Remove purification devices and the purification process thereof of impurity in fluid
Technical field
Oxide, peroxide etc. that the technical field, particularly fish oil based article that the present invention relates to edible fluid class deep removal pollutant remove (dioxin compounds) environmental contaminants, heavy metal and reduce in fish oil.
Background technology
Eicosapentaenoic acid (EPA), docosenoic acid (DHA) belong to omega-3 polyunsaturated fatty acids (PUFA), it is the essential fatty acid that can not synthesize in body, there is different physiological roles, wherein EPA has prevention coronary heart disease, hypotensive, dispelling fatigue, prevention of arterial are atherosis and cerebral thrombus, the physiologically active such as anticancer, can be applicable in the food of angiocardiopathy preventing; And DHA can significantly promote baby power grow, improve cerebral function, improve memory, be called as " docosapentaenoic acid ", can be applicable in baby's intelligence-improving food.
Many chloros hexichol-p-dioxin (Polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (Polychlorinated dibenzofurans PCDDS), PCDFs) usually dioxin is generically and collectively referred to as, they are chloro tricyclic aromatics, because the replacement number of chlorine atom is different with position, form numerous compound.What be identified at present has 419 kinds more than, wherein about has 30 kinds of materials being considered to have human health significant damage.Wherein 2,3,7,8-tetra-chloro dibenzo-p-dioxin (TCDD) is maximum at current known compound Poisoning, and its toxicity ratio potassium cyanide also wants poison more than 1000 times, is called as " poison in century ", and zoopery indicates that it has strong carcinogenicity, be classified as one-level cancer material by international cancer center.And dioxin is distributed widely in global environment medium, its stable chemical nature, be difficult to be degraded by microorganisms, being proved this compounds can enrichment in food chain, it is very easy to accumulate in vivo, is difficult to degraded, belongs to persistent pollutant, once enter human body, all difficult eliminating in 10 years.It produces source has from the organic burning of nature, but the dioxin pollution on the environment that the generation of mode process domestic waste is burned in the dioxin contained by the discarded object mainly discharged in industrial processes, chemical race and city is particularly serious, according to the report of EPA's report, tellurian 90% dioxin is because mankind's activity causes at present.Meanwhile, in food, dioxin is huge to harm, and the mankind more than 90% are by Food Contact dioxin, especially by use meat products, dairy products, fish and shellfish etc.The quality of fish oil liquid matter directly decides it and is worth and application.Therefore the fish oil of high-quality, not only require that its physical and chemical index meets particular range as acid value, color, peroxide value etc., the more important thing is strictly control wherein pollutant as the content of the Polychlorinated biphenyls such as dioxin, class dioxin (PCBs), heavy metal etc.There are some researches show dioxins concentration be less than fish oil that 0.4pg/kg, PCBs content is less than 4.5 μ g/L add to edible in bread after effectively can reduce high fat of blood.European countries pay attention to especially to this pollutant, fish oil class Related product has strict testing process, and China starts late due to fish oil goods, lack corresponding technology and standard, backwardness is relatively paid attention to problems, but the raising along with domestic people's living standard and the attention to food security, problems also obtains everybody and more and more payes attention to.How by high-tech means, improve fish oil liquid matter, strengthen fish oil range of application, just day by day by numerous scientific workers, both at home and abroad enterprise pay close attention to, 21 century starts deep sea fish oil and obtains significant progress at field of food, field of health care products and medicine field.
Current fish oil purification refine is mainly by physics lift-off technology means such as short distance molecule rectifying.The rectifying of short distance molecule is a kind of under high vacuum (<10Pa) condition, heating surface is arrived cryosurface by the molecule evaporated through distance short as far as possible and carries out condensation, thus realize the still-process of liquid-liquid separation.When the distance of heating surface and cryosurface is less than or equal to the mean free path by vapor molecule operated at vacuum and temperature, this still-process is also referred to as molecular clock.Can learn from the correlative study of Julshamn etc., molecule rectifying or the rectifying of short distance molecule may be used for the separation of fish oil Pesticide Residues DDT and its metabolite, but in this kind of method its remove the pollutant upper limit be 65% accompany 25% vitamin loss, but the pollutant removal of 65% cannot meet industrial demand.In addition, Anthony etc. report vacuum stripping or film rectifying for removing chloride hydro carbons in grease or fluid, this kind of method only just can reach effective separation of pollutant when high temperature, then easily cause the oxidation of Fish oil, polymerization or side reaction for fish oil high temperature.Jiri Comlik etc. have studied the method that steam peels off the free acid in physics table oil and molecule rectifying, and physical refining can obtain the fluid of better quality but physics rectifying is very complicated and expensive.In the method for patent WO9524459, first by saturated fatty acid three ester ester and unrighted acid three ester ester exchange reaction, then products therefrom is removed pollutant by the rectifying of multistep molecule, in this technical process, employ the production that enzyme catalyst is unfavorable for Fish oil.Pronova biotech company of Norway adopts fish oil extract as ' cleaning agent ', effectively can remove Fish oil by molecule rectifying lift-off technology and comprise cholesterol, toxaphene and dioxin contamination thing, the PCB total amount of pollutant can reduce to 7.78 ng/g from 427ng/g, PCDD total amount can reduce to 0.83 pg/g from 3.49pg/g, and PCDF total amount can reduce to 1.82 pg/g from 29.6 pg/g.But the method needs to obtain that pure their acquisition obviously exists certain difficulty not containing the low boiling fish oil of the pollutant such as PCDF, PCDD, dioxin, need first to obtain oligosaprobic fish oil and then obtain low boiler cut through repeatedly rectifying.How the current domestic research and development without correlation technique, control the content of pollutant in final products by buying low stain Fish oil crude oil, therefore development of new technology Purified fish oil to remove in fish oil the pollutants such as dioxin and has bright prospects.
Summary of the invention
The technical problem to be solved in the present invention is: to overcome in prior art the deficiency that impurity or pollutant in fluid are difficult to remove, provide a kind of purification devices removing impurity in fluid, reduce the impurity in fluid, improve the purity of fluid.
The technical solution adopted for the present invention to solve the technical problems is: a kind of purification devices removing impurity in fluid, comprise tank body, porous material assembly and condensing unit are set in tank body, described porous material assembly will be divided into inside and outside two regions in tank body, described condensing unit is arranged at the interior zone of porous material assembly; The interior zone place that described tank body top is positioned at porous material assembly is provided with the oil-in joined by fluid on porous material assembly, and the perimeter place that tank body top is positioned at porous material assembly is provided with working media and blasts mouth; Described tank base is positioned at porous material component internal region and is provided with oil-out.The aperture of porous material scope of described porous material assembly is 0.1nm ~ 10 μm, porosity 5 ~ 65%.
Further, described tank body top is provided with the fluid entered by oil-in and gets rid of to the revolving vane on porous material assembly, and the interior zone that described tank body top is positioned at porous material assembly is provided with the vacuum extractor regulating tank body vacuum to reduce boiling point substance to be separated.Vacuum extractor, while making tank body keep negative pressure, makes to present pressure reduction inside and outside porous material assembly, is convenient to impurity and is separated from fluid.
Further, the inner side of described porous material assembly is provided with at least one and rotates in a circumferential direction for by homodisperse for material scraper component.Operationally, scraper component rotates and makes fluid material dispersion even, is beneficial to magazins' layout.
Further, for better collecting the impurity condensed on condensing unit, the lower area of described condensing unit is provided with the impurity container receiving impurity, and described impurity container bottom has blowoff line.
Further, be separated from fluid for ease of impurity, described tank body is provided with heater.
As the porous material of key equipment, the porous material of described porous material assembly is inorganic material, described inorganic material is stainless steel, aluminium, copper, zinc, silver, cadmium, titanium, nickel, manganese etc. and alloy material thereof, aluminium oxide, silica, pottery, carbon, carbide, nitride, boride.
As the porous material of key equipment, the porous material of described porous material assembly is organic material, and described organic material is polyvinyl chloride, polyurethane foam, phenol formaldehyde foam, TPO, Polymethacrylimide, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl chloride, polysulfones, polyether sulfone, polyacrylonitrile, polyamide, polyimides, polyamidoimide, PEI, cellulose acetate, polyaniline, polypyrrole, polyether-ether-ketone, polybenzimidazoles and composition thereof.
Described working media is nitrogen, carbon dioxide, methane, ethane, hexane, ammonia, cyclohexane, heptane, water, methyl alcohol, ethanol, isopropyl alcohol, butanols, benzene, toluene, chloroform, ethyl acetate, sec-butyl acetate, ethyl butyrate, glyceryl triacetate, ethyl acetoacetate, ethyl acetate, isobutyl acetate, isopropyl acetate, isoamyl acetate, pentyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, methyl acetate, benzyl acetate, phenethyl acetate, butyl formate, propyl formate, formic acid n-pentyl ester, diethyl carbonate, dimethyl carbonate, phthalic acid two (2-ethylhexyl) ester, di-n-octyl phthalate, diisononyl phthalate, acetone, ether, acetonitrile, carbon disulfide, methyl-sulfoxide, formaldehyde, acetaldehyde, propionic aldehyde, at least one in butyraldehyde.
Adopt said apparatus to remove a method for impurity in fluid, working media is connected working media and blasts mouth; Condensing unit is started working; The pressure controlling the perimeter of porous material assembly is greater than more than pressure 0.2 atmospheric pressure of interior zone; Temperature in control tank body is in room temperature to 200 DEG C; Fluid is added in tank body from oil-in; Impurity in fluid, under the effect of carrying secretly of working media, condensing unit condenses; Fluid after purifying is discharged from oil-out.
Further, the fluid after purified adds in tank body again, repeats purifying once.
The invention has the beneficial effects as follows, a kind of purification devices and purification process thereof removing impurity in fluid of the present invention, novel, mainly based on acceleration distillation technology, introduced by working media and have in the tank body of porous material assembly, what utilize working media carries function secretly by impurity removals such as the polluters in fluid.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is first example structure schematic diagram of the purification devices of impurity in removal fluid of the present invention;
Fig. 2 is second example structure schematic diagram of the purification devices of impurity in removal fluid of the present invention;
Fig. 3 is the 3rd example structure schematic diagram of the purification devices of impurity in removal fluid of the present invention;
Fig. 4 is the 4th example structure schematic diagram of the purification devices of impurity in removal fluid of the present invention;
In figure: 1. tank body, 11. oil-ins, 12. working medias blast mouth, 13. oil-outs, 2. porous material assembly, 3. condensing unit, 4. vacuum extractor, 5. scraper component, 6. impurity container, 61. blowoff lines.
Detailed description of the invention
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, only basic structure of the present invention are described in a schematic way, and therefore it only shows the formation relevant with the present invention.
The present invention as shown in Figure 1 removes first embodiment of the purification devices of impurity in fluid, comprise tank body 1, porous material assembly 2 and condensing unit 3 are set in tank body 1, described porous material assembly 2 will be divided into inside and outside two regions in tank body 1, described condensing unit 3 is arranged at the interior zone of porous material assembly 2; The interior zone place that described tank body 1 top is positioned at porous material assembly 2 is provided with the oil-in 11 joined by fluid on porous material assembly 2, and the perimeter place that tank body 1 top is positioned at porous material assembly 2 is provided with working media and blasts mouth 12; Be positioned at porous material assembly 2 interior zone bottom described tank body 1 and be provided with oil-out 13.
As shown in Figure 2, second embodiment of the purification devices of impurity in removal fluid of the present invention, be with the difference of first embodiment, described tank body top is provided with the fluid entered by oil-in and gets rid of to the revolving vane on porous material assembly, and the interior zone that described tank body 1 top is positioned at porous material assembly 2 is provided with the vacuum extractor 4 regulating tank body 1 vacuum to reduce boiling point substance to be separated.Vacuum extractor 4, while making tank body 1 keep negative pressure, makes to present pressure reduction inside and outside porous material assembly 2, is convenient to impurity and is separated from fluid.
As shown in Figure 3,3rd embodiment of the purification devices of impurity in removal fluid of the present invention, be with the difference of second embodiment, further, the inner side of described porous material assembly 2 is provided with at least one and rotates in a circumferential direction for by homodisperse for material scraper component 5.Operationally, scraper component 5 rotates and makes fluid material dispersion even, is beneficial to magazins' layout.
As shown in Figure 4,4th embodiment of the purification devices of impurity in removal fluid of the present invention, be with the difference of the 3rd embodiment, further, for better collecting the impurity condensed on condensing unit 3, the lower area of described condensing unit 3 is provided with the impurity container 6 receiving impurity, has blowoff line 61 bottom described impurity container 6.
Further, be separated from fluid for ease of impurity, described tank body 1 is provided with heater (not shown).
As the porous material of key equipment, the porous material of described porous material assembly 2 is inorganic material, described inorganic material is stainless steel, aluminium, copper, zinc, silver, cadmium, titanium, nickel, manganese etc. and alloy material thereof, aluminium oxide, silica, pottery, carbon, carbide, nitride, boride.
As the porous material of key equipment, the porous material of described porous material assembly 2 is organic material, and described organic material is polyvinyl chloride, polyurethane foam, phenol formaldehyde foam, TPO, Polymethacrylimide, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl chloride, polysulfones, polyether sulfone, polyacrylonitrile, polyamide, polyimides, polyamidoimide, PEI, cellulose acetate, polyaniline, polypyrrole, polyether-ether-ketone, polybenzimidazoles and composition thereof.
Described working media is nitrogen, carbon dioxide, methane, ethane, hexane, ammonia, cyclohexane, heptane, water, methyl alcohol, ethanol, isopropyl alcohol, butanols, benzene, toluene, chloroform, ethyl acetate, sec-butyl acetate, ethyl butyrate, glyceryl triacetate, ethyl acetoacetate, ethyl acetate, isobutyl acetate, isopropyl acetate, isoamyl acetate, pentyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, methyl acetate, benzyl acetate, phenethyl acetate, butyl formate, propyl formate, formic acid n-pentyl ester, diethyl carbonate, dimethyl carbonate, phthalic acid two (2-ethylhexyl) ester, di-n-octyl phthalate, diisononyl phthalate, acetone, ether, acetonitrile, carbon disulfide, methyl-sulfoxide, formaldehyde, acetaldehyde, propionic aldehyde, at least one in butyraldehyde.Working media is torpescence material, has in the volatile characteristic of working environment, and what be convenient to realize working media carries effect secretly, to discharge impurity.
The present invention can be used for fish oil, shrimp sauce, rape oil, phosphatide wet goods or its mixture, and form is triglycerides, diglyceride, monoglyceride, ethyl ester, phosphatide or its mixture.
Adopt said apparatus to remove a method for impurity in fluid, working media is connected working media and blasts mouth; Condensing unit is started working; The pressure controlling the perimeter of porous material assembly is greater than more than pressure 0.2 atmospheric pressure of interior zone; Temperature in control tank body is in room temperature to 200 DEG C; Fluid is added in tank body from oil-in; Impurity in fluid, under the effect of carrying secretly of working media, condensing unit condenses; Fluid after purifying is discharged from oil-out.
Generally according to its temperature of variety control of fluid, under the prerequisite not affecting Oil Quality, temperature is high, is conducive to pollutant and discharges.Those skilled in the art can select different operating temperatures according to different fluid.
Further, the fluid after purified adds in tank body again, repeats purifying once.
With fish oil 1050EE for raw material, take carbon dioxide as working media, gas flow rate is 50ml/min, at the temperature of 120 DEG C, material is added with the speed of 200ml per hour, then again processed by collected oil-out material, and be working media with water, it is 20g/ hour that water adds speed, at the temperature of 120 DEG C, add material with the speed of 200ml per hour, collect oil-out gained material and analyze, its analysis result is as follows:
Table 1
Detect kind
|
Unit
|
Before purifying
|
After purifying
|
Arsenic |
mg/kg |
0.2 |
≤0.05 |
Plumbous |
mg/kg |
0.3 |
≤0.01 |
Mercury |
mg/kg |
0.2 |
≤0.001 |
Cadmium |
mg/kg |
0.3 |
≤0.01 |
Biconjugate chlorphenyl trichloroethanes { two (the 4-chlorphenyl)-1,1 of 2,2-, 1-trichloroethanes, neighbour, to '-DDT, P, P '-DDT, the chloro-2-of 1-[the chloro-1-of 2,2-bis-(4-chlorphenyl) ethyl] benzene, 1, two (rubigan) ethane of 1-bis-chloro-2,2-} |
μg/kg |
70 |
≤0.01 |
Hexachloro-benzene |
μg/kg |
12 |
≤1 |
Lindane |
μg/kg |
5 |
≤1 |
Polychlorinated biphenyls |
μg/kg |
10 |
≤1 |
Dioxin Polychlorinated biphenyls |
pg /g |
5.1 |
0.1 |
Many chloros dioxin+phenyl polychloride furans |
pg /g |
35 |
0.5 |
Dioxin+furans+two is disliked because of class Polychlorinated biphenyls |
pg /g |
29 |
0.3 |
Cholesterol |
mg/Kg |
1.2 |
0.1 |
Acid value |
mg KOH/g |
2.3 |
0.1 |
|
|
|
|
Peroxide value |
Meq/Kg |
7 |
0.8 |
Styrax acid number |
|
13 |
4 |
With fish oil 1050TG for raw material, take carbon dioxide as working media, gas flow rate is 50ml/min, at the temperature of 120 DEG C, material is added with the speed of 200ml per hour, then again processed by collected discharging opening material, and be working media with water, it is 20g/ hour that water adds speed, at the temperature of 120 DEG C, add material with the speed of 200ml per hour, collect discharging opening gained material and analyze, its analysis result is as follows:
Table 2.
Detect kind
|
Unit
|
Before purifying
|
After purifying
|
Arsenic |
mg/kg |
0.1 |
≤0.05 |
Plumbous |
mg/kg |
0.2 |
≤0.01 |
Mercury |
mg/kg |
0.1 |
≤0.001 |
Cadmium |
mg/kg |
0.3 |
≤0.01 |
Biconjugate chlorphenyl trichloroethanes { two (the 4-chlorphenyl)-1,1 of 2,2-, 1-trichloroethanes, neighbour, to '-DDT, P, P '-DDT, the chloro-2-of 1-[the chloro-1-of 2,2-bis-(4-chlorphenyl) ethyl] benzene, 1, two (rubigan) ethane of 1-bis-chloro-2,2-} |
μg/kg |
47 |
≤0.01 |
Hexachloro-benzene |
μg/kg |
10 |
≤1 |
Lindane |
μg/kg |
5 |
≤1 |
Polychlorinated biphenyls |
μg/kg |
96 |
≤1 |
Dioxin Polychlorinated biphenyls |
pg /g |
4.3 |
0.1 |
Many chloros dioxin+phenyl polychloride furans |
pg /g |
30 |
0.3 |
Dioxin+furans+two is disliked because of class Polychlorinated biphenyls |
pg /g |
27 |
0.2 |
Cholesterol |
mg/Kg |
3.1 |
0.1 |
Acid value |
mg KOH/g |
5.2 |
0.1 |
Peroxide value |
Meq/Kg |
10.8 |
0.6 |
Styrax acid number |
|
31 |
3.5 |
Make when above two embodiments are small lot experiment.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.