CN105695104A - Intra-tower pump suction type high vacuum distillation method and device for precise separation of C16-C22 fatty acids - Google Patents

Intra-tower pump suction type high vacuum distillation method and device for precise separation of C16-C22 fatty acids Download PDF

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CN105695104A
CN105695104A CN201610187103.2A CN201610187103A CN105695104A CN 105695104 A CN105695104 A CN 105695104A CN 201610187103 A CN201610187103 A CN 201610187103A CN 105695104 A CN105695104 A CN 105695104A
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rectifying column
fatty acid
pump
methyl ester
tower
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CN105695104B (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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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 an intra-tower pump suction type high vacuum distillation method and device for precise separation of C16-C22 fatty acids. The high vacuum distillation method comprises the following steps: firstly taking heat sensitive materials with a high additional value, such as animal and vegetable oil, as raw materials, adopting plasma liquid and the like as an esterification and transesterification catalyst, and obtaining mixture of multiple fatty acid methyl esters with high yield in one step; secondly, in a distillation tower with almost zero pressure drop, carrying out high vacuum distillation operation on the formed multiple fatty acid methyl esters through catalysis; and finally separating and purifying, so that single fatty acid methyl esters such as timnodonic acid methyl ester, docosahexoenoic acid methyl ester, methyl palmitate, methyl stearate, methyl oleate and methyl linoleate with the mass fraction more than 98% respectively are obtained. The whole technological method is simple and clear, the operation is simple, the equipment cost is low, the energy is saved, and the enlargement can be easily realized.

Description

Pump suction type high vacuum rectification method and device in the tower that a kind of C16～C22 series fatty acid precision separates
Technical field
The present invention relates to chemical industry mass transfer and separation field, particularly relate to pump suction type high vacuum rectification method and device in the tower that a kind of C16～C22 series fatty acid precision separates。
Background technology
China's marine resources enrich, wherein the yield of fresh-water fishes position especially is at the forefront in the world, therefore produced fish oil substantial amounts in every production activity, and fish oil still contains substantial amounts of high added value fatty acid, i.e. eicosapentaenoic acid (EPA) and docosahexenoic acid (DHA), two both of which are the indispensable important nutrients of human body, wherein eicosapentaenoic acid can effectively help to reduce the content of cholesterol and triglyceride, promote saturated fat acid metabolic in human body, thus playing reduction blood viscosity, promote blood circulation, improve tissue oxygen supply and allaying tiredness；For docosahexenoic acid, cranial nerve growth promoter, baby's visual development, child intelligence are grown critically important effect of playing by it, and it also has antiallergic, strengthens the effects such as immunity simultaneously。Except fish oil, all containing abundant oils and fats in the cell such as algal oil, plant seed, sarcocarp, Fructus Maydis, content is different with raw material, for instance the oil content of Testa oryzae is about 12%～20%, and the oil content of dry coconut flesh is about 63%～70%。General milling process or solvent extraction method obtain。Some Vegetable oil lipoproteines in Oleum Arachidis hypogaeae semen, Oleum Ricini the fatty acid of triglyceride except Palmic acid, stearic acid, oleic acid, linoleic acid, except linolenic acid etc., sometimes also have special erucic acid, arachidic acid, eleostearic acid, ricinoleic acid etc.。These fatty acids are widely used in the numerous areas such as the preparation of auxiliary agent, oil dope, surfactant, lubricant and other organic chemicals, closely related with people's productive life。
Therefore comprehensive china natural resources advantage, widen animals and plants product deep processing value space, reduce the wasting of resources and according to fish oil and Semen Maydis wet goods oils and fats ingredient feature, the animal and plant fat preparative separation such as fish oil are utilized to purify the fatty acid obtaining high added value therein, it is possible not only to promote the economic worth of raw material, the high assignments fatty acid purified can meet medicine and health-product market, meets the grand strategy of overall sustainable development。
For separating-purifying aspect, common means have urea clathration, supercritical extraction, molecular distillation, low temperature crystallization, chromatographic isolation, solvent extraction, the method such as silver ion complexation and metal salt precipitate, but separation purity is not high on the one hand for above method, it is typically only capable to the saturated fatty acid methyl ester class obtaining higher degree and unsaturated fatty acid methyl ester series products, and almost cannot obtain single high purity fatty acid methyl ester, particularly with methyl stearate, methyl oleate and methyl linoleate, on the other hand, currently also all there is instability in these methods, separation difficulty, the problem such as solvent recovery and environmental pollution。In Fig. 1, (a) is methyl hexadecanoate (C16:0)；B () is methyl stearate (C18:0)；C () is methyl oleate (C18:1)；D () is methyl linoleate (C18:2), in Fig. 2, (a) is methyl eicosapentaenoic acid (C20:5)；B () is docosahexenoic acid (C22:6)。As shown in Figure 1, rear three difference structurally is only one to two double bonds, and this difference resulted between rear three in physicochemical properties is only small, and conventional separation means rarely has can by completely isolated for these three kinds of materials；For the methyl eicosapentaenoic acid in Fig. 2 and Methyl docosahexaenoate, again because it contains substantial amounts of double bond structure, therefore the two space structure is complicated, and to sensitive, perishable, both all cannot be efficiently separated and obtain substantial amounts of simple substance sterling by the aforementioned separation means being previously mentioned。
As isolation technics rectification between material widely used in current chemical field, can also serve as the means of high added value fatty acid in separating-purifying animal and plant fat。But animal and plant fat and separate the high added value fatty acid obtained from which and broadly fall into heat-sensitive substance, heat-sensitive substance refers to thermally sensitive material, when it is heated to a certain degree, this material will go bad, and namely generates other chemical substances by reactions such as decomposition, polymerizations。And want separating-purifying to obtain these heat sensitive materials, tradition rectification mode is difficult to。Therefore, the general problem solved in tradition rectification has two kinds of ways, and one is by adding inhibitor, slows down the speed of heat sensitive material decomposition or polymerization；Another kind of way is then the vacuum improving tower top, tower reactor, improve vacuum on the one hand and can increase the relative volatility between the heat-sensitive substance that physical property is similar, can be easily obtained the single heat-sensitive substance that high purity yield is big, on the other hand, improve vacuum and can reduce the boiling point of heat-sensitive substance, make its boiling point as far as possible lower than temperature time perishable, thus ensureing that heat-sensitive substance is not destroyed。For the method for purification of a lot of heat sensitive materials, the method for membrane distillation also can being adopted in practical application to purify, membrane distillation is little due to vacuum resistance, makes to realize between material separating under high vacuum condition。This is advantageous for the process of heat sensitive material。
But for first method, although adding inhibitor can the product purity improving heat-sensitive substance to a certain extent and can slow down the speed that heat-sensitive substance is rotten when producing, but the interpolation of inhibitor not only increases cost, whether environment all can be improved the production cost of heat-sensitive substance separating-purifying by the subsequent recovery of inhibitor and inhibitor simultaneously；For second method, prior art can improve the vacuum of corresponding rectifying column tower top, but the vacuum of uncontrollable tower reactor, and to obtain purity height, heat-sensitive substance that yield is high, the height of rectifying column need to improve accordingly, and the vacuum of tower reactor decreases, bottom temperature increases, the danger that heat-sensitive substance now can go bad。Therefore, for this situation, for improving the vacuum of tower reactor, make bottom temperature reduce frequently with multitower serial operation, increase the vacuum of tower reactor, but equipment cost can increase accordingly, and produce huge energy consumption。In addition, the another kind of technology improving rectifying tower vacuum degree is to add pressure regulator inside rectifying column, to reduce pressure drop, but rectifying column internal pressure-regulating device has only small compression ratio due to the structure of its fan blade, when relatively rough vacuum, there is certain effect, along with the raising of vacuum, the voltage regulation result of fan blade is lost gradually, so the tower problem of pressure drop of high vacuum rectification can not be solved。Owing to the resistance of molecular distillation is only small, can realize between material separating under high vacuum condition, therefore, purify the method that heat-sensitive substance may be used without molecular distillation, but molecular distillation only has the separation efficiency of single-stage column plate, still cannot accomplish high efficiency separation。
In sum, methyl eicosapentaenoic acid is rarely had report with Methyl docosahexaenoate or the completely isolated technology obtaining the significantly high single fat acid methyl ester of purity of methyl stearate, methyl oleate and methyl linoleate, this seriously inhibits the research further of high purity fatty acid methyl ester and application。
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, pump suction type high vacuum rectification method and device in the tower that a kind of C16～C22 series fatty acid precision separates is provided, the method and device are possible not only to while improving rectifying column height to remain to accomplish to reduce tower reactor pressure, improve the vacuum of tower reactor, and it is adiabatic in can ensure that tower, heat loss is minimum, considerably reduce energy consumption, can purify and obtain mass percent methyl eicosapentaenoic acid more than 98% respectively, Methyl docosahexaenoate, methyl hexadecanoate, methyl stearate, fatty acid esters such as methyl oleate and methyl linoleate and simple to operate。
The present invention is achieved through the following technical solutions:
Pump suction type high vacuum rectification method in the tower that a kind of C16～C22 series fatty acid precision separates, it comprises the following steps:
(1) pretreatment of oils and fats, concretely comprises the following steps:
A catalyst, oils and fats and methanol are added in reaction vessel by () jointly, then reaction vessel is placed in 50～100 DEG C of water baths, stirs mixed liquor in this container until oils and fats and methanol are fully obtained by reacting multiple fatty acid methyl ester admixture pretreatment product under catalyst action；
B () reaction terminates after, will separate in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel；
(c) by surplus materials in reaction vessel after at 90～150 DEG C, rotary evaporation reclaims a small amount of methanol and water, recycling；
(2) adopt fine vacuum precision to separate isolated multiple fatty acid methyl ester admixture, concretely comprise the following steps:
A multiple fatty acid methyl ester is pumped into temperature in the feed preheater of 40～180 DEG C by charging dosing pump with the flow velocity of 2.5～100mL/min by () from raw material storage tank, then enter rectifying column from the charging aperture of rectifying column, be evenly distributed in the stripping section of rectifying column via feed distributor with after heat fatty acid methyl ester raw material；
B () enters the fatty acid methyl ester moiety vaporization of rectifying column and rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, it is further continued for being flowed downward by the gap of Roots vaccum pump internal gear, entering in reboiler eventually through rectifying column stripping section, the temperature of described reboiler is 100～180 DEG C and pressure is 2～200Pa；
C the fatty acid methyl ester in () reboiler is through heating, rise after part vaporization, the fine vacuum that then passing through Roots vaccum pump provides sequentially enters stripping section and the rectifying section of rectifying column, and the fatty acid methyl ester vaporized in the process realizes gas-liquid mass transfer with the liquid flow down from rectifying column internal upper part；
D the gaseous component in () rectifying column is finally entered into liquefaction in condenser by the rectifying tower top that tower top pressure is 0.65～200Pa and forms light component condensed fluid, then under the control of reflux ratio controller, a part of condensed fluid is back in rectifying column with the reflux ratio of 1～10, another part condensed fluid enters in cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, according to overhead product sequencing out, collect the mass percent purity that obtains of rectifying tower top respectively and comprise methyl hexadecanoate more than 98%, methyl stearate, methyl oleate, methyl linoleate, the product of the single component of methyl eicosapentaenoic acid and Methyl docosahexaenoate；
E the adjustment by discharging proportional divider of the fatty acid methyl ester moiety in () reboiler, a part is back to the stripping section of rectifying column respectively with reboiler under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction；
Described oils and fats includes rich in stearic acid, oleic acid and linoleic animal and plant fat or rich in the one in the useless fish oil of eicosapentaenoic acid, the algal oil of docosahexenoic acid, fish oil and the acid number high acid value more than 2 or waste oil。
Pump suction type high vacuum rectification device in the tower that a kind of C16～C22 series fatty acid precision separates, it includes rectifying column, described rectifying column has charging aperture, described rectifying column comprises rectifying section, stripping section and reboiler three part, tower top at described rectifying column is connected to condenser, described condenser is connected with vacuum system by vacuum tube, the condensate outlet of described condenser is connected with the inlet of reflux ratio controller, one liquid outlet of described reflux ratio controller by vacuum tube successively with cooler and steam thing extraction pump and be connected, another liquid outlet of described reflux ratio controller is connected with the inlet of backflow vacuum tube, the liquid outlet of described backflow vacuum tube is inserted in rectifying column by the refluxing opening of rectifying column, one reflux splitter is arranged in the rectifying column below backflow vacuum tube, reboiler and discharging proportional divider it is being connected with in turn at the bottom of the tower of described rectifying column, one outlet of described discharging proportional divider connects heavy constituent extraction pump by vacuum tube and another outlet connects heavy constituent reflux pump by vacuum tube, the liquid outlet of described heavy constituent reflux pump is respectively through the bottom filling valvular heavy constituent backflow vacuum tube and the stripping section of rectifying column, the liquid return hole of reboiler is connected, one heavy constituent reflux splitter is arranged in the rectifying column below heavy constituent backflow vacuum tube exit, one raw material storage tank by vacuum tube successively with charging dosing pump, effusion meter, the charging aperture of feed preheater and rectifying column is connected, one feed distributor is arranged in the rectifying column below charging aperture place, rectifying section at rectifying column is separately installed with at least one Roots vaccum pump with stripping section。
Compared with currently existing technology, the major advantage of the present invention is mainly reflected in:
1. the experimental provision of the present invention and the vitals of experimental technique are Roots vaccum pumps, it has the bigger speed of evacuation and high efficiency under a high vacuum, withdrawing fluid is utilized to can overcome the disadvantages that the problem that under high temperature, Roots vaccum pump gear clearance is excessive, downward passage is provided to withdrawing fluid, it is to avoid additionally increase the liquid trap between tower joint because increasing the use of Roots vaccum pump while making Roots vaccum pump compression ratio improve。
2. the method adding Roots vaccum pump in high vacuum rectification device, thoroughly solves the existence of high vacuum rectification tower reactor and king-post endogenous cause of ill pressure drop and causes the problem that in tower, vacuum is low, and this allows full tower become a reality without pressure drop high vacuum rectification。The present invention reduces the pressure of tower reactor greatly, so that bottom temperature reduces, this not only protects heat-sensitive substance not to be destroyed, and increases the relative volatility between component simultaneously, allows this experimental provision have the feature of high efficiency separation ability。
3. the phase component heating region time of staying in experimental provision of the present invention is short, such that it is able to reduce the generation of the metamorphic reaction of heat-sensitive substance further；
4. the experimental provision of the present invention and method can make the heating-up temperature of reboiler be greatly lowered, and not only expand the range of application of high vacuum rectification, also act as effect that is energy-conservation and that reduce equipment manufacturing cost。Provide a kind of novel distillation theory for separating-purifying heat-sensitive substance, there is broad prospect of application。Adopting this experimental provision and experimental technique can purify single fat acid fat such as obtaining mass percent methyl eicosapentaenoic acid more than 98%, Methyl docosahexaenoate, methyl hexadecanoate, methyl stearate, methyl oleate and methyl linoleate respectively, this method is energy-conservation, simple to operate and environmental protection is pollution-free。
5. this experimental provision can ensure that adiabatic supercharging in tower, and heat loss is only small, considerably reduces energy consumption。
6. the rectification height of this experimental provision and the visual concrete condition of the number of Roots vaccum pump determine, therefore, are applicable to the system that this device is easily separated extensive, and this experimental provision has, and the production capacity amplitude of accommodation is big and the feature of flexible and convenient operation。
Accompanying drawing explanation
Fig. 1 is contained main fatty acid methyl ester molecular structural formula in the biodiesel prepared with vegetable oil for raw material；
Fig. 2 is high added value fatty acid methyl ester molecular structural formula contained in the biodiesel prepared with fish oil etc. for raw material；
Fig. 3 is heat sensitive material eicosapentaenoic acid with docosahexenoic acid (EPA+DHA) content in time and temperature variation curve (P=2kPa)；
Fig. 4 is that heat-sensitive substance eicosapentaenoic acid varies with temperature curve (P=200Pa, t=5h) with docosahexenoic acid (EPA, DHA) content；
Fig. 5 is pump suction type high-vacuum installation structural representation in the tower that C16～C18 of the present invention and C20～C22 series fatty acid precision separate。
Detailed description of the invention
Being below the specific embodiment of the present invention, described embodiment is for the present invention is further elaborated, rather than the restriction present invention。
First, with the heat sensitive material rich in high added value for raw material, such as animal and plant fat, carrying out being esterified and transesterification under catalyst action, a step just can obtain the multiple fatty acid methyl ester admixture of high yield, i.e. biodiesel, and this reaction condition is gentle。Meanwhile, when adopting ionic liquid, solid acid and solid base etc. as catalyst, convenient catalyst reclaims and can repeatedly use, environmental protection；
Secondly, utilize the present invention can increase the experimental provision of high vacuum rectification tower tower reactor and the vacuum in tower, when in Full distillation tower almost without pressure drop, the biodiesel that catalysis is formed carries out high vacuum rectification operation, is finally recovered and purifies single fat acid methyl ester such as respectively obtaining mass fraction all methyl eicosapentaenoic acids more than 98%, Methyl docosahexaenoate, methyl hexadecanoate, methyl stearate, methyl oleate and methyl linoleate；Integrated artistic method is simple and clear, simple to operate, equipment cost is low, energy-conservation and environmental protection, great Economic Application prospect。
Simultaneously, by Fig. 3 and Fig. 4, eicosapentaenoic acid (EPA) and docosahexenoic acid (DHA) at high temperature a period of time can go bad, and the present invention can effectively avoid the rotten minimizing of high added value component that the heat sensitive material containing such as EPA and DHA etc. causes because retaining a percentage of the total profits for the enterprise's own use overlong time in high temperature system。
According to principles above, pump suction type high vacuum rectification method in the tower that a kind of C16～C22 series fatty acid precision of employing the invention described above separates, it comprises the following steps:
(1) pretreatment of oils and fats, concretely comprises the following steps:
A catalyst, oils and fats and methanol are added in reaction vessel by () jointly, the ratio wherein adding the catalyst in reaction vessel, thermal sensitivity oils and fats and methanol is not limit, but at least ensure that the fatty acid part glyceride transfer from free fatty Yu more difficult utilization as much as possible in thermal sensitivity oils and fats becomes feasible to the fatty acid methyl ester of unified production application, then reaction vessel is placed in 50～100 DEG C of water baths, stirs mixed liquor in this container until oils and fats and methanol are fully obtained by reacting multiple fatty acid methyl ester admixture pretreatment product under catalyst action；
B () reaction terminates after, separating in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel, multiple fatty acid methyl ester admixture is biodiesel；
(c) by surplus materials in reaction vessel after at 90～150 DEG C, rotary evaporation reclaims a small amount of methanol and water, recycling；
(2) adopt fine vacuum precision to separate isolated multiple fatty acid methyl ester admixture, concretely comprise the following steps:
A multiple fatty acid methyl ester is pumped into temperature in the feed preheater of 40～180 DEG C by charging dosing pump with the flow velocity of 2.5～100mL/min by () from raw material storage tank, then enter rectifying column from the charging aperture of rectifying column, be evenly distributed in the stripping section of rectifying column via feed distributor with after heat fatty acid methyl ester raw material；
B () enters the fatty acid methyl ester moiety vaporization of rectifying column and rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, it is further continued for being flowed downward by the gap of Roots vaccum pump internal gear, entering in reboiler eventually through rectifying column stripping section, the temperature of described reboiler is 100～180 DEG C and pressure is 2～200Pa；
C the fatty acid methyl ester in () reboiler is through heating, rise after part vaporization, the fine vacuum that then passing through Roots vaccum pump provides sequentially enters stripping section and the rectifying section of rectifying column, and the fatty acid methyl ester vaporized in the process realizes gas-liquid mass transfer with the liquid flow down from rectifying column internal upper part；
D the gaseous component in () rectifying column is finally entered into liquefaction in condenser by the rectifying tower top that tower top pressure is 0.65～200Pa and forms light component condensed fluid, then under the control of reflux ratio controller, a part of condensed fluid is back in rectifying column with the reflux ratio of 1～10, another part condensed fluid enters in cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, according to overhead product sequencing out, the mass percent purity that collection rectifying tower top obtains respectively methyl hexadecanoate more than 98%, methyl stearate, methyl oleate, methyl linoleate, the product of the single components such as methyl eicosapentaenoic acid and Methyl docosahexaenoate；
E the adjustment by discharging proportional divider of the fatty acid methyl ester moiety in () reboiler, a part is back to the stripping section of rectifying column respectively with reboiler under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Described oils and fats includes rich in stearic acid, oleic acid and linoleic animal and plant fat or rich in the one in eicosapentaenoic acid, the algal oil of docosahexenoic acid, fish oil and the acid number high acid value more than 2 useless fish oil, trench wet goods。
Described catalyst is ionic liquid or with KOH, CaO, H2SO4And Amberlyst15 etc. represent acid, alkali etc.；Wherein said ionic-liquid catalyst includes with [BHSO3MIM]HSO4、[(CH2)3SO3HMIM][HSO3] imidazoles that represents with [(CH3CH2)3N(CH2)3SO3H][C7H7O3S] for the quaternary ammonium salt of representativeAcidic ion liquid, with [Bmim] Br-CuCl2、[Bmim]Br-FeCl3、[Bmim]Br-CuCl、[Bmim]Br-Fe2Cl6、[Bmim]Br-Ni2Cl4For represent Lewis acidic ion liquid, with [HO3S-(CH2)3-NEt3]Cl-FeCl3、[BSO3HMIM]HSO4-Fe2(SO4)3For the bisgallic acid type ionic liquid represented, the alkali ionic liquid being representative with [BTBD] OH, [TBA] OH, [Hnmm] OH, with the mixture of any one in the heteropoly acid type ionic liquid that [PyPS] PW, [TMAPS] PW, [MIMPS] PW and [QPS] PW are representative or any at least two ionic liquid。
The ratio of described addition catalyst reactor, thermal sensitivity oils and fats and methanol is without particular/special requirement, it is recommended that the mol ratio of methanol and thermal sensitivity oils and fats is at least 3:1, catalyst amount is at least the 1% of methanol and thermal sensitivity oils and fats molar content。
Described rectifying column is made up of multiple towers joint, and the packed height in each tower saves is 0.1～2.5m。
The tower diameter of described rectifying column is 5～1000mm。
Described rectifying column filler includes the structured packings such as screen waviness plate, ripple packing；The random packings such as Pall ring, cascade ring, θ ring filler, glass spring filler。
Described reboiler is Wiped Film Evaporator or other heating kettles etc., and when reboiler is Wiped Film Evaporator, scraper plate rotating speed is 20～1000r/min；Ensureing that bottom temperature remains to have quite or exceed well over tradition rectification separating effect while relatively low。
As shown in Figure 3, realize the inventive method a kind of C16～C22 series fatty acid precision separate tower in pump suction type high vacuum rectification device, it includes rectifying column, described rectifying column has charging aperture, described rectifying column comprises rectifying section 5, stripping section 7 and reboiler 9 three part, tower top at described rectifying column is connected to condenser 1, described condenser 1 is connected with vacuum system 13 by the first vacuum tube, the condensate outlet of described condenser 1 is connected with the inlet of reflux ratio controller 14, one liquid outlet of described reflux ratio controller 14 by the second vacuum tube successively with cooler 15 and steam thing extraction pump 16 and be connected, another liquid outlet of described reflux ratio controller 14 is connected with the inlet of backflow vacuum tube, the liquid outlet of described backflow vacuum tube is inserted in rectifying column 2 by the refluxing opening of rectifying column 2, one reflux splitter 4 is arranged in the rectifying column 2 below backflow vacuum tube, reboiler 9 and discharging proportional divider 11 it is being connected with in turn at the bottom of the tower of described rectifying column 2, one outlet of described discharging proportional divider 11 connects heavy constituent extraction pump 10 by vacuum tube and another outlet connects heavy constituent reflux pump 12 by vacuum tube, the liquid outlet of described heavy constituent reflux pump 12 refluxes respectively through the heavy constituent equipped with valve 21 bottom of stripping section 7 of vacuum tube and rectifying column 2, the liquid return hole of reboiler 9 is connected, one heavy constituent reflux splitter 8 is arranged in the rectifying column 2 below heavy constituent backflow vacuum tube exit, one raw material storage tank 19 by the 3rd vacuum tube successively with charging dosing pump 20, effusion meter 18, the charging aperture of feed preheater 17 and rectifying column 2 is connected, one feed distributor 6 is arranged in the rectifying column 2 below charging aperture place, rectifying section 5 at rectifying column 2 is separately installed with at least one Roots vaccum pump 3 with stripping section 7。
Described Roots vaccum pump can be built-in Roots vaccum pump or external Roots vaccum pump, and when using built-in Roots vaccum pump, this vacuum pump is placed in rectifying column；When using external Roots vaccum pump, rectifying column and external Roots vaccum pump are that screw is connected and sealing means employing magnetic seal between rectifying column and external Roots vaccum pump。
Described Roots vaccum pump adopts at least two leaf roots rotors。
Described Roots vaccum pump adopts Roots's profile of tooth。
Described Roots vaccum pump uses number no less than two, specifically can according to corresponding operating condition operating mode。
Embodiment 1
The raw material that this example adopts is certain high acid value vegetable oil, and measuring acid number through standard GB/T-T5530-2005 method is 23.6mgKOH/g。
(1) pretreatment of vegetable oil, concretely comprises the following steps:
A () takes ionic liquid [Bmim] Br-CuCl, vegetable oil and methanol that mass ratio is 1:2:34 and adds in reaction vessel in common；Reaction vessel is placed in 50 DEG C of water baths, stirs mixed liquor in this container until vegetable oil and methanol fully react under the catalytic action of ionic liquid [Bmim] Br-CuCl generates the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C (), by isolated [Bmim] Br-CuCl ionic liquid after at 90 DEG C, rotary evaporation removes a small amount of methanol and water, recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.19mgKOH/g。
(2) C16～C18 fatty acid methyl ester fine vacuum fine separation, concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 180 DEG C by charging dosing pump with the flow velocity of 2.5mL/min, then enter height for 0.1m, internal diameter be 300mm, with screen waviness plate for the rectifying column of structured packing, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 100 DEG C, pressure be 2Pa heating kettle in；
C fatty acid methyl ester is heated in () heating kettle after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 0.65Pa, become light component, and liquefy under condensed water cooling effect；It is back in rectifying column under the control of reflux ratio controller (reflux ratio is 1), light component fluids portion collection is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl hexadecanoate C16:0 and methyl stearate C18:0, methyl oleate C18:1 with methyl linoleate C18:2 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) heating kettle, a part is back in packed tower stripping section and heating kettle respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 2
The raw material that this example adopts is certain high acid value vegetable oil of embodiment 1。
(1) pretreatment of vegetable oil, concretely comprises the following steps:
A () takes mass ratio is that the CaO of 1:2:28, vegetable oil and methanol add in reaction vessel in common；Reaction vessel is placed in 100 DEG C of water baths, stirs mixed liquor in this container until vegetable oil and methanol are fully obtained by reacting multiple fatty acid methyl ester admixture under the catalytic action of CaO；
B () reaction terminates after, separating in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel, multiple fatty acid methyl ester admixture is biodiesel；
C in () reaction vessel, surplus materials is after at 100 DEG C, rotary evaporation reclaims a small amount of methanol and water, recycling。
(2) C16～C18 fatty acid methyl ester fine vacuum fine separation, concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 150 DEG C by charging dosing pump with the flow velocity of 50mL/min, then enter height for 1.8m, internal diameter be 700mm, with screen waviness plate for the rectifying column of structured packing, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 100 DEG C, pressure be 30Pa heating kettle in；
C fatty acid methyl ester is heated in () heating kettle after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 30Pa, become light component, and liquefy under condensed water cooling effect；It is back in rectifying column under the control of reflux ratio controller (reflux ratio is 1), light component fluids portion collection is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl hexadecanoate C16:0 and methyl stearate C18:0, methyl oleate C18:1 with methyl linoleate C18:2 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) heating kettle, a part is back in packed tower stripping section and heating kettle respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 3
The raw material that this example adopts is certain discarded Semen Maydis oil, and measuring acid number through standard GB/T-T5530-2005 method is 10.1mgKOH/g。
(1) pretreatment of discarded Semen Maydis oil, concretely comprises the following steps:
A () takes ionic liquid [BTBD] OH that mass ratio is 1:6:20, discarded Semen Maydis oil adds in reaction vessel in common with methanol；Reaction vessel is placed in 55 DEG C of water baths, stirs mixed liquor in this container until vegetable oil and methanol fully react under the catalytic action of ionic liquid [BTBD] OH generates the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C (), by isolated [BTBD] OH ionic liquid after at 100 DEG C, rotary evaporation removes a small amount of methanol and water, recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.21mgKOH/g。
(2) C16～C18 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 150 DEG C by charging dosing pump with the flow velocity of 40mL/min, then enter height for 1.0m, internal diameter be 5mm, with ripple packing for the rectifying column of structured packing, be evenly distributed in rectifying column stripping section via feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 170 DEG C, pressure is 160Pa, rotating speed be 250r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column is finally entered in condenser by the rectifying tower top that tower top pressure is 160Pa, become light component, and liquefy under condensed water cooling effect；It is 7 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids of another part is collected to cooler, and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl hexadecanoate C16:0 and methyl stearate C18:0, methyl oleate C18:1 with methyl linoleate C18:2 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in packed tower stripping section and Wiped Film reboiler respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 4
The raw material that this example adopts is certain discarded Semen Maydis oil of embodiment 3。
(1) pretreatment of discarded Semen Maydis oil, concretely comprises the following steps:
A () takes the H that mass ratio is 1:4:202SO4, discarded Semen Maydis oil adds in reaction vessel in common with methanol；Reaction vessel is placed in 75 DEG C of water baths, stirs mixed liquor in this container until vegetable oil and methanol are at H2SO4Catalytic action under be fully obtained by reacting multiple fatty acid methyl ester admixture；
B () reaction terminates after, separating in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel, multiple fatty acid methyl ester admixture is biodiesel；
(c) by surplus materials in reaction vessel after at 110 DEG C, rotary evaporation reclaims a small amount of methanol and water, recycling。
(2) C16～C18 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 130 DEG C by charging dosing pump with the flow velocity of 55mL/min, then enter height for 1.4m, internal diameter be 20mm, with ripple packing for the rectifying column of structured packing, be evenly distributed in rectifying column stripping section via feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 175 DEG C, pressure is 120Pa, rotating speed be 210r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column is finally entered in condenser by the rectifying tower top that tower top pressure is 120Pa, become light component, and liquefy under condensed water cooling effect；It is 7 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids of another part is collected to cooler, and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl hexadecanoate C16:0 and methyl stearate C18:0, methyl oleate C18:1 with methyl linoleate C18:2 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in packed tower stripping section and Wiped Film reboiler respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 5
The raw material that this example adopts is certain discarded Petiolus Trachycarpi oil, and measuring acid number through standard GB/T-T5530-2005 method is 16.3mgKOH/g。
(1) discarded palmitic pretreatment, concretely comprises the following steps:
A () takes ionic liquid [MIMPS] PW that mass ratio is 1:4:48, discarded Petiolus Trachycarpi oil adds in reaction vessel in common with methanol；Reaction vessel is placed in 60 DEG C of water baths, stirs mixed liquor in this container until vegetable oil and methanol fully react under the catalytic action of ionic liquid [MIMPS] PW generates the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C (), by isolated [MIMPS] PW ionic liquid after at 110 DEG C, rotary evaporation removes a small amount of methanol and water, recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.24mgKOH/g。
(2) C16～C18 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 130 DEG C by charging dosing pump with the flow velocity of 100mL/min, then enter height for 2m, internal diameter be 350mm, with Pall ring for the rectifying column of filler, be evenly distributed in rectifying column stripping section via feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 120 DEG C, pressure is 20Pa, rotating speed is the Wiped Film reboiler of 850r/min；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 20Pa, become light component, and liquefy under condensed water cooling effect；It is 4 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids portion collection of another part is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl hexadecanoate C16:0 and methyl stearate C18:0, methyl oleate C18:1 with methyl linoleate C18:2 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in rectifying column stripping section and Wiped Film reboiler respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 6
The raw material that this example adopts is the useless fish oil of certain high acid value, and measuring acid number through standard GB/T-T5530-2005 method is 20.9mgKOH/g。
(1) pretreatment of the useless fish oil of high acid value, concretely comprises the following steps:
A () takes the ionic liquid [(CH that mass ratio is 1:4.5:312)3SO3HMIM][HSO3], the useless fish oil of high acid value adds in reaction vessel in common with methanol；Reaction vessel is placed in 65 DEG C of water baths, stirs mixed liquor in this container until the useless fish oil of high acid value and methanol are at ionic liquid [(CH2)3SO3HMIM][HSO3] catalytic action under fully reaction generate the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C () is by isolated [(CH2)3SO3HMIM][HSO3] ionic liquid is after at 120 DEG C, rotary evaporation removes a small amount of methanol and water, recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.31mgKOH/g。
(2) C20～C22 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 110 DEG C by charging dosing pump with the flow velocity of 75mL/min, then enter height for 2m, internal diameter be 800mm, with cascade ring for the rectifying column of filler, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 110 DEG C, pressure is 10Pa, rotating speed be 700r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 10Pa, become light component, and liquefy under condensed water cooling effect；It is 2 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids portion collection of another part is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl eicosapentaenoic acid C20:5 and Methyl docosahexaenoate C22:6 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in rectifying column stripping section and Wiped Film reboiler respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 7
The raw material that this example adopts is the useless fish oil of certain high acid value in embodiment 6。
(1) pretreatment of the useless fish oil of high acid value, concretely comprises the following steps:
A () takes solid acid Amberlyst15, the useless fish oil of high acid value and methanol that mass ratio is 1:6:33 and adds in reaction vessel in common；Reaction vessel is placed in 60 DEG C of water baths, stirs mixed liquor in this container until the useless fish oil of high acid value is fully obtained by reacting multiple fatty acid methyl ester admixture with methanol under the catalytic action of solid acid Amberlyst15；
B () reaction terminates after, separating in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel, multiple fatty acid methyl ester admixture is biodiesel；
(c) by surplus materials in reaction vessel after at 120 DEG C, rotary evaporation receives a small amount of methanol and water, by filtration and recyclable solid acid Amberlyst15 catalyst。
(2) C20～C22 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 115 DEG C by charging dosing pump with the flow velocity of 65mL/min, then enter height for 2.3m, internal diameter be 450mm, with cascade ring for the rectifying column of filler, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 110 DEG C, pressure is 80Pa, rotating speed be 450r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 80Pa, become light component, and liquefy under condensed water cooling effect；It is 3 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids portion collection of another part is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl eicosapentaenoic acid C20:5 and Methyl docosahexaenoate C22:6 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in rectifying column stripping section and Wiped Film reboiler respectively to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 8
The raw material that this example adopts is algal oil, and measuring acid number through standard GB/T-T5530-2005 method is 3.1mgKOH/g。
(1) pretreatment of algal oil, concretely comprises the following steps:
A () takes the ionic liquid [BHSO that mass ratio is 1:3:393MIM]HSO4, algal oil and methanol adds in reaction vessel in common；Reaction vessel is placed in 70 DEG C of water baths, stirs mixed liquor in this container until algal oil and methanol are at ionic liquid [BHSO3MIM]HSO4Catalytic action under fully reaction generate the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C () is by isolated [BHSO3MIM]HSO4Ionic liquid is after at 130 DEG C, rotary evaporation removes a small amount of methanol and water, and recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.31mgKOH/g。
(2) C20～C22 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 80 DEG C by charging dosing pump with the flow velocity of 51.2mL/min, then enter height for 2.5m, internal diameter be 1000mm, with θ ring for the rectifying column of filler, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 150 DEG C, pressure is 140Pa, rotating speed be 501r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that pressure is 140Pa, become light component, and liquefy under condensed water cooling effect；It is 9 by reflux ratio controller by control of reflux ratio, the light component fluids of part is back in rectifying column, the light component fluids portion collection of another part is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl eicosapentaenoic acid C20:5 and Methyl docosahexaenoate C22:6 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, to keep still liquid without light component in a part of stripping section being back to rectifying column under the effect of heavy constituent reflux pump respectively and Wiped Film reboiler, another part passes through heavy constituent discharging pump extraction。
Embodiment 9
The raw material that this example adopts is fish oil, and measuring acid number through standard GB/T-T5530-2005 method is 4mgKOH/g。
(1) pretreatment of fish oil, concretely comprises the following steps:
A () takes ionic liquid [Bmim] Br-CuCl that mass ratio is 1:2:362, fish oil and methanol adds in reaction vessel in common；Reaction vessel is placed in 75 DEG C of water baths, stirs mixed liquor in this container until fish oil and methanol are at ionic liquid [Bmim] Br-CuCl2Catalytic action under fully reaction generate the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C () is by isolated [Bmim] Br-CuCl2Ionic liquid is after at 140 DEG C, rotary evaporation removes a small amount of methanol and water, and recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.19mgKOH/g。
(2) C20～C22 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 60 DEG C by charging dosing pump with the flow velocity of 20mL/min, then enter height for 1.7m, internal diameter be 500mm, with glass spring filler for the rectifying column of dumped packing, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B () enters the fatty acid methyl ester in rectifying column, part is vaporized rising, another part then declines in the Roots vaccum pump arriving stripping section by filler, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 180 DEG C, pressure is 200Pa, rotating speed be 100r/min Wiped Film reboiler in；
C fatty acid methyl ester is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that tower top pressure is 200Pa, become light component, and liquefy under condensed water cooling effect；Controlling reflux ratio by reflux ratio controller is 10, the light component fluids of part is back in rectifying column, the light component fluids portion collection of another part is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl eicosapentaenoic acid C20:5 and Methyl docosahexaenoate C22:6 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part is back in rectifying column stripping section and Wiped Film reboiler to keep still liquid without light component under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Embodiment 10
This example adopts the fish oil in embodiment 9 as raw material。
(1) pretreatment of fish oil, concretely comprises the following steps:
A () takes ionic liquid mixture [Bmim] Br-Ni that mass ratio is 1:6:242Cl4Add in reaction vessel in common with [QPS] PW, fish oil and methanol；Reaction vessel is placed in 80 DEG C of water baths, stirs mixed liquor in this container until fish oil and methanol are at ionic liquid mixture [Bmim] Br-Ni2Cl4Under catalytic action with [QPS] PW, fully reaction generates the acid number multiple fatty acid methyl ester admixture less than 1；
B () reaction terminates after, the multiple fatty acid methyl ester admixture less than 1 by decant separating ionic liquid and acid number, multiple fatty acid methyl ester admixture is biodiesel；
C () is by isolated ionic liquid mixture [Bmim] Br-Ni2Cl4With [QPS] PW after at 150 DEG C, rotary evaporation removes a small amount of methanol and water, recovery is reused；The biodiesel obtained is measured its acid number by standard GB/T-T5530-2005 method: S=0.21mgKOH/g。
(2) C20～C22 fatty acid methyl ester fine vacuum precision separates, and concretely comprises the following steps:
A () takes the multiple fatty acid methyl ester admixture obtained in step 1 and puts in head tank, and from raw material storage tank, it is pumped to temperature in the preheater of 40 DEG C by charging dosing pump with the flow velocity of 85mL/min, then enter height for 1.3m, internal diameter be 750mm, with cascade ring for the rectifying column of filler, be evenly distributed in rectifying column stripping section by feed distributor with after heat fatty acid methyl ester raw material；
B fatty acid methyl ester moiety vaporization that () enters in rectifying column rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, be further continued for being flowed downward by the gap of Roots vaccum pump internal gear, eventually through rectifying column stripping section enter temperature be 150 DEG C, pressure is 101Pa, rotating speed be 20r/min Wiped Film reboiler in；
C fatty acid methyl ester heavy constituent is heated in () Wiped Film reboiler after, rising, and the fine vacuum provided by Roots vaccum pump sequentially enters rectifying column stripping section, rectifying section after part vaporization, the liquid flow down with top realizes gas-liquid mass transfer；
D the gaseous component in () rectifying column finally enters in condenser via the rectifying tower top that pressure is 101Pa, become light component, and liquefy under condensed water cooling effect；Under the control of the reflux ratio controller that reflux ratio is 6, the light component fluids of part is back in rectifying column, another part, light component fluids portion collection is to cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, collects the fluid product that percent mass purity contains methyl eicosapentaenoic acid C20:5 and Methyl docosahexaenoate C22:6 single component more than 98% respectively。
The adjustment by discharging proportional divider of the fatty acid methyl ester moiety in (e) Wiped Film reboiler, a part be back under the effect of heavy constituent reflux pump above stripping section packed tower joint with Wiped Film reboiler in keep still liquid without light component, another part is by heavy constituent discharging pump extraction。
The method of the present invention has been carried out concrete description by above detailed description of the invention, but content of the present invention is not restricted to above case study on implementation, as long as without departing from, in the main scope of the present invention, can experiment condition and method be changed flexibly。

Claims (10)

1. pump suction type high vacuum rectification method in the tower of C16～C22 series fatty acid precision separation, it is characterised in that it comprises the following steps:
(1) pretreatment of oils and fats, concretely comprises the following steps:
A catalyst, oils and fats and methanol are added in reaction vessel by () jointly, then reaction vessel is placed in 50～100 DEG C of water baths, stirs mixed liquor in this container until oils and fats and methanol are fully obtained by reacting multiple fatty acid methyl ester admixture pretreatment product under catalyst action；
B () reaction terminates after, will separate in multiple fatty acid methyl ester admixture pretreatment product mixture from reaction vessel；
(c) by surplus materials in reaction vessel after at 90～150 DEG C, rotary evaporation reclaims a small amount of methanol and water, recycling；
(2) adopt fine vacuum precision to separate isolated multiple fatty acid methyl ester admixture, concretely comprise the following steps:
A multiple fatty acid methyl ester is pumped into temperature in the feed preheater of 40～180 DEG C by charging dosing pump with the flow velocity of 2.5～100mL/min by () from raw material storage tank, then enter rectifying column from the charging aperture of rectifying column, be evenly distributed in the stripping section of rectifying column via feed distributor with after heat fatty acid methyl ester raw material；
B () enters the fatty acid methyl ester moiety vaporization of rectifying column and rises, another part is then declined by filler and arrives in the Roots vaccum pump of stripping section, it is further continued for being flowed downward by the gap of Roots vaccum pump internal gear, entering in reboiler eventually through rectifying column stripping section, the temperature of described reboiler is 100～180 DEG C and pressure is 2～200Pa；
C () enters the fatty acid methyl ester in reboiler through heating, rise after part vaporization, the fine vacuum that then passing through Roots vaccum pump provides sequentially enters stripping section and the rectifying section of rectifying column, and the fatty acid methyl ester vaporized in the process realizes gas-liquid mass transfer with the liquid flow down from rectifying column internal upper part；
D the gaseous component in () rectifying column is finally entered into liquefaction in condenser by the rectifying tower top that tower top pressure is 0.65～200Pa and forms light component condensed fluid, then under the control of reflux ratio controller, a part of condensed fluid is back in rectifying column with the reflux ratio of 1～10, another part condensed fluid enters in cooler and by steaming thing extraction pump extraction, finally it is sampled detection to analyze, according to overhead product sequencing out, collect the mass percent purity that obtains of rectifying tower top respectively and comprise methyl hexadecanoate more than 98%, methyl stearate, methyl oleate, methyl linoleate, the product of the single component of methyl eicosapentaenoic acid and Methyl docosahexaenoate；
E the adjustment by discharging proportional divider of the fatty acid methyl ester moiety in () reboiler, a part is back to the stripping section of rectifying column respectively with reboiler under the effect of heavy constituent reflux pump, and another part passes through heavy constituent discharging pump extraction。
Described oils and fats includes rich in stearic acid, oleic acid and linoleic animal and plant fat or rich in the one in the useless fish oil of eicosapentaenoic acid, the algal oil of docosahexenoic acid, fish oil and the acid number high acid value more than 2 or waste oil。
2. pump suction type high vacuum rectification method in the tower that C16～C22 series fatty acid precision according to claim 1 separates, it is characterised in that: described catalyst is ionic liquid or with KOH, CaO, H2SO4And the acid that Amberlyst15 is representative or alkali；Wherein said ionic-liquid catalyst includes with [BHSO3MIM]HSO4、[CH23SO3HMIM][HSO3] imidazoles that represents with [CH3CH23NCH23SO3H][C7H7O3S] for the quaternary ammonium salt of representativeAcidic ion liquid, with [Bmim] Br-CuCl2、[Bmim]Br-FeCl3、[Bmim]Br-CuCl、[Bmim]Br-Fe2Cl6、[Bmim]Br-Ni2Cl4For represent Lewis acidic ion liquid, with [HO3S-CH23-NEt3]Cl-FeCl3、[BSO3HMIM]HSO4-Fe2SO4For the bisgallic acid type ionic liquid represented, the alkali ionic liquid being representative with [BTBD] OH, [TBA] OH, [Hnmm] OH, with the mixture of any one in the heteropoly acid type ionic liquid that [PyPS] PW, [TMAPS] PW, [MIMPS] PW and [QPS] PW are representative or any at least two ionic liquid。
3. pump suction type high vacuum rectification device in the tower that C16～C22 series fatty acid precision that a kind realizes described in claims 1 or 2 separates, it includes rectifying column, described rectifying column has charging aperture, described rectifying column comprises rectifying section, stripping section and reboiler three part, tower top at described rectifying column is connected to condenser, described condenser is connected with vacuum system by the first vacuum tube, the condensate outlet of described condenser is connected with the inlet of reflux ratio controller, one liquid outlet of described reflux ratio controller by the second vacuum tube successively with cooler and steam thing extraction pump and be connected, another liquid outlet of described reflux ratio controller is connected with the inlet of backflow vacuum tube, the liquid outlet of described backflow vacuum tube is inserted in rectifying column by the refluxing opening of rectifying column, one reflux splitter is arranged in the rectifying column below backflow vacuum tube, it is characterized in that: at the bottom of the tower of described rectifying column, be connected with reboiler and discharging proportional divider in turn, one outlet of described discharging proportional divider connects heavy constituent extraction pump by vacuum tube and another outlet connects heavy constituent reflux pump by vacuum tube, the liquid outlet of described heavy constituent reflux pump is respectively through the bottom filling valvular heavy constituent backflow vacuum tube and the stripping section of rectifying column, the liquid return hole of reboiler is connected, one heavy constituent reflux splitter is arranged in the rectifying column below heavy constituent backflow vacuum tube exit, one raw material storage tank by the 3rd vacuum tube successively with charging dosing pump, effusion meter, the charging aperture of feed preheater and rectifying column is connected, one feed distributor is arranged in the rectifying column below charging aperture place, rectifying section at rectifying column is separately installed with at least one Roots vaccum pump with stripping section。
4. pump suction type high vacuum rectification device in the tower that C16～C22 series fatty acid precision according to claim 3 separates, it is characterized in that: described Roots vaccum pump is built-in Roots vaccum pump or external Roots vaccum pump, when using built-in Roots vaccum pump, this thermal insulation Roots vaccum pump is placed in rectifying column；When using external Roots vaccum pump, rectifying column and external Roots vaccum pump are that screw is connected and sealing means employing magnetic seal between rectifying column and external Roots vaccum pump。
5. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterised in that: described Roots vaccum pump adopts at least two leaf roots rotors。
6. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterised in that: described Roots vaccum pump adopts Roots's profile of tooth。
7. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterised in that: described rectifying column is made up of multiple towers joint, and the height of the filler in each tower saves is 0.1～2.5m。
8. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterised in that: the tower diameter of described rectifying column is 5～1000mm。
9. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterised in that: the filler in described rectifying column is the one in screen waviness plate, ripple packing, Pall ring, cascade ring, θ ring filler or glass spring filler。
10. pump suction type high vacuum rectification device in the tower that the C16～C22 series fatty acid precision according to claim 3 or 4 separates, it is characterized in that: described reboiler is Wiped Film Evaporator or heating kettle, when reboiler is Wiped Film Evaporator, scraper plate rotating speed is 20～1000r/min。
CN201610187103.2A 2016-03-29 2016-03-29 In-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids Active CN105695104B (en)

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CN105132189A (en) * 2015-08-06 2015-12-09 天津大学 Fine separation method of C18 series and C20-C22 series fatty acid methyl esters
CN105498262A (en) * 2015-12-01 2016-04-20 欧阳丁一 Vacuum rectification apparatus with built-in roots vacuum pumps

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CN103055529A (en) * 2012-12-27 2013-04-24 淄博特普化工技术有限公司 Reduced-pressure batch rectification tower with inner pressure adjustment device and use method thereof
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