CN105695104B - In-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids - Google Patents

In-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids Download PDF

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CN105695104B
CN105695104B CN201610187103.2A CN201610187103A CN105695104B CN 105695104 B CN105695104 B CN 105695104B CN 201610187103 A CN201610187103 A CN 201610187103A CN 105695104 B CN105695104 B CN 105695104B
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acid methyl
methyl ester
fatty acid
rectifying tower
tower
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CN105695104A (en
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丁辉
齐金龙
施民育
徐世民
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C11C1/10—Refining by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B01D3/106—Vacuum distillation with the use of a pump for creating vacuum and for removing the distillate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/42—Regulation; Control
    • B01D3/4205—Reflux ratio control splitter
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention discloses a pumping type high vacuum rectification method and a device in a tower for precisely separating C16-C22 fatty acids, which comprise the following steps: firstly, taking thermosensitive materials rich in high added value as raw materials, such as animal and vegetable oil, adopting ionic liquid and the like as esterification and transesterification catalysts, obtaining a plurality of fatty acid methyl ester mixtures with high yield in one step, secondly, carrying out high vacuum rectification operation on the plurality of fatty acid methyl esters which are formed by catalysis in a rectifying tower with almost no pressure drop, and finally separating and purifying to obtain single fatty acid methyl esters such as eicosapentaenoic acid methyl ester, docosahexaenoic acid methyl ester, palmitic acid methyl ester, stearic acid methyl ester, oleic acid methyl ester, linoleic acid methyl ester and the like with the mass fractions of more than 98 percent respectively; the whole process method is simple, the operation is simple, the equipment cost is low, the energy is saved, and the amplification is easy.

Description

In-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids
Technical Field
The invention relates to the field of chemical mass transfer and separation, in particular to an in-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids.
Background
The sea resources in China are rich, the yield of freshwater fish is more in the forefront of the world, so that the quantity of fish oil produced in various production activities is huge, and the fish oil still contains a large quantity of high-added-value fatty acids, namely eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), which are important nutrient elements indispensable for human bodies, wherein the eicosapentaenoic acid can effectively help to reduce the content of cholesterol and triglyceride and promote the metabolism of saturated fatty acids in the human bodies, thereby reducing blood viscosity, improving blood circulation, improving oxygen supply of tissues and eliminating fatigue; the docosahexaenoic acid plays an important role in the growth and development of brain nerves, the visual development of infants and the intelligent development of children, and also has the functions of resisting allergy, enhancing immunity and the like. Besides fish oil, algae oil, plant seeds, pulp, corn germs and other cells are rich in grease, the content of which varies with raw materials, for example, the oil content of rice bran is about 12% -20%, and the oil content of copra pulp is about 63% -70%. Is generally obtained by a squeezing method or a solvent extraction method. Some vegetable oils and fats such as peanut oil, castor oil, and triglycerides of fatty acids include, in addition to common palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc., specific erucic acid, arachic acid, eleostearic acid, ricinoleic acid, etc. The fatty acids are widely applied to the fields of preparation of auxiliary agents, oil additives, surfactants, lubricants, other organic chemicals and the like, and are closely related to the production and life of people.
Therefore, the method combines the advantages of resources in China, widens the deep processing value space of animal and plant products, reduces the resource waste, utilizes the animal and plant oil such as fish oil and corn oil to prepare, separate and purify the fatty acid with high added value according to the characteristics of the components contained in the oil such as the fish oil and the corn oil, not only can improve the economic value of raw materials, but also can meet the market of medicines and health-care products, and accords with the important strategy of comprehensive sustainable development.
For separation and purification, common means include urea inclusion, supercritical extraction, molecular distillation, low-temperature crystallization, chromatographic separation, solvent extraction, silver ion complexation, metal salt precipitation and other methods, but on the one hand, the separation purity of the above methods is not high, and generally only saturated fatty acid methyl esters and unsaturated fatty acid methyl esters products with higher purity can be obtained, but almost no single high-purity fatty acid methyl ester can be obtained, especially for methyl stearate, methyl oleate and methyl linoleate, on the other hand, the methods also have the problems of instability, difficult separation, solvent recovery, environmental pollution and the like at present. In FIG. 1, (a) is methyl palmitate (C16:0); (b) methyl stearate (C18:0); (C) is methyl oleate (C18:1); (d) Methyl linoleate (C18:2), and methyl eicosapentaenoate (C20:5) in FIG. 2 (a); (b) is docosahexaenoic acid (C22:6). As can be seen from FIG. 1, the difference in structure between the three is only one to two double bonds, which results in small difference in physical and chemical properties between the three, and conventional separation means are rarely capable of completely separating the three substances; for the eicosapentaenoic acid methyl ester and the docosahexaenoic acid methyl ester in fig. 2, the two have complex space structures because of a large number of double bond structures, are sensitive to high temperature and are easy to be deformed, and the separation means can not effectively separate the eicosapentaenoic acid methyl ester and the docosahexaenoic acid methyl ester to obtain a large number of simple substance pure products.
The method is used as a widely used inter-substance separation technology in the chemical industry field at present, namely rectification, and can also be used as a means for separating and purifying high-added-value fatty acid in animal and vegetable oil. However, animal and vegetable oils and fatty acids with high added value separated therefrom are heat-sensitive substances, which are temperature-sensitive substances that undergo deterioration when heated to a certain extent, that is, other chemical substances are generated by decomposition, polymerization, etc. The heat sensitive materials are separated and purified, which is difficult to achieve in the traditional rectification mode. Therefore, there are two general approaches to solving the problems of conventional rectification, one is to slow down the rate of decomposition or polymerization of heat sensitive materials by adding inhibitors; the other method is to increase the vacuum degree of the tower top and the tower bottom, on one hand, the vacuum degree can increase the relative volatility among the thermosensitive substances with similar physical properties, so that the single thermosensitive substance with high purity and high yield can be easily obtained, and on the other hand, the vacuum degree can reduce the boiling point of the thermosensitive substance to ensure that the boiling point is as lower than the temperature when the thermosensitive substance is easy to be degraded as possible, thereby ensuring that the thermosensitive substance is not damaged. For many heat-sensitive materials, the method of thin film distillation can be used for purification in practical application, and the thin film distillation can realize separation of substances under extremely high vacuum condition due to small vacuum resistance. This is advantageous for the handling of heat sensitive materials.
However, for the first method, the addition of the inhibitor can improve the product purity of the heat-sensitive substances to a certain extent and slow down the deterioration rate of the heat-sensitive substances during production, but the addition of the inhibitor not only improves the cost, but also improves the production cost of separating and purifying the heat-sensitive substances due to the subsequent recovery of the inhibitor and whether the inhibitor pollutes the environment; for the second method, the prior art can improve the vacuum degree of the tower top of the corresponding rectifying tower, but cannot control the vacuum degree of the tower bottom, so that the thermosensitive substance with high purity and high yield is obtained, the height of the rectifying tower needs to be correspondingly improved, the vacuum degree of the tower bottom is correspondingly reduced, the temperature of the tower bottom is correspondingly increased, and the thermosensitive substance is in danger of deterioration at the moment. Therefore, in order to increase the vacuum degree of the tower kettle, a multi-tower serial operation is often adopted to reduce the temperature of the tower kettle and increase the vacuum degree of the tower kettle, but the equipment cost is correspondingly increased, and huge energy consumption is generated. In addition, another technology for improving the vacuum degree of the rectifying tower is to add a pressure regulator inside the rectifying tower to reduce pressure drop, but the pressure regulator inside the rectifying tower has a small compression ratio due to the structure of the fan blade, has a certain effect when the vacuum degree is lower, and gradually loses the pressure regulating effect of the fan blade along with the improvement of the vacuum degree, so that the problem of tower pressure drop of high vacuum rectification cannot be solved. Because the molecular distillation has small resistance, the substances can be separated under extremely high vacuum condition, and therefore, the method of molecular distillation can be adopted for purifying thermosensitive substances, but the molecular distillation only has the separation efficiency of a single-stage tower plate, and still cannot realize high-efficiency separation.
In summary, there are few reports on the technology of completely separating eicosapentaenoic acid methyl ester from docosahexaenoic acid methyl ester or methyl stearate, oleic acid methyl ester and linoleic acid methyl ester to obtain single fatty acid methyl ester with very high purity, which seriously hinders further research and application of high-purity fatty acid methyl ester.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a pumping type high vacuum rectification method and a device in a tower for precisely separating C16-C22 series fatty acids, which not only can improve the height of the rectification tower, but also can reduce the pressure of the tower kettle and improve the vacuum degree of the tower kettle, ensure the heat insulation in the tower, have extremely small heat loss, greatly reduce energy consumption, and can purify and obtain fatty acid esters such as eicosapentaenoic acid methyl ester, docosahexaenoic acid methyl ester, palmitic acid methyl ester, methyl stearate, oleic acid methyl ester, linoleic acid methyl ester and the like with the mass percentages of more than 98 percent respectively.
The invention is realized by the following technical scheme:
an in-tower pumping type high vacuum rectification method for precisely separating C16-C22 fatty acids comprises the following steps:
(1) The pretreatment of the grease comprises the following specific steps:
(a) Adding a catalyst, grease and methanol into a reaction container together, then placing the reaction container into a water bath at 50-100 ℃, and stirring the mixed solution in the container until the grease and the methanol fully react under the action of the catalyst to obtain a plurality of fatty acid methyl ester mixture pretreatment products;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel;
(c) Rotary evaporating the residual substances in the reaction vessel at 90-150 ℃ to recover a small amount of methanol and water, and then recovering and treating the residual substances;
(2) The separated mixture of various fatty acid methyl esters is precisely separated in high vacuum, and the specific steps are as follows:
(a) Pumping a plurality of fatty acid methyl esters into a feed preheater with the temperature of 40-180 ℃ from a raw material storage tank through a feed metering pump at the flow rate of 2.5-100 mL/min, then entering a rectifying tower from a feed inlet of the rectifying tower, and then uniformly distributing hot fatty acid methyl ester raw materials into a stripping section of the rectifying tower through a feed distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and rises, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, finally enters the reboiler through the stripping section of the rectifying tower, and the temperature of the reboiler is 100-180 ℃ and the pressure is 2-200 Pa;
(c) The fatty acid methyl ester in the reboiler is heated, partially vaporized and then rises, then the high vacuum provided by the Roots vacuum pump sequentially enters a stripping section and a rectifying section of the rectifying tower, and the vaporized fatty acid methyl ester and liquid flowing down from the upper part in the rectifying tower realize gas-liquid mass transfer in the process;
(d) The gas phase components in the rectifying tower finally enter a condenser from the rectifying tower top with the tower top pressure of 0.65-200 Pa to be liquefied to form light component condensate, then one part of condensate flows back into the rectifying tower with the reflux ratio of 1-10 under the control of a reflux ratio controller, the other part of condensate enters a cooler and is extracted by a distilled product extraction pump, finally sampling detection analysis is carried out, and products which are obtained from the rectifying tower top and contain single components of methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, eicosapentaenoic acid methyl ester and docosahexaenoic acid methyl ester with the mass percent purity of more than 98% are respectively collected according to the sequence of the products from the tower top;
(e) The fatty acid methyl ester part in the reboiler is regulated by a discharging proportion distributor, one part of the fatty acid methyl ester part is respectively refluxed to the stripping section of the rectifying tower and the reboiler under the action of a heavy component reflux pump, and the other part of the fatty acid methyl ester part is extracted by a heavy component discharging pump;
The grease comprises animal and vegetable grease rich in stearic acid, oleic acid and linoleic acid or one of seaweed oil rich in eicosapentaenoic acid and docosahexaenoic acid, fish oil and waste fish oil with a high acid value of more than 2 or swill-cooked dirty oil.
A high-vacuum rectifying device for the precise separation of C16-C22 fatty acids in a tower comprises a rectifying tower, wherein a feed inlet is formed in the rectifying tower, the rectifying tower comprises a rectifying section, a stripping section and a reboiler, the top of the rectifying tower is connected with a condenser, the condenser is connected with a vacuum system through a vacuum pipe, a condensate outlet of the condenser is communicated with the feed inlet of a reflux ratio controller, one liquid outlet of the reflux ratio controller is sequentially communicated with a cooler and a distilled product extraction pump through a vacuum pipe, the other liquid outlet of the reflux ratio controller is sequentially communicated with the feed inlet of the reflux vacuum pipe, the liquid outlet of the reflux vacuum pipe is inserted into the rectifying tower through the reflux inlet of the rectifying tower, one reflux distributor is arranged in the rectifying tower below the reflux vacuum pipe, the bottom of the rectifying tower is sequentially connected with a reboiler and a discharge proportional distributor, one outlet of the discharge proportional distributor is connected with the feed inlet of the reflux ratio controller through the vacuum pipe, one reflux ratio controller is sequentially connected with the feed inlet of the reflux pump through the reflux ratio controller, the other reflux ratio controller is respectively arranged at the position of the rectifying tower, the reflux pump is sequentially connected with the feed inlet of the reflux ratio controller, the reflux pump is respectively arranged at the position of the rectifying tower, and the reflux section is sequentially communicated with the feed inlet of the reflux section through the reflux section, and the reflux pump.
Compared with the prior art, the main advantages of the invention are mainly as follows:
1. the main component of the experimental device and the experimental method of the invention is the Roots vacuum pump, which has larger air extraction speed and high efficiency under high vacuum, and can make up the problem of overlarge gear clearance of the Roots vacuum pump under high temperature by using the reflux liquid, so that the compression ratio of the Roots vacuum pump is improved, and a downward channel is provided for the reflux liquid, thereby avoiding the additional increase of a liquid collector between tower sections due to the increase of the use of the Roots vacuum pump.
2. The method of adding the Roots vacuum pump into the high vacuum rectifying device thoroughly solves the problem of low vacuum degree in the high vacuum rectifying tower kettle and the tower column caused by pressure drop, and the whole tower is enabled to realize pressure-drop-free high vacuum rectification. The invention greatly reduces the pressure of the tower kettle, thereby reducing the temperature of the tower kettle, protecting heat-sensitive substances from being damaged, and increasing the relative volatility among components at the same time, so that the experimental device has the characteristic of high-efficiency separation capability.
3. The residence time of the gas-liquid phase component in the heating area of the experimental device is short, so that the occurrence of deterioration reaction of the heat-sensitive substances can be further reduced;
4. The experimental device and the method can greatly reduce the heating temperature of the reboiler, expand the application range of high vacuum rectification, and play the roles of saving energy and reducing the manufacturing cost of equipment. Provides a novel rectification concept for separating and purifying heat-sensitive substances, and has wide application prospect. The experimental device and the experimental method can be used for respectively purifying and obtaining single fatty acid esters such as eicosapentaenoic acid methyl ester, docosahexaenoic acid methyl ester, palmitic acid methyl ester, stearic acid methyl ester, oleic acid methyl ester, linoleic acid methyl ester and the like with the mass percent of more than 98 percent.
5. The experimental device can ensure the adiabatic pressurization in the tower, has small heat loss and greatly reduces the energy consumption.
6. The rectification height of the experimental device and the number of the Roots vacuum pumps can be determined according to specific conditions, so that the experimental device can be widely applied to the separation of the device, and has the characteristics of large production capacity adjustment range and flexible and convenient operation.
Drawings
FIG. 1 shows the molecular structural formula of main fatty acid methyl ester contained in biodiesel prepared from vegetable oil as raw material;
FIG. 2 is a molecular structural formula of high value-added fatty acid methyl ester contained in biodiesel prepared from fish oil and the like;
Fig. 3 is a graph of eicosapentaenoic acid and docosahexaenoic acid (epa+dha) content of heat sensitive materials over time and temperature (p=2 kPa);
fig. 4 is a graph showing the content of the thermosensitive substances eicosapentaenoic acid and docosahexaenoic acid (EPA, DHA) as a function of temperature (p=200 pa, t=5 h);
FIG. 5 is a schematic diagram of the structure of the high vacuum device of the invention for precisely separating C16-C18 fatty acids and C20-C22 fatty acids in the tower.
Detailed Description
The following are specific embodiments of the present invention, which are presented to further illustrate, but not limit, the invention.
Firstly, taking heat-sensitive materials rich in high added value as raw materials, such as animal and vegetable oil, and carrying out esterification and transesterification under the action of a catalyst, so that a plurality of fatty acid methyl ester mixtures with high yield, namely biodiesel, can be obtained in one step, and the reaction condition is mild. Meanwhile, when ionic liquid, solid acid, solid alkali and the like are adopted as the catalyst, the catalyst is convenient to recycle and can be repeatedly used for a plurality of times, so that the catalyst is environment-friendly;
secondly, by utilizing the experimental device capable of increasing the vacuum degree in the tower kettle and the tower of the high-vacuum rectifying tower, under the condition that almost no pressure drop exists in the whole rectifying tower, the biodiesel which is formed through catalysis is subjected to high-vacuum rectifying operation, and finally single fatty acid methyl esters such as eicosapentaenoic acid methyl ester, docosahexaenoic acid methyl ester, palmitic acid methyl ester, stearic acid methyl ester, oleic acid methyl ester, linoleic acid methyl ester and the like with the mass fractions of more than 98% are respectively obtained through separation and purification; the whole process method is simple, the operation is simple, the equipment cost is low, the energy is saved, the environment is protected, and the economic application prospect is very good.
Meanwhile, through the figures 3 and 4, eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) can be modified at high temperature for a period of time, and the modification of high added value components of heat-sensitive materials containing EPA, DHA and the like caused by overlong extraction time in a high-temperature system can be effectively avoided.
According to the principle, the invention relates to an in-tower pumping type high vacuum rectification method for precisely separating C16-C22 fatty acids, which comprises the following steps:
(1) The pretreatment of the grease comprises the following specific steps:
(a) Adding a catalyst, grease and methanol into a reaction container together, wherein the proportion of the catalyst, the thermosensitive grease and the methanol added into the reaction container is not limited, but at least the fatty acid part in the thermosensitive grease is ensured to be changed into fatty acid methyl ester which is easy to uniformly produce and apply from free fatty acid and more difficult to use, then the reaction container is placed into a water bath at 50-100 ℃, and the mixed solution in the container is stirred until the grease and the methanol fully react under the action of the catalyst to obtain a plurality of fatty acid methyl ester mixture pretreatment products;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel, wherein the mixture of the fatty acid methyl esters is biodiesel;
(c) Rotary evaporating the residual substances in the reaction vessel at 90-150 ℃ to recover a small amount of methanol and water, and then recovering and treating the residual substances;
(2) The separated mixture of various fatty acid methyl esters is precisely separated in high vacuum, and the specific steps are as follows:
(a) Pumping a plurality of fatty acid methyl esters into a feed preheater with the temperature of 40-180 ℃ from a raw material storage tank through a feed metering pump at the flow rate of 2.5-100 mL/min, then entering a rectifying tower from a feed inlet of the rectifying tower, and then uniformly distributing hot fatty acid methyl ester raw materials into a stripping section of the rectifying tower through a feed distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and rises, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, finally enters the reboiler through the stripping section of the rectifying tower, and the temperature of the reboiler is 100-180 ℃ and the pressure is 2-200 Pa;
(c) The fatty acid methyl ester in the reboiler is heated, partially vaporized and then rises, then the high vacuum provided by the Roots vacuum pump sequentially enters a stripping section and a rectifying section of the rectifying tower, and the vaporized fatty acid methyl ester and liquid flowing down from the upper part in the rectifying tower realize gas-liquid mass transfer in the process;
(d) The gas phase components in the rectifying tower finally enter a condenser from the rectifying tower top with the tower top pressure of 0.65-200 Pa to be liquefied to form light component condensate, then one part of condensate flows back into the rectifying tower with the reflux ratio of 1-10 under the control of a reflux ratio controller, the other part of condensate enters a cooler and is extracted by a distilled product extraction pump, finally sampling detection analysis is carried out, and the products with single components such as methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl eicosapentaenoate, methyl docosahexaenoic acid and the like with the mass percent purity of more than 98 percent are respectively collected according to the sequence of the products from the tower top;
(e) And the fatty acid methyl ester part in the reboiler is regulated by a discharging proportion distributor, one part of the fatty acid methyl ester part is respectively refluxed to the stripping section of the rectifying tower and the reboiler under the action of a heavy component reflux pump, and the other part of the fatty acid methyl ester part is extracted by a heavy component discharging pump.
The oil comprises one of animal and vegetable oil rich in stearic acid, oleic acid and linoleic acid, or algae oil rich in eicosapentaenoic acid and docosahexaenoic acid, fish oil, and waste fish oil with acid value higher than 2 and swill-cooked dirty oil.
The catalyst is ionic liquid or KOH, caO, H 2 SO 4 Acids, bases, etc. represented by Amberlyst15, etc.; wherein the ionic liquid catalyst comprises at least one of the following components [ BHSO ] 3 MIM]HSO 4 、[(CH 2 ) 3 SO 3 HMIM][HSO 3 ]Representative imidazoles and the use of [ (CH) 3 CH 2 ) 3 N(CH 2 ) 3 SO 3 H][C 7 H 7 O 3 S]Quaternary ammonium salts as representatives
Figure BDA0000952680470000091
Acidic ionic liquid [ Bmim ]]Br-CuCl 2 、[Bmim]Br-FeCl 3 、[Bmim]Br-CuCl、[Bmim]Br-Fe 2 Cl 6 、[Bmim]Br-Ni 2 Cl 4 As a representative Lewis acidic ionic liquid, a method of preparing the same, and a method of preparing the same 3 S-(CH 2 ) 3 -NEt 3 ]Cl-FeCl 3 、[BSO 3 HMIM]HSO 4 -Fe 2 (SO 4 ) 3 As representative of the double acid ionic liquid, the method is characterized by [ BTBD]OH、[TBA]OH、[Hnmm]Basic ionic liquid represented by OH, represented by [ PyPS ]]PW、[TMAPS]PW、[MIMPS]PW and [ QPS ]]PW is any one or a mixture of any at least two ionic liquids in the heteropolyacid ionic liquids.
The ratio of the catalyst to the heat-sensitive grease to the methanol in the reactor is not particularly required, the mol ratio of the methanol to the heat-sensitive grease is recommended to be at least 3:1, and the dosage of the catalyst is at least 1 percent of the mol percentage of the methanol to the heat-sensitive grease.
The rectifying tower consists of a plurality of tower sections, and the height of the packing in each tower section is 0.1-2.5 m.
The diameter of the rectifying tower is 5-1000 mm.
The rectifying tower packing comprises silk screen corrugated plates, corrugated packing and isotatic packing; random packing such as pall rings, ladder rings, theta ring packing, glass spring packing and the like.
The reboiler is a wiped film evaporator or other heating kettles, and when the reboiler is a wiped film evaporator, the rotating speed of the scraping plate is 20-1000 r/min; the temperature of the tower kettle is ensured to be lower and the separation effect of the traditional rectification is still equivalent or far exceeds.
As shown in figure 3, a high vacuum rectifying device for realizing the precise separation of C16-C22 series fatty acids in a tower pump comprises a rectifying tower, a feed inlet is formed in the rectifying tower, the rectifying tower comprises three parts of a rectifying section 5, a stripping section 7 and a reboiler 9, a condenser 1 is connected to the top of the rectifying tower, the condenser 1 is connected with a vacuum system 13 through a first vacuum pipe, a condensate outlet of the condenser 1 is communicated with a feed inlet of a reflux ratio controller 14, one liquid outlet of the reflux ratio controller 14 is sequentially connected with a cooler 15 and a vapor extraction pump 16 through a second vacuum pipe, the other liquid outlet of the reflux ratio controller 14 is communicated with the feed inlet of the reflux vacuum pipe, the liquid outlet of the reflux vacuum pipe is inserted into the rectifying tower 2 through a reflux inlet of the rectifying tower 2, one reflux distributor 4 is arranged in the rectifying tower 2 below the reflux vacuum pipe, the condensate outlet of the rectifying tower 1 is sequentially connected with a reflux component outlet of the reflux pump 2 through a reflux pump 11 and a reflux component outlet of the reflux pump 12 in the reflux tower 2 through a reflux inlet of the reflux pump 11, the reflux component is sequentially connected with a reflux component outlet of the reflux component 12 in the reflux pump 2 through a reflux pump 12 and a reflux component outlet of the reflux component 12, and a reflux component is sequentially connected with a reflux component 12 in the reflux component is respectively connected with a reflux component 12 through a reflux component 12 in the reflux component 12 and a reflux component 12 in the reflux component is in the reflux tower through a reflux pump 12 and a reflux component is connected with a reflux component 12 in the reflux component 12, a feed distributor 6 is arranged in the rectifying tower 2 below the feed inlet, and at least one Roots vacuum pump 3 is respectively arranged in the rectifying section 5 and the stripping section 7 of the rectifying tower 2.
The Roots vacuum pump can be an internal Roots vacuum pump or an external Roots vacuum pump, and when the internal Roots vacuum pump is used, the vacuum pump is arranged in the rectifying tower; when the external Roots vacuum pump is used, the rectifying tower is in screw connection with the external Roots vacuum pump, and the sealing mode between the rectifying tower and the external Roots vacuum pump adopts magnetic sealing.
The Roots vacuum pump adopts at least two-lobe Roots rotors.
The Roots vacuum pump adopts a Roots tooth shape.
The number of the Roots vacuum pumps is not less than two, and the Roots vacuum pumps can be particularly operated according to corresponding operating conditions.
Example 1
The raw material adopted in the example is vegetable oil with a certain high acid value, and the acid value is 23.6mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of vegetable oil comprises the following specific steps:
(a) Taking ionic liquid [ Bmim ] Br-CuCl, vegetable oil and methanol with the mass ratio of 1:2:34, and adding the ionic liquid [ Bmim ] Br-CuCl, the vegetable oil and the methanol into a reaction container together; placing the reaction vessel in a water bath at 50 ℃, and stirring the mixed solution in the vessel until vegetable oil and methanol fully react under the catalysis of ionic liquid [ Bmim ] Br-CuCl to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) The separated [ Bmim ] Br-CuCl ionic liquid is subjected to rotary evaporation at 90 ℃ to remove a small amount of methanol and water, and then is recovered for reuse; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.19 mgKOH/g.
(2) The high vacuum fine separation of the fatty acid methyl ester of C16-C18 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 180 ℃ from a raw material storage tank through a feeding metering pump at the flow rate of 2.5mL/min, then entering a rectifying tower with the height of 0.1m and the inner diameter of 300mm and with a wire mesh corrugated plate as a structured packing, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and ascends, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a heating kettle with the temperature of 100 ℃ and the pressure of 2Pa through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the heating kettle is heated, the fatty acid methyl ester is partially vaporized and then rises, and the fatty acid methyl ester sequentially enters a stripping section and a rectifying section of the rectifying tower through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down from the upper part;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 0.65Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) refluxing the mixture into a rectifying tower under the control of a reflux ratio controller (reflux ratio is 1), collecting a light component liquid part into a cooler, extracting the light component liquid part by a distilled product extraction pump, and finally, sampling, detecting and analyzing the light component liquid part to collect liquid products with the mass percent purity of more than 98% and containing single components of methyl palmitate C16:0, methyl stearate C18:0, methyl oleate C18:1 and methyl linoleate C18:2 respectively.
(e) And the fatty acid methyl ester part in the heating kettle is regulated by a discharging proportion distributor, one part of the fatty acid methyl ester part is respectively refluxed to the stripping section of the packing tower and the heating kettle under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of the fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 2
The starting material used in this example was a certain high acid number vegetable oil of example 1.
(1) The pretreatment of vegetable oil comprises the following specific steps:
(a) CaO, vegetable oil and methanol are taken and added into a reaction vessel together according to the mass ratio of 1:2:28; placing the reaction vessel in a water bath at 100 ℃, and stirring the mixed solution in the vessel until vegetable oil and methanol fully react under the catalytic action of CaO to obtain a plurality of fatty acid methyl ester mixtures;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel, wherein the mixture of the fatty acid methyl esters is biodiesel;
(c) The residual substances in the reaction vessel are recovered by rotary evaporation at 100 ℃ to recover a small amount of methanol and water, and then are recovered and treated.
(2) The high vacuum fine separation of the fatty acid methyl ester of C16-C18 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 150 ℃ from the raw material tank at the flow rate of 50mL/min through a feeding metering pump, then entering a rectifying tower with the height of 1.8m and the inner diameter of 700mm and taking a wire mesh corrugated plate as a structured packing, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and ascends, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a heating kettle with the temperature of 100 ℃ and the pressure of 30Pa through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the heating kettle is heated, the fatty acid methyl ester is partially vaporized and then rises, and the fatty acid methyl ester sequentially enters a stripping section and a rectifying section of the rectifying tower through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down from the upper part;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 30Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) refluxing the mixture into a rectifying tower under the control of a reflux ratio controller (reflux ratio is 1), collecting a light component liquid part into a cooler, extracting the light component liquid part by a distilled product extraction pump, and finally, sampling, detecting and analyzing the light component liquid part to collect liquid products with the mass percent purity of more than 98% and containing single components of methyl palmitate C16:0, methyl stearate C18:0, methyl oleate C18:1 and methyl linoleate C18:2 respectively.
(e) And the fatty acid methyl ester part in the heating kettle is regulated by a discharging proportion distributor, one part of the fatty acid methyl ester part is respectively refluxed to the stripping section of the packing tower and the heating kettle under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of the fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 3
The raw material adopted in the example is a waste corn oil, and the acid value is 10.1mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of the waste corn oil comprises the following specific steps:
(a) Taking ionic liquid [ BTBD ] OH, waste corn oil and methanol with the mass ratio of 1:6:20, and adding the ionic liquid [ BTBD ] OH, the waste corn oil and the methanol into a reaction container together; placing the reaction vessel in a water bath at 55 ℃, and stirring the mixed solution in the vessel until vegetable oil and methanol fully react under the catalysis of ionic liquid [ BTBD ] OH to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) The separated [ BTBD ] OH ionic liquid is subjected to rotary evaporation at the temperature of 100 ℃ to remove a small amount of methanol and water, and then is recovered and reused; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.21 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C16-C18 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 150 ℃ from the raw material tank at the flow rate of 40mL/min through a feeding metering pump, then entering a rectifying tower with the height of 1.0m and the inner diameter of 5mm and with corrugated filler as regular filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 170 ℃ and the pressure of 160Pa and the rotating speed of 250r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 160Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) controlling the reflux ratio to be 7 through a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting the liquid through a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of methyl palmitate C16:0, methyl stearate C18:0, methyl oleate C18:1 and methyl linoleate C18:2 respectively.
(e) And the fatty acid methyl ester part in the film scraping type film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to a stripping section of the packing tower and the film scraping type film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 4
The feedstock used in this example was some waste corn oil of example 3.
(1) The pretreatment of the waste corn oil comprises the following specific steps:
(a) Taking H with the mass ratio of 1:4:20 2 SO 4 Adding the waste corn oil and methanol into a reaction container together; placing the reaction vessel in a water bath at 75deg.C, stirring the mixed solution in the vessel until vegetable oil and methanol are mixed in H 2 SO 4 Fully reacting under the catalysis of the catalyst to obtain a plurality of fatty acid methyl ester mixtures;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel, wherein the mixture of the fatty acid methyl esters is biodiesel;
(c) The residual substances in the reaction vessel are recovered by rotary evaporation at 110 ℃ to recover a small amount of methanol and water, and then are recovered and treated.
(2) The high vacuum precise separation of the fatty acid methyl ester of C16-C18 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 130 ℃ from the raw material tank at the flow rate of 55mL/min through a feeding metering pump, then entering a rectifying tower with the height of 1.4m and the inner diameter of 20mm and with corrugated filler as regular filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 175 ℃ and the pressure of 120Pa and the rotating speed of 210r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 120Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) controlling the reflux ratio to be 7 through a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting the liquid through a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of methyl palmitate C16:0, methyl stearate C18:0, methyl oleate C18:1 and methyl linoleate C18:2 respectively.
(e) And the fatty acid methyl ester part in the film scraping type film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to a stripping section of the packing tower and the film scraping type film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 5
The raw material adopted in the example is a certain waste palm oil, and the acid value is 16.3mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of the waste palm oil comprises the following specific steps:
(a) Taking ionic liquid [ MIMPS ] PW, waste palm oil and methanol with the mass ratio of 1:4:48, and adding the ionic liquid [ MIMPS ] PW, the waste palm oil and the methanol into a reaction container together; placing the reaction vessel in a water bath at 60 ℃, and stirring the mixed solution in the vessel until vegetable oil and methanol fully react under the catalysis of ionic liquid [ MIMPS ] PW to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) The separated [ MIMPS ] PW ionic liquid is rotationally evaporated at 110 ℃ to remove a small amount of methanol and water, and then is recovered and reused; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.24 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C16-C18 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 130 ℃ from the raw material tank at the flow rate of 100mL/min through a feeding metering pump, then putting the mixture into a rectifying tower with the height of 2m, the inner diameter of 350mm and taking pall rings as fillers, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and rises, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 120 ℃ and the pressure of 20Pa and the rotating speed of 850r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 20Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) controlling the reflux ratio to be 4 through a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting the liquid through a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of methyl palmitate C16:0, methyl stearate C18:0, methyl oleate C18:1 and methyl linoleate C18:2 respectively.
(e) And the fatty acid methyl ester part in the wiped film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to a stripping section of the rectifying tower and the wiped film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 6
The raw material adopted in the example is waste fish oil with a certain high acid value, and the acid value is 20.9mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of the high acid value waste fish oil comprises the following specific steps:
(a) Taking an ionic liquid [ (CH) with the mass ratio of 1:4.5:31 2 ) 3 SO 3 HMIM][HSO 3 ]Adding the high acid value waste fish oil and methanol into a reaction container together; placing the reaction vessel in a 65 ℃ water bath, and stirring the mixed solution in the vessel until the high acid value waste fish oil and methanol are in ionic liquid [ (CH) 2 ) 3 SO 3 HMIM][HSO 3 ]Fully reacting under the catalysis of the catalyst to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) To separate [ (CH) 2 ) 3 SO 3 HMIM][HSO 3 ]The ionic liquid is recovered for reuse after a small amount of methanol and water are removed by rotary evaporation at 120 ℃; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.31 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C20-C22 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 110 ℃ from the raw material tank at the flow rate of 75mL/min through a feeding metering pump, then putting the mixture into a rectifying tower with the height of 2m, the inner diameter of 800mm and the stepped ring as a filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 110 ℃ and the pressure of 10Pa and the rotating speed of 700r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 10Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) controlling the reflux ratio to be 2 through a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting the light component liquid through a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of eicosapentaenoic acid methyl ester C20:5 and docosahexaenoic acid methyl ester C22:6 respectively.
(e) And the fatty acid methyl ester part in the wiped film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to a stripping section of the rectifying tower and the wiped film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 7
The starting material used in this example was some high acid number waste fish oil from example 6.
(1) The pretreatment of the high acid value waste fish oil comprises the following specific steps:
(a) Taking solid acid Amberlyst15, high acid value waste fish oil and methanol with the mass ratio of 1:6:33, and adding the solid acid Amberlyst15, the high acid value waste fish oil and the methanol into a reaction container together; placing the reaction vessel in a water bath at 60 ℃, and stirring the mixed solution in the vessel until the high acid value waste fish oil and methanol fully react under the catalysis of Amberlyst15 solid acid to obtain a plurality of fatty acid methyl ester mixtures;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel, wherein the mixture of the fatty acid methyl esters is biodiesel;
(c) The residual substances in the reaction vessel are subjected to rotary evaporation at 120 ℃ to collect a small amount of methanol and water, and then the solid acid Amberlyst15 catalyst can be recovered by filtration.
(2) The high vacuum precise separation of the fatty acid methyl ester of C20-C22 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 115 ℃ from the raw material tank at the flow rate of 65mL/min through a feeding metering pump, then entering a rectifying tower with the height of 2.3m, the inner diameter of 450mm and taking a stepped ring as a filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 110 ℃ and the pressure of 80Pa and the rotating speed of 450r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 80Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) controlling the reflux ratio to be 3 through a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting the light component liquid through a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of eicosapentaenoic acid methyl ester C20:5 and docosahexaenoic acid methyl ester C22:6 respectively.
(e) And the fatty acid methyl ester part in the wiped film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to a stripping section of the rectifying tower and the wiped film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 8
The raw material adopted in the example is algae oil, and the acid value is 3.1mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of the algae oil comprises the following specific steps:
(a) Taking ionic liquid [ BHSO ] with mass ratio of 1:3:39 3 MIM]HSO 4 Adding seaweed oil and methanol into a reaction container together; placing the reaction vessel in a water bath at 70deg.C, stirring the mixed solution in the vessel until the algae oil and methanol are in ionic liquid [ BHSO ] 3 MIM]HSO 4 Fully reacting under the catalysis of the catalyst to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) Separating out [ BHSO ] 3 MIM]HSO 4 The ionic liquid is recovered for reuse after a small amount of methanol and water are removed by rotary evaporation at 130 ℃; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.31 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C20-C22 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 80 ℃ from a raw material storage tank through a feeding metering pump at the flow rate of 51.2mL/min, then entering a rectifying tower with the height of 2.5m, the inner diameter of 1000mm and theta rings as a filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 150 ℃ and the pressure of 140Pa and the rotating speed of 501r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser through the top of the rectifying tower with the pressure of 140Pa to become a light component, and is liquefied under the cooling effect of condensed water; and (3) refluxing part of light component liquid with the reflux ratio controlled to be 9 into the rectifying tower through a reflux ratio controller, collecting the other part of light component liquid part into a cooler, extracting the light component liquid part through a distilled product extraction pump, and finally, carrying out sampling detection analysis to respectively collect liquid products with the mass percent purity of more than 98% and containing single components of eicosapentaenoic acid methyl ester C20:5 and docosahexaenoic acid methyl ester C22:6.
(e) And the fatty acid methyl ester part in the film scraping type film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is respectively refluxed to the stripping section of the rectifying tower and the film scraping type film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
Example 9
The raw material adopted in the example is fish oil, and the acid value is 4mgKOH/g measured by the method of national standard GB-T5530-2005.
(1) The pretreatment of fish oil comprises the following specific steps:
(a) Taking ionic liquid [ Bmim ] with mass ratio of 1:2:36]Br-CuCl 2 Adding fish oil and methanol into a reaction container together; the reaction vessel is placed in a water bath with the temperature of 75 ℃, and the mixed solution in the vessel is stirred until the fish oil and the methanol are in ionic liquid [ Bmim ]]Br-CuCl 2 Fully reacting under the catalysis of the catalyst to generate a plurality of fatty acid methyl ester mixtures with acid values smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) Isolating [ Bmim ]]Br-CuCl 2 The ionic liquid is recovered for reuse after a small amount of methanol and water are removed by rotary evaporation at 140 ℃; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.19 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C20-C22 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 60 ℃ from the raw material tank at the flow rate of 20mL/min through a feeding metering pump, then entering a rectifying tower with the height of 1.7m and the inner diameter of 500mm and using glass spring filler as bulk filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower, part of the fatty acid methyl ester is vaporized and rises, the other part of the fatty acid methyl ester is lowered into a Roots vacuum pump reaching a stripping section through a filler, then the fatty acid methyl ester continuously flows downwards through a gap of an internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 180 ℃ and the pressure of 200Pa and the rotating speed of 100r/min through the stripping section of the rectifying tower;
(c) After the fatty acid methyl ester in the film scraping type film reboiler is heated, the fatty acid methyl ester rises after being partially vaporized, and enters a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the rectifying tower top with the tower top pressure of 200Pa to become a light component, and is liquefied under the cooling effect of condensed water; and controlling the reflux ratio to be 10 by a reflux ratio controller, refluxing part of light component liquid into a rectifying tower, collecting the other part of light component liquid into a cooler, extracting by a distilled product extraction pump, and finally, sampling, detecting and analyzing to collect liquid products with the mass percent purity of more than 98% and containing single components of eicosapentaenoic acid methyl ester C20:5 and docosahexaenoic acid methyl ester C22:6 respectively.
(e) And the fatty acid methyl ester part in the wiped film reboiler is regulated by a discharge proportion distributor, one part of fatty acid methyl ester part is refluxed to a stripping section of the rectifying tower and the wiped film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharge pump.
Example 10
This example used the fish oil of example 9 as a starting material.
(1) The pretreatment of fish oil comprises the following specific steps:
(a) Taking an ionic liquid mixture [ Bmim ] with the mass ratio of 1:6:24]Br-Ni 2 Cl 4 And [ QPS ]]PW, fish oil and methanol are added into a reaction vessel together; the reaction vessel was placed in a water bath at 80℃and the mixture was stirred until the fish oil and methanol were mixed in an ionic liquid [ Bmim ]]Br-Ni 2 Cl 4 And [ QPS ]]Fully reacting under the catalysis of PW to generate a plurality of fatty acid methyl ester mixtures with acid value smaller than 1;
(b) After the reaction is finished, separating the ionic liquid and a plurality of fatty acid methyl ester mixtures with acid values smaller than 1 by decantation, wherein the plurality of fatty acid methyl ester mixtures are biodiesel;
(c) Separating the ionic liquid mixture [ Bmim ]]Br-Ni 2 Cl 4 And [ QPS ]]PW is recovered for reuse after rotary evaporation at 150 ℃ to remove a small amount of methanol and water; the acid value of the obtained biodiesel is measured by a national standard GB-T5530-2005 method: s=0.21 mgKOH/g.
(2) The high vacuum precise separation of the fatty acid methyl ester of C20-C22 comprises the following specific steps:
(a) Putting the mixture of various fatty acid methyl esters obtained in the step 1 into a raw material tank, pumping the mixture into a preheater with the temperature of 40 ℃ from the raw material tank at the flow rate of 85mL/min through a feeding metering pump, then entering a rectifying tower with the height of 1.3m and the inner diameter of 750mm and taking a stepped ring as a filler, and then uniformly distributing the hot fatty acid methyl ester raw material into a stripping section of the rectifying tower through a feeding distributor;
(b) The fatty acid methyl ester enters the rectifying tower to be partially vaporized and ascended, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then the fatty acid methyl ester continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, and finally enters a wiped film reboiler with the temperature of 150 ℃ and the pressure of 101Pa and the rotating speed of 20r/min through the stripping section of the rectifying tower;
(c) After the heavy components of fatty acid methyl ester in the film scraping type film reboiler are heated, the heavy components are partially vaporized and then rise, and the heavy components enter a stripping section and a rectifying section of the rectifying tower in sequence through high vacuum provided by a Roots vacuum pump, so that gas-liquid mass transfer is realized with liquid flowing down above the stripping section and the rectifying section;
(d) The gas phase component in the rectifying tower finally enters a condenser from the top of the rectifying tower with the pressure of 101Pa to become a light component, and is liquefied under the cooling action of condensed water; under the control of a reflux ratio controller with the reflux ratio of 6, part of light component liquid flows back into the rectifying tower, the other part of light component liquid is collected into the cooler and is extracted by a distilled matter extraction pump, and finally, sampling detection analysis is carried out, and liquid products with the mass percent purity of more than 98% and containing single components of eicosapentaenoic acid methyl ester C20:5 and docosahexaenoic acid methyl ester C22:6 are respectively collected.
(e) And the fatty acid methyl ester part in the wiped film reboiler is regulated by a discharging proportion distributor, one part of fatty acid methyl ester part is refluxed to the upper part of the stripping section filler tower section and the wiped film reboiler under the action of a heavy component reflux pump so as to keep the kettle liquid free of light components, and the other part of fatty acid methyl ester part is extracted by a heavy component discharging pump.
The above embodiments have specifically described the method of the present invention, but the present invention is not limited to the above embodiments, and experimental conditions and methods may be flexibly changed without departing from the spirit of the present invention.

Claims (2)

1. An in-tower pumping type high vacuum rectification method for precisely separating C16-C22 fatty acids is characterized by comprising the following steps:
(1) The pretreatment of the grease comprises the following specific steps:
(a) Adding a catalyst, grease and methanol into a reaction container together, then placing the reaction container into a water bath at 50-100 ℃, and stirring the mixed solution in the container until the grease and the methanol fully react under the action of the catalyst to obtain a plurality of fatty acid methyl ester mixture pretreatment products;
(b) After the reaction is finished, separating a mixture pretreatment product of a plurality of fatty acid methyl esters from the mixture in the reaction vessel;
(c) Rotary evaporating the residual substances in the reaction vessel at 90-150 ℃ to recover a small amount of methanol and water, and then recovering and treating the residual substances;
(2) The separated mixture of various fatty acid methyl esters is precisely separated in high vacuum, and the specific steps are as follows:
(a) Pumping a plurality of fatty acid methyl esters into a feed preheater with the temperature of 40-180 ℃ from a raw material storage tank through a feed metering pump at the flow rate of 2.5-100 mL/min, then entering a rectifying tower from a feed inlet of the rectifying tower, and then uniformly distributing hot fatty acid methyl ester raw materials into a stripping section of the rectifying tower through a feed distributor;
(b) The fatty acid methyl ester entering the rectifying tower is partially vaporized and rises, the other part of the fatty acid methyl ester descends through the filler and reaches the Roots vacuum pump of the stripping section, then continuously flows downwards through the gap of the internal gear of the Roots vacuum pump, finally enters the reboiler through the stripping section of the rectifying tower, and the temperature of the reboiler is 100-180 ℃ and the pressure is 2-200 Pa;
(c) The fatty acid methyl ester entering the reboiler is heated, partially vaporized and then ascended, and then the high vacuum provided by the Roots vacuum pump sequentially enters a stripping section and a rectifying section of the rectifying tower, and the vaporized fatty acid methyl ester and liquid flowing down from the upper part in the rectifying tower realize gas-liquid mass transfer in the process;
(d) The gas phase components in the rectifying tower finally enter a condenser from the rectifying tower top with the tower top pressure of 0.65-200 Pa to be liquefied to form light component condensate, then one part of condensate flows back into the rectifying tower with the reflux ratio of 1-10 under the control of a reflux ratio controller, the other part of condensate enters a cooler and is extracted by a distilled product extraction pump, finally sampling detection analysis is carried out, and products which are obtained from the rectifying tower top and contain single components of methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, eicosapentaenoic acid methyl ester and docosahexaenoic acid methyl ester with the mass percent purity of more than 98% are respectively collected according to the sequence of the products from the tower top;
(e) The fatty acid methyl ester part in the reboiler is regulated by a discharging proportion distributor, one part of the fatty acid methyl ester part is respectively refluxed to the stripping section of the rectifying tower and the reboiler under the action of a heavy component reflux pump, and the other part of the fatty acid methyl ester part is extracted by a heavy component discharging pump;
the grease comprises animal and vegetable grease rich in stearic acid, oleic acid and linoleic acid or one of seaweed oil rich in eicosapentaenoic acid and docosahexaenoic acid, fish oil and waste fish oil with a high acid value of more than 2 or swill-cooked dirty oil.
2. The method for in-column pumping high vacuum rectification of C16 to C22 series fatty acids according to claim 1, wherein the method comprises the steps of: the catalyst is ionic liquid or KOH, caO, H 2 SO 4 An acid or a base represented by Amberlyst 15; wherein the ionic liquid catalyst comprises at least one of the following components [ BHSO ] 3 MIM]HSO 4 、[(CH 2 ) 3 SO 3 HMIM][HSO 3 ]Representative imidazoles and the use of [ (CH) 3 CH 2 ) 3 N(CH 2 ) 3 SO 3 H][C 7 H 7 O 3 S]Quaternary ammonium salts as representatives
Figure QLYQS_1
Acidic ionic liquid [ Bmim ]]Br-CuCl 2 、[Bmim]Br-FeCl 3 、[Bmim]Br-CuCl、[Bmim]Br-Fe 2 Cl 6 、[Bmim]Br-Ni 2 Cl 4 As a representative Lewis acidic ionic liquid, a method of preparing the same, and a method of preparing the same 3 S-(CH 2 ) 3 -NEt 3 ]Cl-FeCl 3 、[BSO 3 HMIM]HSO 4 -Fe 2 (SO 4 ) 3 As representative of the double acid ionic liquid, the method is characterized by [ BTBD]OH、[TBA]OH、[Hnmm]Basic ionic liquid represented by OH, represented by [ PyPS ]]PW、[TMAPS]PW、[MIMPS]PW and [ QPS ]]PW is any one or a mixture of any at least two ionic liquids in the heteropolyacid ionic liquids. />
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