-screw squeezing machine to ensure that the materials contain 50 percent of water; the washing water is reused for washing raw materials after being processed.
The squeezed materials are sent into a screw extrusion spray blaster, and the retention time of the materials in the body is adjusted for 150s by controlling the rotating speed of the screw; the screw rod spray blasting machine utilizes the rotation of the screw rod to push the material to advance, and realizes the sealing, pressurization and temperature rise of the material by means of the friction between the plant fiber and the screw rod. The temperature is controlled at 180 ℃ and the pressure is controlled at 1.9MPa, when the material reaches the outlet, the material is compacted, and the temperature is raised to a certain degree due to frictional heat. Because the material contains a certain amount of water, when the material is continuously discharged from the slit die, high-temperature and high-pressure water in the material is instantaneously discharged to generate huge explosive force, so that the fasciculate tissue structure of plant fibers is damaged, the dissociation of plant fiber cells is realized, the hemicellulose is degraded into xylose, and the jet-exploded material containing the xylose is obtained; the washing water is recycled after being treated. The spray blasting material containing xylose is prepared into slurry with the concentration of 20% by water, the slurry is evenly stirred and pumped into a high-concentration mill by a pump to be ground into slurry, and the fiber is ground into fine powder to ensure that the xylose is more fully dissolved out. The ground pulp enters a xylose extractor to be subjected to countercurrent extraction by hot water at the temperature of 80 ℃, xylose and other harmful substances such as acetic acid and the like which inhibit hydrolytic fermentation are extracted, meanwhile, the extractor washes the fiber after xylose extraction, controls the pH to 6-7, and extrudes the fiber until the water content is 80-90%. The organic acid in the countercurrent extraction was neutralized to pH7 with NaOH and then desalted by electrodialysis to facilitate the refining of xylose. And (3) obtaining a refined xylose liquid with the content of 25% by adopting a microfiltration membrane, a nanofiltration membrane and a reverse osmosis membrane as a countercurrent extracting solution. Preparing 15% fiber pulp from fiber materials with water content of 80-90%, and hydrolyzing with 1.2% sulfuric acid to fully hydrolyze hemicellulose in the raw materials, which is beneficial to the subsequent hydrolysis fermentation; the hydrolysis temperature is 120 deg.C, and the hydrolysis time is 45 min. Carrying out filter pressing on the hydrolyzed material, and washing filter residues with clear water to a pH value of 5; the press filtrate is combined with the former extract to extract xylose. Adjusting the pH value of a material containing 15% of fibers after xylose extraction to 4.8, adding cellulase and yeast, wherein the addition amounts are respectively 7.5IU/g of cellulase (calculated by absolute dry raw materials) and 35IU/g of tree trunk pichia stipitis (calculated by absolute dry raw materials), the production period is 55h, carrying out synchronous diastatic fermentation to obtain ethanol fermentation liquor, carrying out solid-liquid separation on the ethanol fermentation liquor by a horizontal centrifuge, and rectifying the separated liquid to obtain a finished product of ethanol. The ethanol yield was 52%. The solid rape stalk fermentation residue separated by the centrifuge is mainly composed of lignin, potassium, iron, phosphorus, urea and the like, and is prepared into the slow-release compound fertilizer by a conventional method.
Every 1 ton of ethanol is prepared, about 12 tons of ethanol waste liquid is generated, and in order to avoid environmental pollution, the ethanol waste liquid is recycled after being treated by adopting a membrane technology.
Example 3:
rape straws are crushed by a hammer crusher, the core working devices of the hammer crusher are a hammer sheet and a sieve plate, when the hammer crusher works, the hammer sheet starts to do high-speed rotation motion and continuously hits straws, so that the structure of the straws is damaged, the rape straws meeting the requirement of 1-3cm are discharged through sieve plate holes, the hammer sheet still continuously hits the straws which do not meet the requirement, when the straws are crushed to meet the requirement, the straws are discharged from the sieve holes, dust is removed, and impurities and dust are removed; the dedusted rape straws still carry partial soil and other impurities, and in order to remove the impurities and soften the rape straws for facilitating blasting, hot water with the temperature of 85 ℃ is used for carrying out countercurrent washing in a spiral grass washer, the grass washer is an inclined spiral, water enters from the lower part, the rape straws enter from the upper part, and the temperature is maintained by introducing steam from a jacket outside the grass washer. The rape straws washed by hot water are squeezed by a single-screw squeezing machine to ensure that the materials contain 50 percent of water; the washing water is reused for washing raw materials after being processed.
The squeezed materials are sent into a screw extrusion spray blaster, and the retention time of the materials in the body is adjusted for 150s by controlling the rotating speed of the screw; the screw rod spray blasting machine utilizes the rotation of the screw rod to push the material to advance, and realizes the sealing, pressurization and temperature rise of the material by means of the friction between the plant fiber and the screw rod. The temperature is controlled at 180 ℃ and the pressure is controlled at 1.9MPa, when the material reaches the outlet, the material is compacted, and the temperature is raised to a certain degree due to frictional heat. Because the material contains a certain amount of water, when the material is continuously discharged from the slit die, high-temperature and high-pressure water in the material is instantaneously discharged to generate huge explosive force, so that the fasciculate tissue structure of plant fibers is damaged, the dissociation of plant fiber cells is realized, the hemicellulose is degraded into xylose, and the jet-exploded material containing the xylose is obtained; the washing water is recycled after being treated. The spray blasting material containing xylose is prepared into slurry with the concentration of 20% by water, the slurry is evenly stirred and pumped into a high-concentration mill by a pump to be ground into slurry, and the fiber is ground into fine powder to ensure that the xylose is more fully dissolved out. The ground pulp enters a xylose extractor to be subjected to countercurrent extraction by hot water at the temperature of 80 ℃, xylose and other harmful substances such as acetic acid and the like which inhibit hydrolytic fermentation are extracted, meanwhile, the extractor washes the fiber after xylose extraction, controls the pH to 6-7, and extrudes the fiber until the water content is 80-90%. The organic acid in the countercurrent extraction was neutralized to pH7 with NaOH and then desalted by electrodialysis to facilitate the refining of xylose. And (3) obtaining a refined xylose liquid with the content of 25% by adopting a microfiltration membrane, a nanofiltration membrane and a reverse osmosis membrane as a countercurrent extracting solution. Preparing 20% fiber pulp from fiber materials with water content of 80-90%, and hydrolyzing with 1.2% sulfuric acid to fully hydrolyze hemicellulose in the raw materials, which is beneficial to the subsequent hydrolysis fermentation; the hydrolysis temperature is 120 deg.C, and the hydrolysis time is 45 min. Carrying out filter pressing on the hydrolyzed material, and washing filter residues with clear water to a pH value of 5; the press filtrate is combined with the former extract to extract xylose. Adjusting the pH value of a material containing 15% of fibers after xylose extraction to 4.8, adding cellulase and yeast, wherein the addition amounts are respectively 7.5IU/g of cellulase (calculated by absolute dry raw materials) and 35IU/g of tree trunk pichia stipitis (calculated by absolute dry raw materials), the production period is 55h, carrying out synchronous diastatic fermentation to obtain ethanol fermentation liquor, carrying out solid-liquid separation on the ethanol fermentation liquor by a horizontal centrifuge, and rectifying the separated liquid to obtain a finished product of ethanol. The ethanol yield was 55%. The solid rape stalk fermentation residue separated by the centrifuge is mainly composed of lignin, potassium, iron, phosphorus, urea and the like, and is prepared into the slow-release compound fertilizer by a conventional method.
Every 1 ton of ethanol is prepared, about 12 tons of ethanol waste liquid is generated, and in order to avoid environmental pollution, the ethanol waste liquid is recycled after being treated by adopting a membrane technology.
Example 4
The conditions were the same as in example 1, except that the hydrolysis step was omitted, and the ethanol yield was 45%.
Example 5
The conditions were the same as in example 1, except that the blasting step was omitted, and the ethanol yield was 40%.
The ethanol yields under the different process conditions are given in the following table
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A rape straw resource full utilization method is characterized by comprising the following steps:
(1) pretreatment of
Crushing rape straws into 1-3cm in length by using a hammer mill, and removing impurities and soil by using a dust remover; putting the dedusted rape straws into a hot water washer, washing off residual soil and water-soluble pigment substances at 80-100 ℃, and softening; then conveying the pretreated rape straws to a squeezing machine to ensure that the water content of the materials is 40-60 wt%;
(2) screw extrusion spray blasting
Feeding the material processed in the step (1) into a screw extrusion flash evaporation blasting machine, kneading and extruding the material by using a screw extruder, moving forward under the pushing of the screw extruder, and ejecting out flash explosion from an outlet; controlling the temperature at 140 ℃ and 220 ℃, the pressure at 1.4-3.0MPa and the retention time at 80-150 s; spray explosion materials containing xylose and a small amount of byproduct organic acid are obtained;
(3) extraction of xylose
Preparing the blasting material into slurry with the concentration of 15-25% by using water, and grinding the slurry by using a high-concentration mill; performing countercurrent extraction on the ground pulp in an extractor by using hot water at the temperature of 60-90 ℃, extracting xylose and impurities in the ground pulp, and simultaneously pressing and drying the fiber pulp until the water content is 50-60%; treating the extract with a membrane to recover xylose;
(4) the acid hydrolysis is carried out on the mixture,
preparing the fiber pulp into 20-30% fiber pulp, hydrolyzing with 1-2% dilute sulfuric acid at the hydrolysis temperature of 110-; mixing the press filtrate with the extracting solution in the step (3) to extract xylose;
(5) fermentation for preparing ethanol
Synchronous diastatic fermentation is adopted, namely enzymolysis of lignocellulose and fermentation of glucose are carried out simultaneously, the cellulose concentration is 10-20%, the cellulose dosage is 7.5IU/g calculated by absolute dry raw materials, the pichia stipitis is 30-40IU/g calculated by absolute dry raw materials, the production period is 50-60h, and the synchronous diastatic fermentation is carried out to obtain ethanol fermentation liquor;
(6) centrifuging and filtering the fermentation liquid, and refining the filtrate to obtain a finished product ethanol; the filter residue is used for producing organic compound fertilizer; the fermentation wastewater is recycled after being treated by a membrane.
2. The rape straw resource full utilization method according to claim 1, which is characterized in that: the dedusted rape straws are washed in a spiral straw washer in a countercurrent mode, the straw washer is of an inclined spiral structure, water enters from the lower portion, the rape straws enter from the upper portion, the temperature is maintained by introducing steam from a jacket outside the straw washer, and the rape straws washed by hot water are squeezed by a single spiral squeezing machine; the washing water is reused for washing raw materials after being processed.
3. The rape straw resource full utilization method as claimed in claim 1, which is characterized in that: and (3) washing the fiber after the ground pulp enters a xylose extractor for countercurrent extraction, controlling the pH value to be 6-7, and extruding until the water content is 80-90%.
4. The rape straw resource full utilization method according to claim 3, which is characterized in that: the organic acid in the countercurrent extract was neutralized to pH7 with NaOH and then desalted by electrodialysis to facilitate xylose purification.
5. The rape straw resource full utilization method as claimed in claim 1, which is characterized in that: and (4) performing solid-liquid separation on the fermentation liquid in the step (6) by using a horizontal centrifuge.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964767A (en) * | 2004-04-13 | 2007-05-16 | 埃欧金能量有限公司 | Recovery of inorganic salt during processing of lignocellulosic feedstocks |
| CN101899478A (en) * | 2010-07-26 | 2010-12-01 | 安徽丰原发酵技术工程研究有限公司 | Method for producing ethanol by simultaneous high-efficiency saccharification half enzymolysis and fermentation of straw lignocellulose |
| CN102061323A (en) * | 2010-11-10 | 2011-05-18 | 山东龙力生物科技股份有限公司 | Comprehensive utilization process of wood cellulose |
| CN102251010A (en) * | 2011-05-18 | 2011-11-23 | 广州优锐生物科技有限公司 | Method for producing ethanol by high-efficiency simultaneous saccharification and cofermentation |
| CN103589762A (en) * | 2013-11-12 | 2014-02-19 | 湖南农业大学 | Pretreatment method for improving saccharification efficiency of rape stalks |
| WO2015148288A1 (en) * | 2014-03-25 | 2015-10-01 | Api Intellectual Property Holdings, Llc | Processes for co-producing xylitol with ethanol or other fermentation products |
| CN108179646A (en) * | 2018-01-05 | 2018-06-19 | 四川金象赛瑞化工股份有限公司 | With the method for plant fiber material production xylose, high-boiling alcohol lignin and fiber |
-
2018
- 2018-08-24 CN CN201810971386.9A patent/CN109136293B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964767A (en) * | 2004-04-13 | 2007-05-16 | 埃欧金能量有限公司 | Recovery of inorganic salt during processing of lignocellulosic feedstocks |
| CN101899478A (en) * | 2010-07-26 | 2010-12-01 | 安徽丰原发酵技术工程研究有限公司 | Method for producing ethanol by simultaneous high-efficiency saccharification half enzymolysis and fermentation of straw lignocellulose |
| CN102061323A (en) * | 2010-11-10 | 2011-05-18 | 山东龙力生物科技股份有限公司 | Comprehensive utilization process of wood cellulose |
| CN102251010A (en) * | 2011-05-18 | 2011-11-23 | 广州优锐生物科技有限公司 | Method for producing ethanol by high-efficiency simultaneous saccharification and cofermentation |
| CN103589762A (en) * | 2013-11-12 | 2014-02-19 | 湖南农业大学 | Pretreatment method for improving saccharification efficiency of rape stalks |
| WO2015148288A1 (en) * | 2014-03-25 | 2015-10-01 | Api Intellectual Property Holdings, Llc | Processes for co-producing xylitol with ethanol or other fermentation products |
| CN108179646A (en) * | 2018-01-05 | 2018-06-19 | 四川金象赛瑞化工股份有限公司 | With the method for plant fiber material production xylose, high-boiling alcohol lignin and fiber |
Non-Patent Citations (1)
| Title |
|---|
| 油菜秆酸水解糖化及水解液生产酒精的研究;马黎等;《酿酒科技》;20091231(第8期);第55-57页 * |
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