CN105985864B - Device and method for continuously adsorbing and deacidifying biodiesel - Google Patents
Device and method for continuously adsorbing and deacidifying biodiesel Download PDFInfo
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- CN105985864B CN105985864B CN201510069371.XA CN201510069371A CN105985864B CN 105985864 B CN105985864 B CN 105985864B CN 201510069371 A CN201510069371 A CN 201510069371A CN 105985864 B CN105985864 B CN 105985864B
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Abstract
The invention relates to a device and a method for continuously adsorbing and deacidifying biodiesel. The method comprises two working modes, wherein the mode A is that the adsorption separation tower (1) adsorbs deacidification, and the adsorption separation tower (2) desorbs and dealcoholizes and regenerates; and the mode B is that the adsorption separation tower (2) adsorbs deacidification, the adsorption separation tower (1) desorbs and dealcoholizes and regenerates, and when the acid value of the biodiesel flowing out of the adsorption separation tower is unqualified, the adsorption deacidification device is switched between the mode A and the mode B, so that the continuous operation of the adsorption deacidification device is realized. The invention particularly adopts a method for dealcoholizing the biodiesel with low acid value, realizes the continuous adsorption deacidification, desorption and dealcoholization of the biodiesel, obtains the biodiesel product with the acid value less than 0.50mgKOH/g, can meet the requirements of the existing BD100 and the national standard of the new generation, has low gas consumption, energy consumption and cost, and does not influence other properties of the biodiesel.
Description
Technical Field
The invention relates to a device and a method for continuous adsorption deacidification of biodiesel.
Background
The biodiesel has the characteristics of no toxicity, no sulfur, full combustion, biodegradability, excellent lubricating property and the like, and has great significance for reducing air pollution and greenhouse gas emission. With the increasing consumption and decreasing reserves of fossil energy, the worsening of the environment and the aggravation of the greenhouse effect, renewable clean energy biodiesel is receiving wide attention.
In recent years, the research on the preparation of biodiesel by using waste oils and fats such as waste cooking oil and acidified oil as raw materials has become a hotspot, the acid value of the oils and fats is greatly different, the acid value of some acidified oils and fats can even reach 170mgKOH/g, and when the biodiesel is prepared by using the oils and fats with high acid value, the acid value of the product is generally larger than or even far larger than the BD100 acid value standard (less than or equal to 0.80mg KOH/g). In order to further improve the product quality of the biodiesel, the international standard is adopted, and China intends to modify the standard of the biodiesel BD100 into the standard of which the acid value is less than or equal to 0.50mgKOH/g, so that the deacidification difficulty of the esterification reaction of the biodiesel is further increased. Therefore, it is necessary to develop a deacidification method for reducing the acid value of the biodiesel to be below 0.80mgKOH/g, even below 0.50 mgKOH/g.
The alkaline washing is a classical deacidification process, many researches at home and abroad use alkaline solutions such as sodium hydroxide and the like to perform neutralization reaction with free fatty acid, the obtained fatty acid sodium salt is separated from oil products, the free fatty acid is obtained through acidification, the reaction process can be completed instantly, but an emulsification phenomenon is easy to generate in the reaction process. Moreover, the alkali liquor is greatly lost along with the processed products, and the sodium hydroxide solution cannot be regenerated.
The conversion of free fatty acids to biodiesel by esterification is a better process, but the more difficult the deacidification of the esterification reaction is when the acid value is closer to 0.80mgKOH/g, leading to higher energy consumption of the process.
CN101993776A provides a method for deacidifying biodiesel, which comprises the following steps: mixing the biodiesel to be deacidified with a deacidification agent containing water-soluble alcohol, water-soluble amine and water, separating an oil phase and a water phase after layering, and refining the oil phase to obtain the biodiesel with qualified acid value.
CN101735845A relates to a method for separating and purifying biodiesel. The method comprises the following steps: 1) degassing and distilling the crude product of the biodiesel by using a film evaporator to obtain the biodiesel with the methyl ester content of more than 96 percent; 2) alkaline soil deacidification is carried out on the product separated in the step 1) to obtain the purified biodiesel with the acid value meeting the national standard. The disadvantages of this method are: 1. free fatty acid is lost and cannot be processed into biodiesel. 2. Alkaline soils cannot be regenerated.
CN101550364A relates to a method for preparing biodiesel by comprehensively utilizing high-acid-value oil, which is to perform multistage (n is more than or equal to 1) extraction operation on the high-acid-value oil by methanol to obtain a methanol phase and a low-acid-value glyceride phase in the operation process. Wherein most of free fatty acid in the grease is dissolved in a methanol phase, and the biodiesel is prepared by acid catalysis after enrichment; and preparing the biodiesel by alkali catalysis of the low acid value glyceride phase. The disadvantages of this method are: 1. the operating cost is high. 2. Can not be used for product refining.
US249366 uses excess alkali to neutralize free fatty acid to reduce the acid value of high acid value grease, and performs methyl esterification reaction, the soap formed by alkali and free fatty acid is added with sulfuric acid after methyl esterification to perform reaction to obtain free fatty acid, the free fatty acid is esterified under the action of acid catalysis, and the obtained material is neutralized, filtered and rectified to obtain methyl ester. The disadvantages of this method are: 1. and excessive alkali and sulfuric acid are adopted, so that the production cost is high. 2. Low value by-product sulfate is produced.
Disclosure of Invention
The invention aims to provide a device and a method for continuously adsorbing and deacidifying biodiesel, aiming at the problems that the biodiesel with a lower acid value is difficult to further deacidify and the gas consumption and the energy consumption are high in the nitrogen purging or vacuumizing dealcoholization process.
The invention provides a biodiesel continuous adsorption deacidification device, which comprises: an adsorption separation tower 1 and an adsorption separation tower 2, a biodiesel storage tank 3 with qualified acid value, an alcohol distillation tower 4, an alcohol storage tank 5, a biodiesel storage tank 6 containing free fatty acid, a low acid value biodiesel storage tank 7, a pipeline 8 and a pipeline 9 for conveying biodiesel crude products with unqualified acid value to the adsorption separation tower 1, a pipeline 8 and a pipeline 10 for conveying biodiesel crude products with unqualified acid value to the adsorption separation tower 2, a pipeline 11 and a pipeline 13 for conveying biodiesel with qualified acid value from the adsorption separation tower 1 to the biodiesel storage tank 3, a pipeline 12 and a pipeline 13 for conveying biodiesel with qualified acid value from the adsorption separation tower 2 to the biodiesel storage tank 3, a pipeline 16 and a pipeline 17 for conveying biodiesel with unqualified acid value from the adsorption separation tower 1 to the alcohol distillation tower 4, a pipeline 19 and a pipeline 17 for conveying biodiesel with unqualified acid value from the adsorption separation tower 2 to the alcohol distillation tower 4, line 14 and line 15 for introducing nitrogen into the adsorption separation column 1, line 14, line 28 and line 18 for introducing nitrogen into the adsorption separation column 2, line 20 for transporting distilled alcohol from the alcohol distillation column 4 to the alcohol storage tank 5, line 21 for transporting alcohol-removed biodiesel containing more free fatty acids to the biodiesel storage tank 6, line 22 for transporting alcohol-removed low acid value biodiesel to the low acid value biodiesel storage tank 7, line 23, line 24, line 25 and line 15 for transporting alcohol from the alcohol storage tank 5 to the adsorption separation column 1, line 23, line 24, line 26 and line 18 for transporting alcohol from the alcohol storage tank 5 to the adsorption separation column 2, line 27, line 24, line 25 and line 15 for transporting biodiesel from the low acid value biodiesel storage tank 7 to the adsorption separation column 1, line 27, line 25 and line 15 for transporting biodiesel from the low acid value biodiesel storage tank 7 to the adsorption separation column 2, Line 24, line 26 and line 18, line 29 for transporting acid value-qualified biodiesel from storage tank 3 to low acid value biodiesel storage tank 7. Each pipeline is provided with a delivery pump, a valve and a sampling port, the delivery of materials and the monitoring of technical indexes can be controlled, and the delivery pump, the valve and the like are automatically controlled by a central control room.
The continuous adsorption deacidification method provided by the invention comprises two working modes, wherein the mode A is that an adsorption separation tower 1 adsorbs deacidification, and an adsorption separation tower 2 desorbs and dealcoholizes and regenerates; and the mode B is that the adsorption separation tower 2 adsorbs deacidification, the adsorption separation tower 1 desorbs and dealcoholizes and regenerates, and when the acid value of the biodiesel coming out from the adsorption separation tower 1 or the adsorption separation tower 2 is unqualified, the adsorption deacidification device is switched between the mode A and the mode B, so that the continuous operation of the adsorption deacidification device is realized.
The case of mode a operation is as follows:
the adsorption deacidification method of the adsorption separation tower 1 comprises the following steps: the biodiesel with unqualified acid value is conveyed to an adsorption separation tower 1 through a pipeline 8 and a pipeline 9 for adsorption deacidification, and the biodiesel with qualified acid value enters a biodiesel storage tank 3 through a pipeline 11 and a pipeline 13.
The desorption method of the adsorption separation tower 2 comprises the following steps: the alcohol desorbent delivered from the alcohol storage tank 5 enters the adsorption separation tower 2 through a pipeline 23, a pipeline 24, a pipeline 26 and a pipeline 18, the free fatty acid adsorbed by the adsorption separation tower 2 is eluted, the eluent enters the alcohol distillation tower 4 through a pipeline 19 and a pipeline 17, the alcohol desorbent is evaporated from the top of the alcohol distillation tower 4 and enters the alcohol storage tank 5, and the biodiesel containing the free fatty acid and the alcohol is removed enters the biodiesel containing the free fatty acid storage tank 6.
The dealcoholization regeneration method of the adsorption separation tower 2 comprises the following steps: the alcohol in the adsorption separation column 2 is topped with an inert gas from the line 19 and the line 17 to the alcohol distillation column 4 or directly to the alcohol storage tank 5 through the line 14, the line 28 and the line 18, and the low acid value biodiesel is transferred from the low acid value biodiesel storage tank 7 to the adsorption separation column 2 from the line 27, the line 24, the line 26 and the line 18. The biodiesel containing alcohol and with low acid value enters a distillation tower 4 through a pipeline 19 and a pipeline 17, the alcohol is distilled out from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the biodiesel with low acid value, from which the alcohol is removed, enters a biodiesel storage tank 7 with low acid value through a pipeline 22. When the mass percentage of the alcohol in the biodiesel from the adsorption separation tower 2 is qualified, the dealcoholization regeneration of the adsorption separation tower 2 is completed for later use.
The low acid value biodiesel in the low acid value biodiesel storage tank 7 is sourced from the biodiesel storage tank 3 with qualified acid value, and the low acid value biodiesel is conveyed to the low acid value biodiesel storage tank 7 through a pipeline 29.
The case of mode B operation is as follows:
the adsorption deacidification method of the adsorption separation tower 2 comprises the following steps: the biodiesel with unqualified acid value is conveyed to an adsorption separation tower 2 for adsorption deacidification through a pipeline 8 and a pipeline 10, and the biodiesel with qualified acid value enters a biodiesel storage tank 3 through a pipeline 12 and a pipeline 13.
The desorption method of the adsorption separation tower 1 comprises the following steps: the alcohol desorbent delivered from the alcohol storage tank 5 enters the adsorption separation tower 1 through a pipeline 23, a pipeline 24, a pipeline 25 and a pipeline 15, the free fatty acid adsorbed by the adsorption separation tower 1 is eluted, the eluent enters the alcohol distillation tower 4 through a pipeline 16 and a pipeline 17, the alcohol desorbent is evaporated from the top of the alcohol distillation tower 4 and enters the alcohol storage tank 5 through a pipeline 20, and the biodiesel containing the free fatty acid from which the alcohol is removed enters a biodiesel containing the free fatty acid storage tank 6.
The dealcoholization regeneration method of the adsorption separation tower 1 comprises the following steps: the eluate in the adsorption separation column 1 is pushed up from the line 16 and the line 17 to the alcohol distillation column 4 or directly to the alcohol storage tank 5 by an inert gas through the line 14 and the line 15, and the low acid value biodiesel is sent from the low acid value biodiesel storage tank 7 to the adsorption separation column 1 from the line 27, the line 24, the line 25 and the line 15. The biodiesel containing alcohol with low acid value enters a distillation tower 4 through a pipeline 16 and a pipeline 17, the alcohol is distilled out from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the biodiesel with low acid value and without alcohol enters a biodiesel storage tank 7 with low acid value. When the mass percentage of the alcohol in the biodiesel from the adsorption separation tower 1 is qualified, the dealcoholization regeneration of the adsorption separation tower 1 is completed for standby.
The adsorption separation tower of the invention is a fixed bed filled with adsorption resin. Wherein the adsorption resin is loaded with basic groups, the basic groups can be strong basic groups or weak basic groups, and one or more of hydroxyl, primary amine, secondary amine, tertiary amine, quaternary ammonium groups and the like are preferred.
The acid value of the biodiesel with unqualified acid value is 0.5-5.0 mgKOH/g, and preferably 0.5-2.0 mgKOH/g.
According to the invention, when the adsorption separation tower is used for performing fixed bed adsorption deacidification operation, the temperature is between room temperature and 100 ℃, and preferably between room temperature and 60 ℃. The liquid hourly space velocity of the biodiesel in the fixed bed adsorption separation tower is 0.2-10 h-1Preferably 0.6 to 5.0 hours-1. The operating pressure is 0.1 to 1.0MPa, preferably 0.1 to 0.30 MPa.
The alcohol desorbent used in the method of the invention is C1-C4 aliphatic alcohol, such as methanol, ethanol, propanol, normal or isomeric butanol, and the like, preferably methanol and/or ethanol.
When the acid value of the biodiesel discharged from the adsorption separation column is more than 0.80mgKOH/g, preferably more than 0.50mgKOH/g, it means that the adsorption of the free fatty acid is substantially saturated and the adsorption can be stopped. Switching between mode a and mode B is performed.
When the acid value of the alcohol eluent flowing out of the adsorption separation column is less than 0.10mgKOH/g, preferably 0.050mgKOH/g, it means that the desorption of the free fatty acid is substantially complete, and the desorption can be stopped.
When methanol is used as a desorption agent, the desorption solution is biodiesel containing methanol and with unqualified acid value, the methanol can be separated without distillation and directly returned to the biodiesel preparation process, and the methanol directly participates in the alcoholysis reaction for preparing the biodiesel, so that the energy consumption is reduced.
The inert gas in the method can be nitrogen, air, helium, neon or argon, preferably nitrogen, and the purging temperature is between room temperature and 130 ℃, preferably between room temperature and 70 ℃.
When methanol is used as the desorption agent, the operation temperature of the alcohol distillation tower is between room temperature and 100 ℃, and when ethanol is used as the desorption agent, the operation temperature of the distillation tower can be properly increased.
The method provided by the invention has the following advantages: (1) the dealcoholization is simply and efficiently realized, the gas consumption, the energy consumption and the cost are low, and the adsorbent bed is not easy to damage. (2) Can realize continuous adsorption deacidification of the biodiesel, obtain the biodiesel product with the acid value less than 0.50mgKOH/g, and can meet the requirements of the existing BD100 and the national standard of the new generation. (3) Realizes the continuous operation of the adsorption deacidification process, and the service life of the adsorption resin is long. (4) Does not affect other properties of the biodiesel.
Drawings
FIG. 1 is a schematic flow diagram and an apparatus diagram of the method of the present invention.
Detailed Description
The technical solutions provided by the present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
In the examples, the adsorption resin KIP211 is a strongly basic adsorption resin of quaternary ammonium salt type (functional group is-NR 3OH, R is a hydrocarbon group) and is produced by Hebei Kary chemical Co., Ltd. The adsorption resin can also be selected from other alkaline ion exchange resins produced by Hebei Kary chemical industry, such as KIP200, KIP201, KIP202, KIP203, KIP204, KIP205, KIP206, KIP207, KIP208, KIP209, KIP210 and the like of KIP series, or can be selected from alkaline ion exchange resins produced by southern development university, such as D301R, D301G, D370, D371, D392, D380, D382 and the like, or can be selected from alkaline ion exchange resins imported abroad and alkaline ion exchange resins of other manufacturers at home and abroad.
Example 1
This example illustrates that the present invention can be implemented using a quaternary ammonium salt-based strongly basic adsorption resin KIP211 (manufactured by Hebei Kairyy chemical Co., Ltd.).
Filling a fixed bed adsorption separation tower: 30g of basic adsorption resin KIP211 was packed in each of the fixed-bed adsorption-separation column 1 and the fixed-bed adsorption-separation column 2.
Adsorption deacidification using mode a: feeding the biodiesel with the acid value of 1.65mgKOH/g by using a micro pump, and entering a fixed bed adsorption separation tower 1 for adsorption deacidification through a pipeline 8 and a pipeline 9 at the temperature of 40 ℃, the pressure of 0.2-0.3 MPa and the flow of 40.0g/h, wherein the biodiesel with the qualified acid value enters a biodiesel storage tank 3 through a pipeline 11 and a pipeline 13. When the operation is carried out for 16 hours, the acid value of the product is 0.10mgKOH/g, the biodiesel product with qualified acid value is obtained, and 16 quality indexes of the obtained biodiesel product are all qualified. When the operation is carried out for 26 hours, the acid value of the product is 0.82mgKOH/g, the feeding to the adsorption separation tower 1 is stopped, and the mode B is switched to be adopted for adsorption deacidification.
Desorption using mode a: methanol enters the adsorption separation tower 2 from the methanol storage tank 5 through a pipeline 23, a pipeline 24, a pipeline 26 and a pipeline 18 for desorption and regeneration, the temperature is 50 ℃, the pressure is 0.2-0.3 MPa, the flow is 40.0g/h, and eluent enters the methanol distillation tower 4 through a pipeline 19 and a pipeline 17. When the operation time is 1.0h, the acid value of the methanol solution is 18.2mgKOH/g, and when the operation time is 5.0h, the acid value of the methanol solution is 0.05mgKOH/g, so that the desorption of the free fatty acid is completed.
Dealcoholization regeneration using mode a: nitrogen gas is introduced into the adsorption separation column 2 through the line 14, the line 28 and the line 18, methanol in the adsorption separation column 2 is ejected, and methanol is introduced into the methanol distillation column 4 through the line 19 and the line 17. The adsorption separation column 10 which completes desorption regeneration is ready for use. Then, from the low acid value biodiesel storage tank 7, biodiesel having an acid value of 0.10mgKOH/g was fed from the line 27, the line 24, the line 26 and the line 18 to the adsorption separation column 2. The alcohol-containing biodiesel with low acid value enters a distillation tower 4 through a pipeline 19 and a pipeline 17, the alcohol is distilled out from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the alcohol-removed biodiesel with low acid value enters a biodiesel with low acid value 7. When the mass percentage of the alcohol in the biodiesel from the adsorption separation tower 2 is below 50ppm, the dealcoholization regeneration of the adsorption separation tower 2 is completed for standby.
Adsorption deacidification using mode B: feeding the biodiesel with the acid value of 1.65mgKOH/g by using a micro pump, and feeding the biodiesel into an adsorption separation tower 2 through a pipeline 8 and a pipeline 10 at the temperature of 40 ℃, the pressure of 0.2-0.3 MPa and the flow of 40.0g/h, wherein the biodiesel with the qualified acid value enters a biodiesel storage tank 3 through a pipeline 12 and a pipeline 13. When the operation is carried out for 20 hours, the acid value of the product is 0.15mgKOH/g, and the biodiesel product with qualified acid value is obtained. When the operation time was 28 hours, the acid value of the product was 0.85mgKOH/g, and the feed to the adsorption separation column 2 was stopped. At this time, the adsorption separation column 1 is kept ready and switched to the mode a for adsorption deacidification.
Desorption with mode B: and (3) desorbing and regenerating the adsorption separation tower 1 by methanol from a methanol storage tank 5 through a pipeline 23, a pipeline 24, a pipeline 25 and a pipeline 15 at the temperature of 50 ℃, the pressure of 0.2-0.3 MPa and the flow rate of 40.0g/h, and enabling eluent to enter a methanol distillation tower 4 through a pipeline 16 and a pipeline 17. When the operation is carried out for 5.0h, the acid value of the methanol solution is 0.05mgKOH/g, and the desorption of the free fatty acid is completed.
Dealcoholization regeneration with mode B: methanol in the adsorption separation column 1 was topped with nitrogen from the line 16 and the line 17 to the methanol distillation column 4 through the line 14 and the line 15, and biodiesel having an acid value of 0.10mgKOH/g was transferred from the low acid value biodiesel storage tank 7 to the adsorption separation column 1 from the line 27, the line 24, the line 25 and the line 15. The alcohol-containing biodiesel with low acid value enters a distillation tower 4 through a pipeline 16 and a pipeline 17, methanol is evaporated from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the alcohol-removed biodiesel with low acid value enters a biodiesel with low acid value 7. When the mass percentage of the alcohol coming out of the adsorption separation tower 1 is less than 50ppm, the dealcoholization regeneration of the adsorption separation tower 1 is completed for standby.
The eluent entering the methanol distillation tower is distilled at the temperature of 80 ℃, and the methanol comes out from the top of the tower and enters a methanol storage tank 13. The free fatty acid without methanol is discharged from the bottom of the tower, enters a fatty acid storage tank, then returns to the biodiesel preparation procedure, and enters an ester exchange reactor to be processed into biodiesel.
Example 2
Examples illustrate that the invention can be carried out at different temperatures.
Filling a fixed bed adsorption separation tower: 30g of a strongly basic adsorption resin KIP211 (produced by Hebei Kairyy chemical Co., Ltd.) was packed in the fixed bed adsorption-separation column 1 and the fixed bed adsorption-separation column 2.
Adsorption deacidification using mode a: feeding the biodiesel with the acid value of 1.65mgKOH/g by using a micro pump, and entering a fixed bed adsorption separation tower 1 for adsorption deacidification through a pipeline 8 and a pipeline 9 at the temperature of 70 ℃, the pressure of 0.2-0.3 MPa and the flow of 40.0g/h, wherein the biodiesel with the qualified acid value enters a biodiesel storage tank 3 through a pipeline 11 and a pipeline 13. When the operation is carried out for 16 hours, the acid value of the product is 0.10mgKOH/g, the biodiesel product with qualified acid value is obtained, and 16 quality indexes of the obtained biodiesel product are all qualified. When the operation is carried out for 26 hours, the acid value of the product is 0.83mgKOH/g, the feeding to the adsorption separation tower 1 is stopped, and the mode B is switched to be adopted for adsorption deacidification.
Desorption using mode a: methanol enters the adsorption separation tower 2 from the methanol storage tank 5 through a pipeline 23, a pipeline 24, a pipeline 26 and a pipeline 18 for desorption and regeneration, the temperature is 30 ℃, the pressure is 0.2-0.3 MPa, the flow is 40.0g/h, and eluent enters the methanol distillation tower 4 through a pipeline 19 and a pipeline 17. When the operation time is 1.5h, the acid value of the methanol solution is 17.3mgKOH/g, and when the operation time is 5.0h, the acid value of the methanol solution is 0.020mgKOH/g, so that the desorption of the free fatty acid is completed.
Dealcoholization regeneration using mode a: nitrogen gas is introduced into the adsorption separation column 2 through the line 14, the line 28 and the line 18, methanol in the adsorption separation column 2 is ejected, and methanol is introduced into the methanol distillation column 4 through the line 19 and the line 17. The adsorption separation column 10 which completes desorption regeneration is ready for use. Then, from the low acid value biodiesel storage tank 7, biodiesel having an acid value of 0.10mgKOH/g was fed from the line 27, the line 24, the line 26 and the line 18 to the adsorption separation column 2. The alcohol-containing biodiesel with low acid value enters a distillation tower 4 through a pipeline 19 and a pipeline 17, the alcohol is distilled out from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the alcohol-removed biodiesel with low acid value enters a biodiesel with low acid value 7. When the mass percentage of the alcohol in the biodiesel from the adsorption separation tower 2 is below 50ppm, the dealcoholization regeneration of the adsorption separation tower 2 is completed for standby.
Adsorption deacidification is carried out by adopting a mode B: feeding the biodiesel with the acid value of 1.65mgKOH/g by using a micro pump, and feeding the biodiesel into an adsorption separation tower 2 through a pipeline 8 and a pipeline 10 at the temperature of 65 ℃, the pressure of 0.2-0.3 MPa and the flow of 40.0g/h, wherein the biodiesel with the qualified acid value enters a biodiesel storage tank 3 through a pipeline 12 and a pipeline 13. When the operation is carried out for 20 hours, the acid value of the product is 0.12mgKOH/g, and the biodiesel product with qualified acid value is obtained. When the operation was carried out for 30 hours, the acid value of the product was 0.83mgKOH/g, and the feed to the adsorption separation column 2 was stopped. At this time, the adsorption separation column 1 is kept ready and switched to the mode a for adsorption deacidification.
Desorption with mode B: and (3) desorbing and regenerating the adsorption separation tower 1 by methanol from a methanol storage tank 5 through a pipeline 23, a pipeline 24, a pipeline 25 and a pipeline 15 at the temperature of 35 ℃, the pressure of 0.2-0.3 MPa and the flow rate of 40.0g/h, and enabling eluent to enter a methanol distillation tower 4 through a pipeline 16 and a pipeline 17. When the operation is carried out for 5.0h, the acid value of the methanol solution is 0.05mgKOH/g, and the desorption of the free fatty acid is completed.
Dealcoholization regeneration with mode B: methanol in the adsorption separation column 1 was topped with nitrogen from the line 16 and the line 17 to the methanol distillation column 4 through the line 14 and the line 15, and biodiesel having an acid value of 0.10mgKOH/g was transferred from the low acid value biodiesel storage tank 7 to the adsorption separation column 1 from the line 27, the line 24, the line 25 and the line 15. The alcohol-containing biodiesel with low acid value enters a distillation tower 4 through a pipeline 16 and a pipeline 17, methanol is evaporated from the top of the alcohol distillation tower 4 and enters an alcohol storage tank 5, and the alcohol-removed biodiesel with low acid value enters a biodiesel with low acid value 7. When the mass percentage of the alcohol coming out of the adsorption separation tower 1 is less than 50ppm, the dealcoholization regeneration of the adsorption separation tower 1 is completed for standby.
The eluent entering the methanol distillation tower is distilled at the temperature of 80 ℃, and the methanol comes out from the top of the tower and enters a methanol storage tank 13. The free fatty acid without methanol is discharged from the bottom of the tower, enters a fatty acid storage tank, then returns to the biodiesel preparation procedure, and enters an ester exchange reactor to be processed into biodiesel.
Claims (13)
1. Biodiesel adsorbs deacidification device in succession includes: an adsorption separation tower (1) and an adsorption separation tower (2), a biodiesel storage tank (3) with qualified acid value, an alcohol distillation tower (4), an alcohol storage tank (5), a biodiesel storage tank (6) containing free fatty acid, a low-acid-value biodiesel storage tank (7), a pipeline (8) and a pipeline (9) for conveying biodiesel crude products with unqualified acid value to the adsorption separation tower (1), a pipeline (8) and a pipeline (10) for conveying biodiesel crude products with unqualified acid value to the adsorption separation tower (2), a pipeline (11) and a pipeline (13) for conveying biodiesel with qualified acid value from the adsorption separation tower (1) to the biodiesel storage tank (3), a pipeline (12) and a pipeline (13) for conveying biodiesel with qualified acid value from the adsorption separation tower (2) to the biodiesel storage tank (3), a pipeline (16) and a pipeline (13) for conveying biodiesel with unqualified acid value from the adsorption separation tower (1) to the alcohol distillation tower (4) A line (17), a line (19) and a line (17) for transferring biodiesel having an unacceptable acid value from the adsorption separation column (2) to the alcohol distillation column (4), a line (14) and a line (15) for introducing nitrogen into the adsorption separation column (1), a line (14), a line (28) and a line (18) for introducing nitrogen into the adsorption separation column (2), a line (20) for transferring distilled alcohol from the alcohol distillation column (4) to the alcohol storage tank (5), a line (21) for transferring biodiesel from which alcohol is removed and which contains a large amount of free fatty acids to the biodiesel storage tank (6), a line (22) for transferring biodiesel having a low acid value from which alcohol is removed to the low acid value biodiesel storage tank (7), a line (23), a line (24), a line (25) and a line (15) for transferring alcohol from the alcohol storage tank (5) to the adsorption separation column (1), a line (23), a line (24), a line (26) and a line (18) for transferring alcohol from the alcohol storage tank (5) to the adsorption separation column (2), a line (27), a line (24), a line (25) and a line (15) for transferring biodiesel from the low acid value biodiesel storage tank (7) to the adsorption separation column (1), a line (27), a line (24), a line (26) and a line (18) for transferring biodiesel from the low acid value biodiesel storage tank (7) to the adsorption separation column (2), and a line (29) for transferring biodiesel having an acceptable acid value from the storage tank 3 to the low acid value biodiesel storage tank 7.
2. The apparatus according to claim 1, wherein the adsorption separation column is a fixed bed packed with an adsorption resin.
3. The device of claim 1, wherein the adsorbent resin is loaded with basic groups selected from one or more of hydroxyl, primary amine, secondary amine, tertiary amine, quaternary ammonium groups.
4. The method for continuously adsorbing and deacidifying the biodiesel comprises two working modes, wherein the mode A comprises an adsorption separation tower (1) for adsorption deacidification, an adsorption separation tower (2) for desorption and dealcoholization regeneration; the mode B is that the adsorption separation tower (2) adsorbs deacidification, the adsorption separation tower (1) desorbs and dealcoholizes and regenerates, when the biodiesel acid value flowing out of the adsorption separation tower is unqualified, the adsorption deacidification device is switched between the mode A and the mode B, so that the continuous operation of the adsorption deacidification device is realized;
the dealcoholization regeneration method of the adsorption separation tower (2) comprises the following steps: the alcohol in the adsorption separation column (2) is topped with an inert gas from the line (19) and the line (17) to the alcohol distillation column (4) or directly to the alcohol storage tank (5) through the line (14), the line (28) and the line (18), and the low acid value biodiesel is transferred from the low acid value biodiesel storage tank 7 to the adsorption separation column (2) from the line (27), the line (24), the line (26) and the line (18); the biodiesel containing alcohol with low acid value enters a distillation tower (4) through a pipeline (19) and a pipeline (17), the alcohol is evaporated from the top of the alcohol distillation tower (4) and enters an alcohol storage tank (5), and the biodiesel with low acid value and without alcohol enters a biodiesel with low acid value (7); when the mass percentage of the alcohol in the biodiesel from the adsorption separation tower (2) is qualified, the dealcoholization regeneration of the adsorption separation tower (2) is completed;
the dealcoholization regeneration method for the adsorption separation tower 1 comprises the following steps: the eluent in the adsorption separation tower (1) is jacked to the alcohol distillation tower (4) or directly jacked to the alcohol storage tank 5 from a pipeline (16) and a pipeline (17) by using inactive gas through a pipeline (14) and a pipeline (15), and then the low acid value biodiesel is conveyed to the adsorption separation tower (1) from a pipeline (27), a pipeline (24), a pipeline (25) and a pipeline (15) from a low acid value biodiesel storage tank (7); the biodiesel containing alcohol with low acid value enters a distillation tower (4) through a pipeline (16) and a pipeline (17), the alcohol is distilled out from the top of the alcohol distillation tower (4) and enters an alcohol storage tank (5), and the biodiesel with low acid value and without alcohol enters a biodiesel storage tank (7) with low acid value; when the mass percentage of the alcohol in the biodiesel from the adsorption separation tower (1) is qualified, the dealcoholization regeneration of the adsorption separation tower (1) is completed.
5. The method as set forth in claim 4, wherein the adsorption separation column 1 adsorption deacidification method comprises: the biodiesel with unqualified acid value is conveyed to an adsorption separation tower (1) for adsorption deacidification through a pipeline (8) and a pipeline (9), and the biodiesel with qualified acid value enters a biodiesel storage tank (3) through a pipeline (11) and a pipeline (13).
6. The method according to claim 4, wherein the desorption of the adsorption separation column (2) comprises: the alcohol desorbent delivered from the alcohol storage tank (5) enters the adsorption separation tower (2) through a pipeline (23), a pipeline (24), a pipeline (26) and a pipeline (18), the free fatty acid adsorbed by the adsorption separation tower (2) is eluted, the eluent enters the alcohol distillation tower (4) through a pipeline (19) and a pipeline (17), the alcohol desorbent is evaporated from the top of the alcohol distillation tower (4) and enters the alcohol storage tank (5), and the biodiesel containing the free fatty acid and subjected to alcohol removal enters the biodiesel storage tank (6) containing the free fatty acid.
7. A method according to claim 4, wherein the adsorptive separation column (2) is deacidified by adsorption comprising: the biodiesel with unqualified acid value is conveyed to an adsorption separation tower (2) for adsorption deacidification through a pipeline (8) and a pipeline (10), and the biodiesel with qualified acid value enters a biodiesel storage tank (3) through a pipeline (12) and a pipeline (13).
8. The method according to claim 4, wherein the desorption method of the adsorption separation column (1) comprises: the alcohol desorbent delivered from the alcohol storage tank (5) enters the adsorption separation tower (1) through a pipeline (23), a pipeline (24), a pipeline (25) and a pipeline (15), the free fatty acid adsorbed by the adsorption separation tower (1) is eluted, the eluent enters the alcohol distillation tower (4) through a pipeline (16) and a pipeline (17), the alcohol desorbent is evaporated from the top of the alcohol distillation tower (4) and enters the alcohol storage tank (5) through a pipeline (20), and the biodiesel containing the free fatty acid and subjected to alcohol removal enters the biodiesel storage tank (6) containing the free fatty acid.
9. The method according to claim 5 or 7, wherein the biodiesel having a nonconforming acid value has an acid value of 0.5 to 5.0 mgKOH/g.
10. The method according to claim 5 or 7, wherein the adsorption separation tower is used for adsorption deacidification at the temperature of between room temperature and 100 ℃ and the liquid hourly space velocity of between 0.2 and 10h-1The operating pressure is 0.1-1.0 MPa.
11. The process of claim 6 or 8, wherein the alcohol desorbent is a C1-C4 fatty alcohol.
12. The process of claim 11, wherein the alcohol desorbent is selected from one or more of methanol, ethanol, propanol, and n-or iso-butanol.
13. The method of claim 4, wherein the inert gas is nitrogen, air, helium, neon, or argon.
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