CN103012030B - Method for purifying organic mixture by static melt crystallization - Google Patents
Method for purifying organic mixture by static melt crystallization Download PDFInfo
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Abstract
The invention relates to a method for purifying an organic mixture by static melt crystallization. According to the method, an organic mixture system is placed in a magnetic field in the end of crystallization for product separation. The method comprises the following steps of: adopting a magnetic solid particle as a carrier; suspending the carrier in an organic liquid mixture to form a suspension system; carrying out melt crystallization operations on the suspension system to obtain a crystal; then adding the magnetic field to the periphery of a melt crystallizer; moving solid product particles wrapping the carrier to a specified area of the crystallizer by changing the strength, position, time or direction of the magnetic field, and gathering the solid product particles; separating liquid from solid to obtain liquid and solid; heating and melting the solid to obtain liquid and the carrier; and separating out the carrier for cycle use. As the organic mixture system is placed in the magnetic field in the end of crystallization for product separation, special organic mixtures, which are difficult to purify and separate by the melt crystallization operations in a usual environment (without magnetic force), are purified and separated.
Description
Technical field
The present invention relates to separation technology field, particularly relate in a kind of process of static fusion-crystallization purification organic mixture, utilize the method for externally-applied magnetic field effect fractional crystallization terminal product.
Background technology
Fusion-crystallization technology be a kind of utilize the different melting points of each component in organic mixture to carry out be separated, the technology of purifying, concentrated organic mixture, be widely used in the refining purification of chemical intermediate, medicine intermediate or biochemical product.The organic mixture of fusion-crystallization process: at normal temperatures or through heating after be liquid, the organic mixture be made up of multiple component of dissolving each other, each component fusing point has certain difference.
CN102350271A has invented a kind of melt crystallization separating device, can be widely used in organic separation.The melting crystallizer that CN102423542A provides can be widely used in the obvious isomers of all different melting points, the organic separation of homologue.Above-mentioned two patents all solve the large and problem that operation easier is large of existing melting crystallizer complex structure, volume, and apparatus structure is simple, volume is little and easy to operate, adopt the separation of scraper accelerating solid, decrease organic mixture loss.CN102627531A has invented a kind of method of water fusion-crystallization production needle-like 2,5-xylenol, and after its crystallization, system obtains 2,5-xylenol after whizzer preliminary hydro-extraction and the dehydration of revolution vacuum drier two-stage.This invention can make production safer, reduces production cost.CN102198937A has invented a kind of method of static multistage melting crystallization method for preparing electronic grade phosphoric acid, and namely adopt the method for repeatedly melting → purifying → row's partial mother liquid, the method is simple to operate, and energy consumption is low, and operational condition is gentle, and product purity is higher.
In static fusion-crystallization process, reduced gradually by organic mixture liquid temp, the high and component that solubleness is little of fusing point, with solid-state precipitation, forms crystal seed (also can add crystal seed directly in liquid); Continue the temperature controlling material, until constantly there is solid to adhere to the crystal of growing up to certain size on crystal seed, now, form solid-liquid suspensions.For static fusion-crystallization process, without under the prerequisite of outfield intensifying, the solid particulate now in suspension is subject to the effect of gravity and buoyancy two power simultaneously.According to the size and Orientation of the component sum of two power vertical direction, organic mixture system can be divided into two kinds: the first, the direction of the component sum in two power vertical direction is downward, and solid particulate starts to sink, until be enriched in reactor bottom; The second, the component sum in two power vertical direction is zero, and the solid particulate be suspended in liquid can transfixion.
For above-mentioned the second system, what realize the solid-liquid product in crystallization terminal moment is effectively separated into one of problem to be solved.For some specific systems, because liquid viscosity is large, cannot by filtering the effective separation realizing solid-liquid product; For other specific systems, the solid product particle due to formation is less and density is less, cannot be realized effective separation of solid-liquid product by centrifugal method.The present invention is directed to above-mentioned the second system, a kind of method of magnetic field-intensification fractional crystallization product is provided, namely in the crystallization terminal moment, the additional untouchable power of solid particulate to crystallization---magnetic force, change the stress balance state of solid particulate, realize the orientation movement of solid particulate and be enriched in the designated area of crystallizer, thus realizing effective separation of solid-liquid product.The present invention is applicable to can to realize component by fusion-crystallization and purifies, but cannot be obtained the organic mixture of target product by conventional lock out operation.The present invention is intended to the separation problem of the solid-liquid product solving fusion-crystallization terminal.Its advantage is, by fusion-crystallization technology and the coupling of magnetic field-intensification technology, makes the special organic mixture relying on single fusion-crystallization technology to be difficult to realize purification & isolation be achieved purification & isolation.
Summary of the invention
The object of the invention is to the separation problem of the solid-liquid product solving fusion-crystallization terminal, a kind of method of static fusion-crystallization purification organic mixture is provided, makes the special organic mixture relying on single fusion-crystallization technology to be difficult to realize purification & isolation be achieved purification & isolation.
For reaching this object, the present invention by the following technical solutions:
A method for static fusion-crystallization purification organic mixture, organic mixture system is placed in magnetic field when crystallization terminal and carries out product separation by described method.
Specifically, said method comprising the steps of:
(1) organic mixture is placed in melting crystallizer, makes it melt completely, form liquid I;
(2) in liquid I, add magnetic carrier, make it be uniformly dispersed, form carrier-liquid suspension system II;
(3) decrease temperature crystalline operation is carried out to described suspension system II, form crystallization at surfaces of magnetic carriers, form xln, in melting crystallizer, form suspension system III;
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed, suspension system III is made to be placed in magnetic field completely;
(5) by flux control, make xln enrichment in melting crystallizer, form system IV;
(6) described system IV is carried out solid-liquid separation, the product liquid V obtaining solid product VI and purify.
The method of the invention is optionally carried out:
(7) heated by described solid product VI, melting forms product liquid VII and carrier;
(8) be separated with carrier by product liquid VII, the carrier obtained is reused;
Preferably, product liquid VII carries out recrystallization to extract required component after accumulating.
Through above-mentioned steps, the content that organic mixture is separated into target components in product liquid V and product liquid VII, two kinds of product liquids comparatively in organic mixture component concentration have obvious change, the purification of organic mixture can be realized.
The method of the invention adopts magnetic retention particle to be carrier, carrier is suspended in liquid organic mixture and forms suspension system, suspension system is placed in melting crystallizer and carries out fusion-crystallization operation, the solid product of crystallisation process is attached on carrier also grows up gradually.When fusion-crystallization operation reaches terminal, externally-applied magnetic field around melting crystallizer, by changing the action intensity in magnetic field, position, time or direction, the solid product particle being wrapped in carrier is made to shift to the designated area (being generally one end of crystallizer) of crystallizer and assemble.Solid-liquor separation obtains liquid and solid after opening, and obtain liquid and carrier by after solid heat fused, carrier is separated for recycling.The concrete operations such as heating of the present invention, fusing, cooling, fusion-crystallization, externally-applied magnetic field and modulation magnetic field, solid-liquor separation, all can be carried out according to the common practise of this area by those skilled in the art.
Organic mixture of the present invention includes but are not limited to the mixture that fine chemicals, chemicals, plant milk extract organic mixture medicine, medicine intermediate, sterilizing agent, synthetic perfume, leather chemicals reagent, Western medicine, dyestuff intermediate, standardized solution, waste cooking oil, animal grease, Vegetable oil lipoprotein or coating etc. are made up of organism.
Under the prerequisite that organic mixture physicochemical property do not change, the fusing mode of described step (1) can adopt any type of heating known in those skilled in the art.The present invention can be selected from the one in Direct Contact Heating, liquid bath heating, microwave heating or Infrared Heating, the one further in preferably electrically heated, heating in water bath, oil bath heating or Infrared Heating.
Under the prerequisite that organic mixture physicochemical property do not change, heating rate is unrestricted, and in actually operating, carry out conservative control can realize the object of the invention, can be constant speed heating, also can speed change heating.
Under the prerequisite that organic mixture physicochemical property do not change, the top temperature reached needed for fusing close to or a little more than the fusing point of the highest component of fusing point in organic mixture.Of the present invention " close to or a little more than " refer to heating time top temperature near the fusing point of the highest component of fusing point, organic mixture can be made to melt completely, add to guarantee to be melted to after organic mixture moves to melting crystallizer the moment that magnetic carrier forms suspension system II, separate out without solid organic matters (comprising the sightless micro-solid particle of naked eyes).Those skilled in the art can select this temperature according to the general knowledge of oneself and experience when actually operating, such as, in organic mixture, the fusing point of the highest component of fusing point is 75 DEG C, the highlyest in actually operating is heated to about 76 DEG C organic mixture can be made to melt completely.
The top temperature that step of the present invention (1) melts continues to organic mixture and melts formed till liquid completely.Under the prerequisite that organic mixture physicochemical property do not change, the top temperature duration that described step (1) melts is unrestricted, those skilled in the art carry out conservative control in actually operating, melt completely form liquid (not comprising the sightless micro-solid particle of naked eyes in liquid) for end time with organic mixture.
At carrier not with under the prerequisite of organic materials generation chemical reaction, step of the present invention (2) described carrier is magnetic substance or modified magnetic substance.The magnetic material of all tools well known in the art, all can be used for the present invention.Described modification can be any modification to magnetic substance well known in the art, and chemical method is modified and Physical is modified.
Preferably, described magnetic substance is the combination that is a kind of or at least bi-material in metal simple-substance, magneticalloy or magnetic oxide, further preferable alloy simple substance; The preferred iron of described metal simple-substance, cobalt, nickel, lanthanide series metal simple substance, further preferred iron simple substance.
Preferably, be modified to finishing, outside modification, interior finishing or middle part described in modify.
Preferably, surface finish, etching, coating or parcel is modified to described in; Surface parcel material therefor is plastics and/or pottery, described plastics preferably polytetrafluoroethylene.Various surperficial lapping well known in the art one or both/combination of two or more material, all can be used for the present invention.
Preferably, the shape of carrier be cubes, spheroid, right cylinder or irregularly shaped in a kind of combination of or at least two kinds of shapes; Preferably, described carrier is hollow or half hollow.The prerequisite in organic liquid can be suspended in equably at carrier under, the shape of carrier is unrestricted, can be the regular shapes such as cubes, spheroid, right cylinder, what also can be randomly formed is irregularly shaped, also can be regular shape and erose combination, also can be the different shape of hollow, half hollow.
Can be suspended in the prerequisite in liquid I equably at carrier under, the size of carrier is unrestricted, can be single-size particle, also can be the combination by the different size particle in certain particle size distribution range.
Can be suspended in the prerequisite in liquid I equably at carrier under, in operating temperature range of the present invention, solid support material guarantee not with any component generation chemical reaction of organic mixture, the physico-chemical property of organic mixture can not change.
Melting crystallizer of the present invention is the container of jacketed, and chuck is used for circulation cycle heating or cooling liqs, as water, heat conduction wet goods.Its volume is unrestricted, determines according to production actual needs.Its shape includes but not limited to right cylinder, rectangular parallelepiped and other suitable shapes, is preferably right cylinder or rectangular parallelepiped.Modes of emplacement includes but not limited to vertical type, tilting or horizontal.The material of described melting crystallizer is nonmagnetic material and/or non-metallic material; Described non-metallic material are the combination that is a kind of or at least bi-material in glass, quartz, pottery, high molecular polymer or glass reinforced plastic; Combination that is a kind of or at least bi-material in the preferred synthetic glass of described high molecular polymer, engineering plastics, resin or silica gel.Typical but non-limiting example comprises glass, pottery, glass reinforced plastic, engineering plastics, silica gel, the combination of quartz and pottery, the combination of glass reinforced plastic and synthetic glass, the combination of resin and silica gel, the combination etc. of engineering plastics, resin and silica gel.All temperature of bearing in service temperature variation range of the present invention in prior art, magnetic field can be allowed to pass and can not the single-material well known in the art of remarkably influenced magneticstrength or the combination of two kinds/two or more material, all can be used for implementing the present invention.
Described step (3) cooling method can be the water-bath cooling of chuck internal recycle or chuck internal recycle other fluid temperature reductions well known in the art, also can be other cooling methods well known in the art such as wind cooling temperature lowering, be preferably the cooling of chuck fluid circulating or the wind cooling temperature lowering of melting crystallizer.Rate of temperature fall and terminal temperature are determined according to the physicochemical property of organic mixture, can generate solid and the content of a certain component in solid or certain several component and organic mixture have discernible macroscopical difference for target is to control rate of temperature fall and terminal of lowering the temperature.Can be temperature-reduction at constant speed, also can be speed change cooling, also can be to fall mild heat mixing carry out or hocket.The terminal moment that the terminal temperature time length is the time length with the moment of growing up to demand size of solid particulate in system.
In described step (4), externally-applied magnetic field is the magnetic field that permanent magnet or magnetoresistive effect produce, the magnetic field that other modes well known in the art can also be adopted to produce, and all can be used for implementing the present invention.
The action of a magnetic field position and scope unrestrictedly, are rationally determined to reach the object of the invention.Described magnetic field is lasting magnetic field or pulsed magnetic field.
Magneticstrength can be constant, also can be conversion occurs.Magneticstrength is determined as follows: the component of making a concerted effort in vertical direction of the gravity that the solid particulate that the magnetic force that the action of a magnetic field produces on carrier is enough to overcome parcel carrier is subject to and buoyancy, makes the stress balance state of solid particulate change.
Described step (5) by regulate the intensity of externally-applied magnetic field, position, direction or time chien shih xln magnetic force, gravity and buoyancy three power component sum in vertical direction of being subject to non-vanishing, make xln enrichment.The present invention can take at the uniform velocity to regulate, gearshift adjustment, magnetic field is alternately with or without regulative modes well known in the art such as adjustments, regulate to ensure: the magnetic force that solid particulate is subject to, gravity and buoyancy three power component sum is in vertical direction non-vanishing, xln is moved along desired orientation and in designated area enrichment, be generally the bottom being enriched in melting crystallizer.
The solid-liquid separating method of step of the present invention (6) can adopt solid-liquid separating method well known in the art, is preferably valve blowing, directly topples over, drainage or pumping.
Described step (7) is heated to solid product VI and melts completely.During heating terminal, solid product VI is melted to liquid completely, and carrier can be taken out by ordinary operation mode such as filtrations.The separate mode of described step (8), for filtering or fishing for, other separate modes not changing the physico-chemical property of liquid VII and carrier well known in the art, all can be used for the present invention.
A method for static fusion-crystallization purification organic mixture, described method specifically comprises the following steps:
(1) organic mixture is placed in container, heating makes it melt completely, forms liquid I;
(2) in liquid I, add magnetic carrier, make it be uniformly dispersed, form carrier-liquid suspension system II; Suspension system II is transferred in melting crystallizer, and keeps the suspended state of carrier in suspension system II;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, until solid product to be attached on carrier and to grow up to desired size, form xln, in melting crystallizer, form suspension system III;
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed, suspension system III is made to be placed in magnetic field completely;
(5) regulate the intensity in magnetic field, position, scope, direction or time, make xln enrichment in melting crystallizer, form system IV;
(6) system IV that step (5) obtains is carried out solid-liquid separation, the product liquid V obtaining solid product VI and purify;
(7) solid product VI that step (6) obtains is placed in container, heating container forms product liquid VII and carrier to solid product VI melting;
(8) be separated with carrier by the liquid VII that step (7) obtains, the carrier obtained is reused; Product liquid VII carries out recrystallization to extract required component after accumulating.
Compared with prior art scheme, the present invention has following beneficial effect:
Organic mixture system is placed in magnetic field when crystallization terminal and carries out product separation by the present invention, makes under normal circumstances the fusion-crystallization of (without magnetic force) operate the special organic mixture being difficult to realize purification & isolation and is achieved purification & isolation.
The present invention is intended to the separation problem of the solid-liquid product solving fusion-crystallization terminal.Its advantage is, by fusion-crystallization technology and the coupling of magnetic field-intensification technology, makes the special organic mixture relying on single fusion-crystallization technology to be difficult to realize purification & isolation be achieved purification & isolation.
Accompanying drawing explanation
Fig. 1 is the operational flowchart of the inventive method;
Fig. 2 is the vertical profile structural representation of melting crystallizer;
Fig. 3 is the cross-sectional structural representation of melting crystallizer;
Fig. 4 is carrier stress schematic diagram.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
A method for static fusion-crystallization purification organic mixture, said method comprising the steps of:
(1) organic mixture is at room temperature liquid or solid-state or solid-liquid mixed state, and the material getting certain volume is directly put in container, makes organic mixture be melted to liquid state completely, form liquid I to container heating;
(2) by support dispersion in container, form uniform carrier-liquid suspension system II; Suspension system II is placed in melting crystallizer, and keeps the suspended state of carrier in suspension system II;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, when solid product to be attached on carrier and to grow up to desired size, form suspension system III;
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed of step (3) gained, regulate the intensity of the action of a magnetic field, position, scope, direction or time, the position (being generally one end of crystallizer) solid product being enriched in specify, forms system IV;
(5) system IV that step (4) obtains is carried out solid-liquid separation, obtain product liquid V and solid product VI;
(6) solid product VI that step (5) obtains is placed in container, heating container forms product liquid VII and carrier to solid product VI melting;
(7) be separated with carrier by the liquid VII that step (6) obtains, the carrier obtained is for reusing; Product liquid VII can accumulate be accumulate to a certain amount of after, recrystallization is to extract required component.
Through above-mentioned steps (1)-(7), organic mixture is separated into component concentration in the more former organic mixture of content of target components in product liquid V and product liquid VII, two kinds of product liquids obvious change, can realize the purification of organic mixture.
Be below specific embodiments of the invention:
As shown in Figure 2, following examples are with height h=30cm, internal diameter d for melting crystallizer size
inthe crystallizer of=4cm is example (volume is 376.8ml), when adopting other size melting crystallizers, as long as carry out reasonable operation, can realize the object of the invention.Organic raw material to be purified is at room temperature solid-liquid admixture, and its character is as follows:
Require the concentration of C in purification organic mixture, make its content be not less than 95%.
Embodiment 1
(1) organic mixture is shaken up, get 300ml to be directly put in Glass Containers, container is placed in water bath, start the heating function of water bath, within 30min, bath temperature is risen to 60 DEG C, and at 60 DEG C of constant temperature 30min, make the organic mixture material in container be melted to liquid state completely, form liquid I;
(2) ferric oxide particle (median size is 2mm, and shape is hollow ball shape, and hollow parts spheroid median size is 1.86mm, and surface free is modified) 0.15g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid suspension system II; Suspension system II is placed in melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, suspension system II is lowered the temperature with the rate of temperature fall of 0.1 DEG C/min, be down to 45 DEG C, constant temperature 10h, in suspension system, organic solid product is separated out and is attached on carrier, forms suspension system III.Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed of step (3) gained, whole crystallizer is all in magnetic field range; Produce magnetic field by electromagnetic induction, according to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) be out collected in container by the liquid pumping in crystallizer with pump, obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, electrically heated method is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting mode of fishing for step (6) to be obtained takes out, for reusing.
Embodiment 2
(1) organic mixture is shaken up, get 300ml and be directly put in Glass Containers, container is placed in water bath, start the heating function of water bath, within 30min, bath temperature is risen to 60 DEG C, and at 60 DEG C of constant temperature 30min, make organic materials in container be melted to liquid state completely, form liquid I;
(2) ferric oxide particle (median size is 2mm, and shape is hollow ball shape, and hollow parts spheroid median size is 1.89mm, and surface is through over etching) 0.15g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid suspension system II; Suspension system II is placed in melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, make suspension system II with the 5min that lowers the temperature, the alternate cycles pattern of intensification 1min is lowered the temperature, until be down to 45 DEG C, then constant temperature 10h, solid product is separated out and is attached on carrier, forms suspension system III; Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed of step (3) gained, whole crystallizer is all in magnetic field range; Produce magnetic field by electromagnetic induction, according to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) be out collected in container by the liquid pumping in crystallizer with pump, obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, electrically heated method is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting mode of fishing for step (6) to be obtained takes out, for reusing.
Embodiment 3
(1) organic mixture is shaken up, get 300ml to be directly put in Glass Containers, container is placed in electrothermal oven, thermometer is inserted in the organic mixture in container, then electrothermal oven is started, heating power is adjusted middle-grade, when organic mixture temperature rises to 60 DEG C, is turned down by heating power, and keep a close eye on organic mixture in observation container, when organic mixture is melted to liquid state completely, during invisible micro-solid particle, stop heating, now form liquid I;
(2) ferric oxide particle (median size is 3mm, and shape is the hollow cubic bodily form, and hollow parts spheroid median size is 2.79mm, and surface free is modified) 0.15g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid suspension system II; Suspension system II is placed in vertical melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, make suspension system II with the 5min that lowers the temperature, the alternate cycles pattern of intensification 1min is lowered the temperature, until be down to 45 DEG C, then constant temperature 10h, solid product is separated out and is attached on carrier, forms suspension system III; Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the additional hot-wire coil of the melting crystallizer that suspension system III is housed of step (3) gained, to coil with electric current, produce magnetic field by electromagnetic induction, whole crystallizer is all in magnetic field range; According to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) liquid in crystallizer is collected in container by valve blowing, and obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, the method of heating in water bath is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting filter type step (6) to be obtained takes out, for reusing.
Embodiment 4
(1) organic mixture is shaken up, get 300ml to be directly put in Glass Containers, container is placed in electrothermal oven, thermometer is inserted in the organic mixture in container, then electrothermal oven is started, heating power is adjusted middle-grade, when organic mixture temperature rises to 60 DEG C, is turned down by heating power, and keep a close eye on organic mixture in observation container, when organic mixture is melted to liquid state completely, during invisible micro-solid particle, stop heating, now form liquid I;
(2) ferric oxide particle (median size is 3mm, and shape is the hollow cubic bodily form, and hollow parts spheroid median size is 2.84mm, and surface is through over etching) 0.15g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid suspension system II; Suspension system II is placed in vertical melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, suspension system II is lowered the temperature with the rate of temperature fall of 0.1 DEG C/min, be down to 45 DEG C, constant temperature 10h, solid product is separated out and is attached on carrier, forms suspension system III; Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the additional hot-wire coil of the melting crystallizer that suspension system III is housed of step (3) gained, to coil with electric current, produce magnetic field by electromagnetic induction, whole crystallizer is all in magnetic field range.According to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) liquid in crystallizer is collected in container by valve blowing, and obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, the method of microwave heating is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting filter type step (6) to be obtained takes out, for reusing.
Embodiment 5
(1) organic mixture is shaken up, get 300ml and be directly put in Glass Containers, container is placed in water bath, start the heating function of water bath, within 30min, bath temperature is risen to 60 DEG C, and at 60 DEG C of constant temperature 30min, make organic materials in container be melted to liquid state completely, form liquid I;
(2) ferric oxide particle (median size is 2mm, and shape is hollow ball shape, and hollow parts spheroid median size is 1.92mm, and surface is through over etching) 0.10g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid float system II; Suspension system II is placed in melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, make suspension system II with the 5min that lowers the temperature, the alternate cycles pattern of intensification 1min is lowered the temperature, until be down to 45 DEG C, then constant temperature 10h, solid product is separated out and is attached on carrier, forms suspension system III; Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed of step (3) gained, whole crystallizer is all in magnetic field range; Produce magnetic field by electromagnetic induction, according to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) be out collected in container by the liquid pumping in crystallizer with pump, obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, electrically heated method is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting filter type step (6) to be obtained takes out, for reusing.
Embodiment 6
(1) organic mixture is shaken up, get 300ml and be directly put in Glass Containers, container is placed in water bath, start the heating function of water bath, within 30min, bath temperature is risen to 60 DEG C, and at 60 DEG C of constant temperature 30min, make organic materials in container be melted to liquid state completely, form liquid I;
(2) ferric oxide particle (median size is 2mm, and shape is hollow cubic body, and hollow parts cubes median size is 1.95mm, surface free process) 0.20g is got, as carrier; By support dispersion in container, be stirred to and form uniform carrier-liquid float system II; Suspension system II is placed in melting crystallizer, in melting crystallizer chuck, passes into the recirculated water 5min that temperature is 60 DEG C, keep the state of liquid in crystallizer to be liquid, and carrier is still suspended state;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, recirculated water is lowered the temperature, suspension system II is lowered the temperature with the rate of temperature fall of 0.1 DEG C/min, be down to 45 DEG C, constant temperature 10h, solid product is separated out and is attached on carrier, forms suspension system III; Solid product is simultaneously containing component A, B and C, and wherein the content of component A greatly reduces compared with the content in raw material, and the content of B component and C greatly increases compared with the content in raw material.
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed of step (3) gained, whole crystallizer is all in magnetic field range; Produce magnetic field by electromagnetic induction, according to right-hand screw rule determination magnetic line of force direction, make magneto motive direction suffered by carrier downward, continue to provide electric current and magnetic field, until solid product is enriched in crystalliser feet, this liquid-solid mixture forms system IV;
(5) be out collected in container by the liquid pumping in crystallizer with pump, obtain product liquid V, contained by it, component comprises: about component C(2%), remaining is component A and B component (content sum is: the content of 100%-component C); Remaining solid product takes out and obtains solid product VI, and contained by it, component comprises: about component C(97%), remaining is component A and B component (content sum is: the content of 100%-component C);
(6) solid product VI that step (5) obtains is placed in container, electrically heated method is adopted to heat container, rise to 60 DEG C with the heating rate of 5 DEG C/min, and at 60 DEG C of constant temperature 30min, make solid product VI all melting formation product liquid VII and carriers;
(7) carrier adopting mode of fishing for step (6) to be obtained takes out, for reusing.
Through the inventive method, organic mixture is separated into product liquid V and product liquid VII, in two kinds of product liquids, the content of target components C is respectively 97% and be less than 2%, and in product liquid V, the content of target components is significantly improved, and achieves the purification of organic mixture.
Applicant states, the present invention illustrates method of purification of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned purification step, does not namely mean that the present invention must rely on above-mentioned purification step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of organic mixture selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (33)
1. a method for static fusion-crystallization purification organic mixture, is characterized in that, organic mixture system is placed in magnetic field when crystallization terminal and carries out product separation by described method;
Said method comprising the steps of:
(1) organic mixture is placed in melting crystallizer, makes it melt completely, form liquid I;
(2) in liquid I, add magnetic carrier, make it be uniformly dispersed, form carrier-liquid suspension system II;
(3) decrease temperature crystalline operation is carried out to described suspension system II, form crystallization at surfaces of magnetic carriers, form xln, in melting crystallizer, form suspension system III;
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed, suspension system III is made to be placed in magnetic field completely;
(5) by flux control, make xln enrichment in melting crystallizer, form system IV;
(6) described system IV is carried out solid-liquid separation, the product liquid V obtaining solid product VI and purify.
2. the method for claim 1, is characterized in that, described method is optionally carried out:
(7) heated by described solid product VI, melting forms product liquid VII and carrier;
(8) be separated with carrier by product liquid VII, the carrier obtained is reused.
3. method as claimed in claim 2, is characterized in that, product liquid VII carries out recrystallization to extract required component after accumulating.
4. the method as described in one of claim 1-3, it is characterized in that, described organic mixture comprises fine chemicals, chemicals, plant milk extract organic mixture medicine, medicine intermediate, sterilizing agent, synthetic perfume, leather chemicals reagent, Western medicine, dyestuff intermediate, standardized solution, waste cooking oil, animal grease, Vegetable oil lipoprotein or coating.
5. the method as described in one of claim 1-3, is characterized in that, the fusing mode of described step (1) is the one in Direct Contact Heating, liquid bath heating, microwave heating or Infrared Heating.
6. method as claimed in claim 5, it is characterized in that, the fusing mode of described step (1) is the one in electrically heated, heating in water bath, oil bath heating or Infrared Heating.
7. the method as described in one of claim 1-3, is characterized in that, the constant speed that is molten into of described step (1) heats or speed change heating.
8. the method as described in one of claim 1-3, is characterized in that, the top temperature reached needed for the fusing of described step (1) is close to or higher than the fusing point of the highest component of fusing point in organic mixture.
9. the method as described in one of claim 1-3, is characterized in that, the top temperature that described step (1) melts continues to organic mixture and melts formed till liquid completely.
10. the method as described in one of claim 1-3, is characterized in that, step (2) described magnetic carrier is magnetic substance or modified magnetic substance.
11. methods as claimed in claim 10, is characterized in that, described magnetic substance is the combination that is a kind of or at least bi-material in metal simple-substance, magneticalloy or magnetic oxide.
12. methods as claimed in claim 11, it is characterized in that, described magnetic substance is metal simple-substance.
13. methods as claimed in claim 12, is characterized in that, described metal simple-substance is iron, cobalt, nickel, lanthanide series metal simple substance.
14. methods as claimed in claim 13, it is characterized in that, described metal simple-substance is iron simple substance.
15. methods as claimed in claim 10, is characterized in that, described in be modified to outside to modify, interior finishing or middle part modify.
16. methods as claimed in claim 15, it is characterized in that, described finishing is polishing, etching, coating or parcel; Surface parcel material therefor is plastics and/or pottery.
17. methods as claimed in claim 16, it is characterized in that, described plastics are tetrafluoroethylene.
18. methods as described in one of claim 1-3, is characterized in that, the shape of carrier be cubes, spheroid, right cylinder or irregularly shaped in a kind of combination of or at least two kinds of shapes.
19. methods as described in one of claim 1-3, it is characterized in that, described carrier is hollow or half hollow.
20. methods as described in one of claim 1-3, it is characterized in that, described melting crystallizer is the container of jacketed, and described chuck is used for circulation cycle heating or cooling liqs.
21. methods as claimed in claim 20, is characterized in that, the shape of described melting crystallizer is right cylinder or rectangular parallelepiped; Modes of emplacement is vertical type, tilting or horizontal.
22. methods as claimed in claim 20, is characterized in that, the material of described melting crystallizer is nonmagnetic material and/or non-metallic material; Described non-metallic material are the combination that is a kind of or at least bi-material in glass, quartz, pottery, high molecular polymer or glass reinforced plastic.
23. methods as claimed in claim 22, is characterized in that, described high molecular polymer is the combination that is a kind of or at least bi-material in synthetic glass, engineering plastics, resin or silica gel.
24. methods as claimed in claim 20, is characterized in that, the cooling method of described step (3) is the cooling of chuck fluid circulating or the wind cooling temperature lowering of melting crystallizer.
25. methods as claimed in claim 24, is characterized in that, described cooling is temperature-reduction at constant speed or speed change cooling, and the cooling of described speed change comprises falls mild heat mixing and carry out or the cooling that hockets.
26. methods as described in one of claim 1-3, is characterized in that, in described step (4), externally-applied magnetic field is the magnetic field that permanent magnet or magnetoresistive effect produce.
27. methods as claimed in claim 26, it is characterized in that, described magnetic field is lasting magnetic field or pulsed magnetic field.
28. methods as claimed in claim 27, it is characterized in that, the component of making a concerted effort in vertical direction of the gravity that the solid particulate that the magnetic force that the action of a magnetic field produces on carrier is enough to overcome parcel carrier is subject to and buoyancy, makes the stress balance state of solid particulate change.
29. methods as described in one of claim 1-3, it is characterized in that, described step (5) by regulate the intensity of externally-applied magnetic field, position, direction or time chien shih xln magnetic force, gravity and buoyancy three power component sum in vertical direction of being subject to non-vanishing, make xln enrichment.
30. methods as described in one of claim 1-3, is characterized in that, the solid-liquid separating method of described step (6) is valve blowing, directly topple over, drainage or pumping.
31. methods as claimed in claim 2 or claim 3, is characterized in that, described step (7) is heated to solid product VI and melts completely.
32. methods as claimed in claim 2 or claim 3, is characterized in that, the separate mode of described step (8) is for filtering or fishing for.
33. methods as described in one of claim 1-3, is characterized in that, said method comprising the steps of:
(1) organic mixture is placed in container, heating makes it melt completely, forms liquid I;
(2) in liquid I, add magnetic carrier, make it be uniformly dispersed, form carrier-liquid suspension system II; Suspension system II is transferred in melting crystallizer, and keeps the suspended state of carrier in suspension system II;
(3) decrease temperature crystalline operation is carried out to step (2) gained suspension system II, until solid product to be attached on carrier and to grow up to desired size, form xln, in melting crystallizer, form suspension system III;
(4) to the melting crystallizer externally-applied magnetic field that suspension system III is housed, suspension system III is made to be placed in magnetic field completely;
(5) regulate the intensity in magnetic field, position, scope, direction or time, make xln enrichment in melting crystallizer, form system IV;
(6) system IV that step (5) obtains is carried out solid-liquid separation, the product liquid V obtaining solid product VI and purify;
(7) solid product VI that step (6) obtains is placed in container, heating container forms product liquid VII and carrier to solid product VI melting;
(8) be separated with carrier by the liquid VII that step (7) obtains, the carrier obtained is reused; Product liquid VII carries out recrystallization to extract required component after accumulating.
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| CN201210593899.3A CN103012030B (en) | 2012-12-31 | 2012-12-31 | Method for purifying organic mixture by static melt crystallization |
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| CN102198937B (en) * | 2011-04-18 | 2012-10-03 | 天津大学 | Static multistage melting crystallization method for preparing electronic grade phosphoric acid |
| CN102502530A (en) * | 2011-10-26 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for producing electronic-grade sulfuric acid by static fusion crystallization |
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