CN112479885A - Low-cost environment-friendly production process of ethyl linolenate - Google Patents
Low-cost environment-friendly production process of ethyl linolenate Download PDFInfo
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Abstract
The low-cost environment-friendly production process of the ethyl linolenate comprises the following steps: the method comprises the following steps: saponification; step two: acidifying; step three: esterification; step four: treating esterification waste liquid; step five: complexing and purifying; step six: recovering the high-concentration ethanol; step seven: leaching; step eight: dissolving the filter cake obtained by filter pressing in the fifth step, and sending the filter cake as waste liquid to a primary complexing waste liquid tank; step nine: treating the complexing waste liquid; step ten: treating the upper layer oily clear liquid; step eleven: gradient complexing process; step twelve: collecting waste liquid in the gradient complexing procedure; step thirteen: and (5) treating the gradient complexing waste liquid. The invention provides a low-cost environment-friendly production process of ethyl linolenate, which makes full use of the existing production equipment to separate and extract useful components in waste liquid generated in the production process so as to achieve the purposes of increasing yield, reducing cost and reducing emission.
Description
Technical Field
The invention relates to a production process of ethyl linolenate, in particular to a low-cost environment-friendly production process of ethyl linolenate, belonging to the technical field of linolenic acid production.
Background
The current production process of linolenic acid comprises the following steps: the current production process of linolenic acid comprises the following steps: saponification, acidification, multiple washing, esterification, separation, washing, vacuumizing, urea enveloping and purifying, dehydration, distillation and finished product preparation.
The amount of waste liquid generated in the linolenic acid production process is huge, and statistics shows that about 16.5 tons of waste liquid is generated when every 1 ton of 80-type alpha-ethyl linolenate is produced, more than 800 tons of waste liquid are produced according to 50 tons of factories produced every year, the COD content of the waste liquid reaches 500000-800000 mg/L, the ammonia nitrogen content is 80000-110000mg/L and is far higher than national discharge standards (COD is less than or equal to 50mg/L and ammonia nitrogen is less than or equal to 8 mg/L), the waste liquid generated in the production process needs to be treated and can be discharged after reaching the standard, how to realize low-cost production is realized, and the waste liquid is ensured to reach the standard, which becomes a technical problem troubling the development of the industry.
The linolenic acid production waste liquid contains impurities such as ethanol, ethyl ester, complexing agent, inorganic salt and the like, and the steps of pretreatment → physical treatment for removing particles and suspended matters → primary degradation and decarburization → secondary treatment for dephosphorization and denitrification → biochemical treatment → precipitation → ozone disinfection → clarification and discharge are required, so that the treatment difficulty is high, the period is long, the capital cost is high, the waste liquid of each batch can be treated and finished after 6 shifts, and the sewage treatment cost is 4.2 ten thousand yuan for each ton of products. Meanwhile, the waste liquid contains about 50% of ethanol, about 30% of ethyl linolenate, urea, ammonium sulfate and the like, and the existing production process is not effectively recycled, so that the production cost is high. If the waste liquid is directly purified, the process is complex and the purification cost is high because the waste liquid contains ethanol, ethyl ester, complexing agent, inorganic salt and the like, and is not cost-effective from the cost perspective. Therefore, how to separate and utilize each component in the waste liquid of the ethyl linolenate production is a great problem in the current ethyl linolenate production industry.
Disclosure of Invention
The invention aims to: the provided low-cost environment-friendly production process of the ethyl linolenate makes full use of the existing production equipment to separate and extract useful components in waste liquid generated in the production process so as to achieve the purposes of increasing yield, reducing cost and reducing emission.
In order to realize the purpose, the invention adopts the technical scheme that: 1. the low-cost environment-friendly production process of the ethyl linolenate comprises the following steps of:
the method comprises the following steps: saponification: perilla oil, deionized water and an enzyme catalyst, namely lipolase100L are mixed according to the weight ratio of 1: 0.5-4: adding the mixture into a reaction kettle according to the proportion of 0.01-0.1, heating and stirring, keeping the temperature at 40-70 ℃, and reacting for 2-20 hours under the condition that the pH value of materials in the kettle is controlled at 6.5-7.5;
step two: acidifying: slowly adding 10-90% sulfuric acid into the material obtained after saponification in the first step, stirring, controlling the reaction temperature to be between 40 ℃ and 95 ℃, continuously adding the sulfuric acid to control the pH value of the material to be below 4, keeping the pH value of the material to be below 4 after the stirring of the sulfuric acid is stopped, and finishing the reaction after the pH value of the material is kept below 4 for more than 2 hours; standing the reacted materials for 1-6 hours for layering, discharging the hydrolyzed acidic wastewater at the lower layer into an acidic wastewater storage tank for later use, and feeding the oil layer at the upper layer into an esterification process;
step three: esterification: and (2) enabling the upper oil layer obtained in the step (II) to be fatty acid containing alpha-linolenic acid, and mixing the fatty acid with absolute ethyl alcohol and a concentrated sulfuric acid catalyst with the mass concentration of 90-98% according to the weight ratio of 1.25 kg: 1-2 kg: adding 40-50ml of the mixture into an esterification reaction kettle, heating to 75-100 ℃, reacting for 4-10 hours, standing for 1-6 hours, layering materials in the reaction kettle, cooling to discharge lower-layer esterification wastewater to an esterification wastewater storage tank, and feeding an upper-layer oil layer into the step five complexing purification process;
step four: treating esterification waste liquid: sending the esterification waste liquid in the esterification waste water storage tank into an ethanol recovery device, distilling and recovering ethanol, sending the recovered ethanol to a raw material ethanol storage tank, and sending the acidic esterification waste liquid treated by the ethanol recovery device to an acidic waste water storage tank;
step five: complexing and purifying: and C, mixing the fatty acid ethyl ester containing the alpha-ethyl linolenate obtained in the step three with ethanol and urea according to the mass ratio of 1: 1-5: 1-5, adding into a complex reaction kettle, feeding ethanol-urea-fatty acid ethyl ester containing alpha-ethyl linolenate in sequence, heating to 80-100 ℃, refluxing for 30-60 min, keeping the temperature for 30-60 min, then cooling by stages, firstly cooling to 70 +/-5 ℃, keeping the temperature for 15-40 min, then cooling to 60 +/-5 ℃, keeping the temperature for 15-40 min, then cooling to 50 +/-5 ℃, keeping the temperature for 15-40 min, and finally performing pressure filtration by nitrogen;
step six: recovering high-concentration ethanol: adjusting a steam jacket of the filtrate obtained in the step 5 in a complex reaction kettle, heating to 45-60 ℃, cooling ethanol steam by using a refrigerant at the temperature of-10 ℃ under the vacuum condition of 5-10KPa, distilling and recovering ethanol to obtain ethanol with the content of more than 95%, and stopping heating and distilling when the distilling speed is less than 0.1 liter/minute;
step seven: leaching: leaching the distilled material in the six-stage complexing reaction kettle by using hot water at the temperature of 45-60 ℃, standing and layering to obtain alpha-ethyl linolenate with the purity of more than 82% as an upper-layer oily liquid, and sending the washing waste liquid to a primary complexing waste liquid tank;
step eight: dissolving the filter cake obtained by filter pressing in the step five by using a small amount of hot water at 80 ℃, and sending the filter cake to a primary complexing waste liquid tank as waste liquid after complete dissolution;
step nine: and (3) complex waste liquid treatment: feeding the cleaning waste liquid in the seventh step and the waste liquid in the eighth step into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the pH value ranging from 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 1-6 hours for layering, and feeding the upper-layer oily clear liquid to a tenth-layer oily clear liquid treatment process; sending the bottom liquid of the lower layer to an ethanol recovery device, if the pH value of the bottom liquid of the kettle is more than 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, sending the solution to an ethanol distillation device, distilling and recovering ethanol, and sending the recovered ethanol to a raw material ethanol storage tank; cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank;
step ten: and (3) treating the upper layer oily clear liquid: adding hot water into the oily clear liquid generated in the step nine for washing, continuously washing for 2-5 times, adding vitamin C into the oily clear liquid according to the proportion of 0.1-0.5% during the last washing, stirring for 1 hour, standing for layering, discharging lower clear water, conveying the upper oil layer which is fatty acid ethyl ester to an ethyl ester intermediate storage tank, and using the upper oil layer as a raw material for a gradient complexing process;
step eleven: gradient complexation procedure: the first complexing purification reaction kettle receives the fatty acid ethyl ester treated in the step ten, the fatty acid ethyl ester is fully mixed with ethanol and urea which are added in advance, the mass ratio of the fatty acid ethyl ester to the ethanol to the urea is 1:1-4:1-4, the mixture is heated to 80-100 ℃ and refluxed for 30-60 min, the temperature is kept for 30-60 min, then the temperature is reduced to 50 +/-5 ℃ and then kept for 15-40 min, pressure filtration is carried out by using nitrogen, the filtrate enters a second complexing purification reaction kettle, the same amount of urea is added again, the mixture is heated to 80-100 ℃ and refluxed for 30-60 min, the temperature is kept for 30-60 min, then the temperature is reduced to 50 +/-5 ℃ and then kept for 15-40 min, and finally, nitrogen pressure filtration is carried out again;
step twelve: collecting waste liquid in the gradient complexing procedure: vacuum distilling the filtrate obtained in the eleventh step according to a sixth method to recover high-concentration ethanol, leaching the distilled materials in the second complexation purification reaction kettle according to a seventh method, standing for layering to obtain alpha-ethyl linolenate with the purity of more than 82% as an upper-layer oily liquid, and sending the obtained lower-layer oily liquid to a secondary complexation waste liquid tank; meanwhile, dissolving the filter cake obtained by filter pressing in the eleventh step by using a small amount of hot water at 80 ℃, and sending the filter cake to a secondary complexing waste liquid tank after complete dissolution;
step thirteen: treating gradient complexing waste liquid: sending the waste liquid in the secondary complexing waste liquid tank into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the pH value ranging from 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 1-6 hours for layering, and vacuumizing and drying an oil layer at the upper part to sell the oil layer as a fatty acid ethyl ester byproduct; feeding the bottom liquid of the lower layer to an ethanol recovery device, if the pH value of the bottom liquid of the kettle is greater than or equal to 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, feeding the solution to the ethanol recovery device, distilling and recovering ethanol, and feeding the recovered ethanol to a raw material ethanol storage tank; and (4) cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank.
Preferably, the ethanol recovery device comprises an acid preparation distillation still, a condenser and an ethanol storage tank, the complexing waste liquid in the ninth step and the thirteenth step is subjected to standing, the bottom liquid of the lower kettle is injected into the acid preparation distillation still, meanwhile, the acidic waste water in the acidic waste water storage tank is sprayed into the acid preparation distillation still through a spray head, stirring is started, the acidic waste water is stopped to be added after the pH value of the material in the acid preparation distillation still is below 4, then, steam is introduced into a steam jacket of the acid preparation distillation still for distillation, the distilled steam is condensed by the condenser and then enters the ethanol storage tank to be recycled as a raw material, after the distillation is finished, the bottom residual liquid is discharged from a discharge port of the distillation still, and the ammonia nitrogen fertilizer can be obtained through cooling, concentration and crystallization.
Preferably, the ethanol recovery device is provided with a first ethanol storage tank, a second ethanol storage tank and a third ethanol storage tank, the first ethanol storage tank, the second ethanol storage tank and the third ethanol storage tank are respectively connected with a condensate outlet of the condenser through a first condensing valve, a second condensing valve and a third condensing valve, and the discharge ports of the ethanol storage tanks of the first ethanol storage tank, the second ethanol storage tank and the third ethanol storage tank are respectively connected with the reflux pump through a first reflux valve, a second reflux valve and a third reflux valve.
The invention has the positive and beneficial technical effects that: the method comprises the steps of recovering ethanol in hydrolysis waste liquid and esterification waste liquid to be used as an acidity regulator, performing complex purification stage waste liquid treatment by using the acidity regulator to perform demulsification, using the demulsified waste liquid as a raw material for recovering ethanol, collecting oily liquid at the bottom of a kettle, performing demulsification treatment on the oily liquid, collecting upper-layer recovered oil, washing the recovered oil by water, and adding a reducing agent to achieve the effects of clear appearance and qualified peroxide value. Finally, the content of the effective components of the recovered oil is improved from 40 percent to 80 percent by utilizing a gradient complexing purification method.
The production process of the invention ensures that a large amount of waste liquid is utilized and consumed by multiple channels originally, the waste oil breaks through the prior process of water washing after primary purification, the ethanol solvent in the primary purification is shared, and the secondary complexing purification is completed by supplementing the complexing agent. The high content of recovered alcohol and high content of linolenic acid are obtained from the waste liquid, thereby not only reducing the production cost and the waste water treatment cost, but also improving the yield. The invention forms closed loop with emission reduction and waste utilization, reduces the total amount of waste discharge by more than 95 percent, and adopts a gradient complexing purification method, thereby saving the usage amount of ethanol by 50 percent. The whole process is shortened, secondary washing and vacuumizing processes are omitted, the production cost and the production time are greatly reduced, the production efficiency is improved, the cyclic utilization of the ethanol and the fatty acid ethyl ester is realized, the comprehensive yield of the linolenic acid is improved by 20 percent, the production cost is reduced by 40 percent, and the zero discharge of sewage is basically realized.
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FIG. 1 is a flow chart of the production of one embodiment of the present invention.
Detailed Description
In order to more fully explain the implementation of the present invention, the implementation examples of the present invention are provided, which are merely illustrative of the present invention and do not limit the scope of the present invention.
Example (b): the method comprises the following steps: saponification: 500kg of perilla oil, deionized water and an enzyme catalyst, namely lipolase100L are mixed according to the weight ratio of 1: 1: adding the mixture into a reaction kettle according to the proportion of 0.03, heating and keeping the temperature at 45 ℃, and reacting for 3 hours under the condition that the PH value of materials in the kettle is controlled at 7.0;
step two: acidifying: slowly adding 15% sulfuric acid into the material obtained after saponification in the step one, stirring, controlling the reaction temperature to be 45 ℃, continuously adding sulfuric acid to control the pH value of the material to be below 4, keeping the pH value of the material to be below 4 after the stirring of adding sulfuric acid is stopped, keeping the pH value of the material unchanged for 2 hours, and finishing the reaction; standing the reacted materials for 1.5 hours for layering, discharging the lower layer of acid wastewater into an acid wastewater storage tank for later use, and feeding the upper layer of oil into an esterification process;
step three: esterification: and (2) enabling the upper oil layer obtained in the step (II) to be fatty acid containing alpha-linolenic acid, and mixing the fatty acid with ethanol and a concentrated sulfuric acid catalyst with the mass concentration of 98% according to the weight ratio of 1.25 kg: 1 kg: adding 45ml of the mixture into an esterification reaction kettle, heating to 85 ℃, reacting for 1 hour, standing for 1 hour, layering materials in the reaction kettle, cooling to discharge lower-layer esterification wastewater to an esterification wastewater storage tank, and feeding an upper-layer oil layer into a urine enveloping and purifying process;
step four: treating esterification waste liquid: 300kg of bottom liquid of a lower layer of the esterification reaction is injected into an acid preparation distillation kettle, meanwhile, acid waste water in an acid waste water storage tank is sprayed into the acid preparation distillation kettle through a spray header, stirring is started until the pH value of materials in the acid preparation distillation kettle is below 4, then, steam is introduced into a steam jacket of the acid preparation distillation kettle for distillation, the ethanol steam is condensed through a condenser and then enters an ethanol storage tank to be recycled as a raw material, after the distillation is finished, residual liquid at the bottom of the kettle is discharged from a discharge port of the distillation kettle, ammonia nitrogen fertilizer can be obtained through cooling concentration crystallization, and then, the acid esterification waste liquid is sent to an acid waste water storage tank;
step five: complexing and purifying: and C, mixing 520kg of fatty acid ethyl ester containing alpha-linolenic acid ethyl ester obtained in the step three, ethanol and urea according to the mass ratio of 1: 1.6: 1.6 mixing and adding into a complex reaction kettle, feeding ethanol-urea-fatty acid ethyl ester containing alpha-ethyl linolenate in sequence, heating to 85 ℃, refluxing for 30min, preserving heat for 30min-, then cooling by stages, firstly cooling to 70 ℃, preserving heat for 30min, then cooling to 60 ℃, preserving heat for 15min, then cooling to 50 ℃, preserving heat for 30min, and finally performing filter pressing by nitrogen;
step six: recovering high-concentration ethanol: adjusting a steam jacket of the filtrate in a complex reaction kettle, heating to 55 ℃, cooling ethanol steam by using a refrigerant at the temperature of-10 ℃ under the vacuum condition of 8KPa, distilling and recovering ethanol to obtain ethanol with the content of more than 95 percent, and stopping heating and distilling when the distillation rate is less than 0.1 liter/minute;
step seven: leaching: leaching the materials in the six-complexing reaction kettle by using hot water at 50 ℃, standing and layering to obtain 260 kilograms of alpha-ethyl linolenate with the purity of 82.75% of oily liquid at the upper layer, and sending the obtained aqueous liquid at the lower layer to a primary complexing waste liquid tank;
step eight: dissolving the filter cake obtained by filter pressing in the step five by using a small amount of hot water at 80 ℃, and sending the filter cake to a primary complexing waste liquid tank after complete dissolution;
step nine: and (3) complex waste liquid treatment: feeding the cleaning waste liquid in the seventh step and the waste liquid in the eighth step into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the pH value ranging from about 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 2 hours for layering, and feeding the upper-layer oily clear liquid to an oily clear liquid treatment process; sending the bottom liquid of the lower layer to an ethanol recovery device, if the pH value of the bottom liquid of the kettle is more than 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, sending the solution to an ethanol distillation device, distilling and recovering ethanol, and sending the recovered ethanol to a raw material ethanol storage tank; cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank;
step ten: and (3) treating the upper layer oily clear liquid: adding hot water into oily clear liquid generated in the complexing waste liquid treatment process for washing, continuously washing for 3 times, adding vitamin C into the oily clear liquid according to the proportion of 0.25% during the last washing, stirring for 1 hour, standing for layering, discharging lower clear water, conveying an upper oil layer which is fatty acid ethyl ester to an ethyl ester intermediate storage tank, and using the oil layer as a raw material in the gradient complexing process;
step eleven: gradient complexation procedure: the first complexing purification reaction kettle receives 260 kg of fatty acid ethyl ester treated in the step ten, the fatty acid ethyl ester, the ethanol and the urea are fully mixed with ethanol and urea which are added in advance, the mass ratio of the fatty acid ethyl ester to the ethanol to the urea is 1:3:2, the temperature is increased to 85 ℃, the reflux is carried out for 30min, the temperature is kept for 30min, the temperature is reduced to 50 ℃, the heat is kept for 30min, then filter pressing is carried out, the filtrate enters the second complexing purification reaction kettle, 520kg of urea is added again, the temperature is increased to 85 ℃, the reflux is carried out for 30min, the heat is kept for 30min, the temperature is reduced to 50 ℃, the heat is kept for 30min, and;
step twelve: collecting waste liquid in the gradient complexing process, namely vacuum distilling the filtrate according to the sixth method to recover high-concentration ethanol, leaching the materials in the second complexing purification reaction kettle according to the seventh method, standing and layering to obtain 85 kg of alpha-ethyl linolenate with the purity of 82.27% as upper-layer oily liquid, and sending the lower-layer aqueous liquid which is cleaning waste liquid to a secondary complexing waste liquid tank; meanwhile, dissolving the filter cake obtained by filter pressing in the eleventh step by using a small amount of hot water at 80 ℃, and sending the filter cake to a secondary complexing waste liquid tank after complete dissolution;
step thirteen: treating gradient complexing waste liquid: sending the waste liquid in the secondary complexing waste liquid tank into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the PH value ranging from 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 2 hours for layering, and taking the oil layer on the upper part as a fatty acid ethyl ester byproduct for sale after vacuum-pumping and drying. And (3) conveying the bottom layer kettle liquid to an ethanol recovery device, if the pH value of the bottom layer kettle liquid is greater than 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, conveying the solution to the ethanol recovery device, distilling and recovering ethanol, and conveying the recovered ethanol to a raw material ethanol storage tank. And (4) cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank. In this example, 345 kg of ethyl linolenate with a content of 82.63% was obtained.
After the embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended that all simple modifications, equivalent changes and modifications made to the above embodiments based on the technical spirit of the present invention shall fall within the technical scope of the present invention, and the present invention shall not be limited to the embodiments illustrated in the description.
Claims (3)
1. The low-cost environment-friendly production process of the ethyl linolenate comprises the following raw materials of perilla oil and ethanol, and is characterized in that: the low-cost environment-friendly production process of the ethyl linolenate comprises the following steps:
the method comprises the following steps: saponification: perilla oil, deionized water and an enzyme catalyst, namely lipolase100L are mixed according to the weight ratio of 1: 0.5-4: adding the mixture into a reaction kettle according to the proportion of 0.01-0.1, heating and stirring, keeping the temperature at 40-70 ℃, and reacting for 2-20 hours under the condition that the pH value of materials in the kettle is controlled at 6.5-7.5;
step two: acidifying: slowly adding 10-90% sulfuric acid into the material obtained after saponification in the first step, stirring, controlling the reaction temperature to be between 40 ℃ and 95 ℃, continuously adding the sulfuric acid to control the pH value of the material to be below 4, keeping the pH value of the material to be below 4 after the stirring of the sulfuric acid is stopped, and finishing the reaction after the pH value of the material is kept below 4 for more than 2 hours; standing the reacted materials for 1-6 hours for layering, discharging the hydrolyzed acidic wastewater at the lower layer into an acidic wastewater storage tank for later use, and feeding the oil layer at the upper layer into an esterification process;
step three: esterification: and (2) enabling the upper oil layer obtained in the step (II) to be fatty acid containing alpha-linolenic acid, and mixing the fatty acid with absolute ethyl alcohol and a concentrated sulfuric acid catalyst with the mass concentration of 90-98% according to the weight ratio of 1.25 kg: 1-2 kg: adding 40-50ml of the mixture into an esterification reaction kettle, heating to 75-100 ℃, reacting for 4-10 hours, standing for 1-6 hours, layering materials in the reaction kettle, cooling to discharge lower-layer esterification wastewater to an esterification wastewater storage tank, and feeding an upper-layer oil layer into the step five complexing purification process;
step four: treating esterification waste liquid: sending the esterification waste liquid in the esterification waste water storage tank into an ethanol recovery device, distilling and recovering ethanol, sending the recovered ethanol to a raw material ethanol storage tank, and sending the acidic esterification waste liquid treated by the ethanol recovery device to an acidic waste water storage tank;
step five: complexing and purifying: and C, mixing the fatty acid ethyl ester containing the alpha-ethyl linolenate obtained in the step three with ethanol and urea according to the mass ratio of 1: 1-5: 1-5, adding into a complex reaction kettle, feeding ethanol-urea-fatty acid ethyl ester containing alpha-ethyl linolenate in sequence, heating to 80-100 ℃, refluxing for 30-60 min, keeping the temperature for 30-60 min, then cooling by stages, firstly cooling to 70 +/-5 ℃, keeping the temperature for 15-40 min, then cooling to 60 +/-5 ℃, keeping the temperature for 15-40 min, then cooling to 50 +/-5 ℃, keeping the temperature for 15-40 min, and finally performing pressure filtration by nitrogen;
step six: recovering high-concentration ethanol: adjusting a steam jacket of the filtrate obtained in the step 5 in a complex reaction kettle, heating to 45-60 ℃, cooling ethanol steam by using a refrigerant at the temperature of-10 ℃ under the vacuum condition of 5-10KPa, distilling and recovering ethanol to obtain ethanol with the content of more than 95%, and stopping heating and distilling when the distilling speed is less than 0.1 liter/minute;
step seven: leaching: leaching the materials obtained after ethanol is recovered in the six-stage complexing reaction kettle by using hot water at the temperature of 45-60 ℃, standing and layering to obtain alpha-ethyl linolenate with the purity of more than 82% as an upper-layer oily liquid, and sending the washing waste liquid to a primary complexing waste liquid tank;
step eight: dissolving the filter cake obtained by filter pressing in the step five by using a small amount of hot water at 80 ℃, and sending the filter cake to a primary complexing waste liquid tank as waste liquid after complete dissolution;
step nine: and (3) complex waste liquid treatment: feeding the cleaning waste liquid in the seventh step and the waste liquid in the eighth step into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the pH value ranging from 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 1-6 hours for layering, and feeding the upper-layer oily clear liquid to a tenth-layer oily clear liquid treatment process; sending the bottom liquid of the lower layer to an ethanol recovery device, if the pH value of the bottom liquid of the kettle is more than 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, sending the solution to an ethanol distillation device, distilling and recovering ethanol, and sending the recovered ethanol to a raw material ethanol storage tank; cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank;
step ten: and (3) treating the upper layer oily clear liquid: adding hot water into the oily clear liquid generated in the step nine for washing, continuously washing for 2-5 times, adding vitamin C into the oily clear liquid according to the proportion of 0.1-0.5% during the last washing, stirring for 1 hour, standing for layering, discharging lower clear water, conveying the upper oil layer which is fatty acid ethyl ester to an ethyl ester intermediate storage tank, and using the upper oil layer as a raw material for a gradient complexing process;
step eleven: gradient complexation procedure: the first complexing purification reaction kettle receives the fatty acid ethyl ester treated in the step ten, the fatty acid ethyl ester is fully mixed with ethanol and urea which are added in advance, the mass ratio of the fatty acid ethyl ester to the ethanol to the urea is 1:1-4:1-4, the mixture is heated to 80-100 ℃ and refluxed for 30-60 min, the temperature is kept for 30-60 min, then the temperature is reduced to 50 +/-5 ℃ and then kept for 15-40 min, pressure filtration is carried out by using nitrogen, the filtrate enters a second complexing purification reaction kettle, the same amount of urea is added again, the mixture is heated to 80-100 ℃ and refluxed for 30-60 min, the temperature is kept for 30-60 min, then the temperature is reduced to 50 +/-5 ℃ and then kept for 15-40 min, and finally, nitrogen pressure filtration is carried out again;
step twelve: collecting waste liquid in the gradient complexing procedure: vacuum distilling the filtrate obtained in the eleventh step according to a sixth method to recover high-concentration ethanol, leaching the materials in the second complexing purification reaction kettle according to a seventh method, standing and layering to obtain alpha-ethyl linolenate with the purity of more than 82% as an oily liquid at the upper layer, and sending the obtained aqueous liquid at the lower layer as a cleaning waste liquid to a secondary complexing waste liquid tank; meanwhile, dissolving the filter cake obtained by filter pressing in the eleventh step by using a small amount of hot water at 80 ℃, and sending the filter cake to a secondary complexing waste liquid tank after complete dissolution;
step thirteen: treating gradient complexing waste liquid: sending the waste liquid in the secondary complexing waste liquid tank into a complexing waste liquid reaction kettle, then adding the acidic waste water (with the pH value ranging from 2 to 4) in an acidic waste water storage tank into the complexing waste liquid reaction kettle, heating and stirring for demulsification, standing the demulsified complexing waste liquid for 1-6 hours for layering, and vacuumizing and drying an oil layer at the upper part to sell the oil layer as a fatty acid ethyl ester byproduct; feeding the bottom liquid of the lower layer to an ethanol recovery device, if the pH value of the bottom liquid of the kettle is greater than or equal to 4, pumping a proper amount of acidic wastewater from an acidic wastewater storage tank, adjusting the pH value of the solution to be less than 4, feeding the solution to the ethanol recovery device, distilling and recovering ethanol, and feeding the recovered ethanol to a raw material ethanol storage tank; and (4) cooling the acid waste liquid at the bottom of the kettle to separate out ammonia nitrogen salt crystals, and then discharging the crystals into an acid waste water storage tank.
2. The low-cost environment-friendly production process of ethyl linolenate according to claim 1, characterized in that: the ethanol recovery device comprises an acid preparation distillation still, a condenser and an ethanol storage tank, wherein complexing waste liquid in the ninth step and the thirteenth step is subjected to standing, lower-layer kettle bottom liquid is injected into the acid preparation distillation still, meanwhile, acidic waste water in the acidic waste water storage tank is sprayed into the acid preparation distillation still through a spray head, stirring is started, after the pH value of a material in the acid preparation distillation still is below 4, the acidic waste water is stopped to be added, then, steam is introduced into a steam jacket of the acid preparation distillation still for distillation, the distilled steam is condensed through the condenser and then enters the ethanol storage tank to be recycled as a raw material, after the distillation is finished, kettle bottom residual liquid is discharged from a discharge port of the distillation still, and the ammonia nitrogen fertilizer can be obtained through cooling, concentration and crystallization.
3. The low-cost environment-friendly production process of ethyl linolenate according to claim 2, characterized in that: the ethanol recovery device is provided with a first ethanol storage tank, a second ethanol storage tank and a third ethanol storage tank, the first ethanol storage tank, the second ethanol storage tank and the third ethanol storage tank are respectively connected with a condensate outlet of the condenser through a first condensing valve, a second condensing valve and a third condensing valve, and the discharging openings of the ethanol storage tanks of the first ethanol storage tank, the second ethanol storage tank and the third ethanol storage tank are respectively connected with the reflux pump through a first reflux valve, a second reflux valve and a third reflux valve.
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