Remove purification devices and the purification process thereof of impurity in fluid
Technical field
The technical field, particularly fish oil based article that the present invention relates to edible fluid class deep removal pollutent removes (dioxin compounds) environmental pollutant, heavy metal and reduces oxide compound in fish oil, superoxide etc.
Background technology
Timnodonic acid (EPA), Decosahedaenoic acid (DHA) belong to omega-3 polyunsaturated fatty acids (PUFA), be can not be synthetic in body indispensable fatty acid, there is different physiological roles, wherein EPA has prevention coronary heart disease, hypotensive, Ginseng Extract, prevention of arterial is atherosis and cerebral thrombosis, the physiologically active such as anticancer, can be applicable in the food of preventing cardiovascular disease; And DHA can significantly promote baby power grow, improve cerebral function, improve memory, be called as " DHA (docosahexaenoic acid) ", can be applicable in baby's intelligence-improving food.
Many chloros hexichol-p-Dioxins (Polychlorinated dibenzo-p-dioxins, PCDDS) and many chloros diphenylene-oxide (Polychlorinated dibenzofurans, PCDFs) be conventionally generically and collectively referred to as Dioxins, they are chloro tricyclic aromaticss, 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 approximately has 30 kinds of materials that are considered to human health to have significant damage.Wherein 2,3,7,8-tetrachloro is maximum in current known compound toxic for dibenzo-p-Dioxins (TCDD), and its toxicity, than also malicious more than 1000 times, potassium cyanide, is called as " poison in century ", and experimentation on animals indicates that it has strong carinogenicity, by international cancer center, is classified as one-level cancer material.And Dioxins 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 accumulation in vivo, and hard degradation, belongs to persistent pollutant, once enter human body, all difficult eliminatings in 10 years.It produces source has from the organic burning of nature, but it is particularly serious to be mainly that the contained Dioxins of waste, the chemical race of discharging in Industrial processes and city burning mode are processed the Dioxins pollution on the environment that domestic waste produces, according to the report of EPA's report, tellurian 90% Dioxins is because mankind's activity causes at present.Meanwhile, in food, Dioxins is huge to harm, and the mankind more than 90% are by Food Contact Dioxins, especially by using meat product, milk-product, fish and shellfish etc.The quality of fish oil liquid matter is directly determining its value and application.Therefore high-quality fish oil, not only requires its physical and chemical index to meet specified range as acid value, color, peroxide value etc., the more important thing is strict control wherein pollutent as the content of the polychlorobiphenyl such as Dioxins, class Dioxins (PCBs), heavy metal etc.There are some researches show that dioxins concentration is less than fish oil that 0.4pg/kg, PCBs content be less than 4.5 μ g/L and adds to after edible in bread and can effectively reduce hyperlipidemia.European countries pay attention to especially to this pollutant, fish oil class related products has strict testing process, and China is because fish oil goods are started late, lack corresponding technology and standard, to problems, pay attention to relatively backward, but along with raising and the attention to food safety of domestic people's living standard, problems also obtains everybody and more and more payes attention to.How to pass through hi-tech means, improve fish oil liquid matter, strengthen fish oil range of application, just day by day by numerous scientific workers, domestic and international enterprise, paid close attention to, 21 century starts deep sea fish oil and has obtained significant progress at field of food, field of health care products and medicine field.
Fish oil purification refine is mainly by physics lift-off technology means such as short distance molecule rectifying at present.The rectifying of short distance molecule is a kind of under high vacuum (<10Pa) condition, and the molecule being evaporated on hot face arrives condensing surface through short as far as possible distance and carries out condensation, thereby realizes the still-process of liquid-liquid separation.When the distance of hot face and condensing surface be less than or equal at operation vacuum and temperature be evaporated the mean free path of molecule time, this still-process is also referred to as molecular distillation.From the correlative study of Julshamn etc., can learn, molecule rectifying or the rectifying of short distance molecule can for fish oil Pesticide Residues DDT with and the separation of meta-bolites, yet in this kind of method, it removes and on pollutent, is limited to 65% accompany 25% VITAMIN and runs off, yet 65% pollutant removal cannot meet industrial demand.In addition, Anthony etc. have reported that vacuum stripping or film rectifying are used for removing grease or the chloride hydro carbons of fluid, this kind of method only just can reach effective separation of pollutent when high temperature, then for fish oil high temperature, easily causes oxidation, polymerization or the side reaction of Fish oil.Jiri Comlik etc. has studied the method that water vapour is peeled off the free acid in physics table oil and molecule rectifying, yet that physical refining can obtain the fluid physics rectifying of better quality is very complicated and expensive.In the method for patent WO9524459, first by saturated fatty acid three ester esters and unsaturated fatty acids three ester transesterification reactions, then products therefrom is removed to pollutent by the rectifying of multistep molecule, in this technical process, used enzyme catalyst to be unfavorable for the production of Fish oil.Norway Pronova biotech company adopts fish oil extract as ' clean-out system ', by molecule rectifying lift-off technology, Fish oil be can effectively remove and cholesterol, toxaphene and dioxin contamination thing comprised, 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 need to obtain that pure their acquisition obviously exists certain difficulty not containing the lower boiling fish oil of the pollutents such as PCDF, PCDD, Dioxins, need to first obtain oligosaprobic fish oil and then through rectifying repeatedly, obtain low boiler cut.How the current domestic research and development without correlation technique, control the content of pollutent in the finished product by buying low pollution Fish oil crude oil, so development of new technology purifying fish oil removes the pollutent such as Dioxins in fish oil and has bright prospects.
Summary of the invention
The technical problem to be solved in the present invention is: overcome in prior art in fluid impurity or pollutent and be difficult to the deficiency of removing, a kind of purification devices of removing impurity in fluid is provided, 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 of removing impurity in fluid, comprise tank body, porous material assembly and condensing works are set in tank body, described porous material assembly will be divided into inside and outside two regions in tank body, described condensing works is arranged at the interior region of porous material assembly; The interior region place that described tank body top is positioned at porous material assembly is provided with fluid is joined to the oil-in on porous material assembly, and the place, external region that tank body top is positioned at porous material assembly is provided with working medium and blasts mouth; Described tank base is positioned at porous material component internal region and is provided with oil outlet.The aperture of porous material scope of described porous material assembly is 0.1nm ~ 10 μ m, porosity 5 ~ 65%.
Further, described tank body top is provided with the fluid that oil-in is entered and gets rid of to the revolving vane in porous material member, and the interior region that described tank body top is positioned at porous material assembly is provided with the vacuum extractor that regulates tank body vacuum tightness to reduce material boiling point to be separated.Vacuum extractor when making tank body keep negative pressure, make porous material assembly inside and outside present pressure reduction, be convenient to impurity 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 the homodisperse scraper component of material.When work, scraper component rotation makes fluid material dispersion even, is beneficial to impurity separation.
Further, for better collecting and condense in the impurity on condensing works, the lower region of described condensing works is provided with the impurity container of receiving impurity, and described impurity container bottom has blow-off line.
Further, separated from fluid for ease of impurity, described tank body is provided with heating unit.
Porous material as key equipment, the porous material of described porous material assembly is inorganic materials, described inorganic materials is stainless steel, aluminium, copper, zinc, silver, cadmium, titanium, nickel, manganese etc. and alloy material thereof, aluminum oxide, silicon oxide, pottery, carbon, carbide, nitride, boride.
Porous material as key equipment, the porous material of described porous material assembly is organic materials, and described organic materials is polyvinyl chloride, polyurethane foam, phenol formaldehyde foam, polyolefins, Polymethacrylimide, polyethylene, polypropylene, tetrafluoroethylene, poly(vinylidene fluoride), polyvinyl chloride, polysulfones, polyethersulfone, polyacrylonitrile, polymeric amide, polyimide, polyamidoimide, polyetherimide, cellulose acetate, polyaniline, polypyrrole, polyether-ether-ketone, polybenzimidazole and composition thereof.
Described working medium is nitrogen, carbonic acid gas, methane, ethane, hexane, ammonia, hexanaphthene, heptane, water, methyl alcohol, ethanol, Virahol, butanols, benzene, toluene, chloroform, ethyl acetate, sec-butyl acetate, ethyl butyrate, vanay, methyl aceto acetate, ethyl acetate, isobutyl acetate, isopropyl acetate, Isoamyl Acetate FCC, pentyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, methyl acetate, jasmal, Phenylethyl ethanoate, butyl formate, propyl formate, formic acid n-pentyl ester, diethyl carbonate, methylcarbonate, phthalic acid two (2-ethylhexyl) ester, dinoctyl phthalate, diisononyl phthalate, acetone, ether, acetonitrile, dithiocarbonic anhydride, methyl-sulphoxide, formaldehyde, acetaldehyde, propionic aldehyde, at least one in butyraldehyde.
Adopt said apparatus to remove a method for impurity in fluid, working medium is connected to working medium and blast mouth; Condensing works is started working; The pressure that controls the external region of porous material assembly is greater than 0.2 of the pressure of interior region more than normal atmosphere; Temperature in control tank body is in room temperature to 200 ℃; Fluid is added in tank body from oil-in; Impurity in fluid, under the effect of carrying secretly of working medium, condenses on condensing works; Fluid after purifying is discharged from oil outlet.
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 of removing impurity in fluid of the present invention, novel, mainly based on accelerating distillation technology, working medium is introduced and had in the tank body of porous material assembly, and that utilizes working medium carries function secretly by the impurity removals such as pollution substance 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 mediums blast mouth, 13. oil outlets, 2. porous material assembly, 3. condensing works, 4. vacuum extractor, 5. scraper component, 6. impurity container, 61. blow-off lines.
Embodiment
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, basic structure of the present invention is only described in a schematic way, so it only show 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, interior porous material assembly 2 and the condensing works 3 of arranging of tank body 1, described porous material assembly 2 will be divided into inside and outside two regions in tank body 1, described condensing works 3 is arranged at the interior region of porous material assembly 2; The interior region place that described tank body 1 top is positioned at porous material assembly 2 is provided with fluid is joined to the oil-in 11 on porous material assembly 2, and the place, external region that tank body 1 top is positioned at porous material assembly 2 is provided with working medium and blasts mouthfuls 12; Described tank body 1 bottom is positioned at porous material assembly 2 interior regions and is provided with oil outlet 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 that oil-in is entered and gets rid of to the revolving vane in porous material member, and the interior region that described tank body 1 top is positioned at porous material assembly 2 is provided with the vacuum extractor 4 that regulates tank body 1 vacuum tightness to reduce material boiling point to be separated.Vacuum extractor 4 when making tank body 1 keep negative pressure, make porous material assembly 2 inside and outside present pressure reduction, be convenient to impurity separated from fluid.
As shown in Figure 3, the 3rd of the purification devices of impurity the embodiment 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 the homodisperse scraper component 5 of material.When work, scraper component 5 rotations make fluid material dispersion even, are beneficial to impurity separation.
As shown in Figure 4, the 4th of the purification devices of impurity the embodiment in removal fluid of the present invention, be with the difference of the 3rd embodiment, further, for better collecting and condense in the impurity on condensing works 3, the lower region of described condensing works 3 is provided with the impurity container 6 of receiving impurity, and described impurity container 6 bottoms have blow-off line 61.
Further, separated from fluid for ease of impurity, described tank body 1 is provided with heating unit (not shown).
Porous material as key equipment, the porous material of described porous material assembly 2 is inorganic materials, described inorganic materials is stainless steel, aluminium, copper, zinc, silver, cadmium, titanium, nickel, manganese etc. and alloy material thereof, aluminum oxide, silicon oxide, pottery, carbon, carbide, nitride, boride.
Porous material as key equipment, the porous material of described porous material assembly 2 is organic materials, and described organic materials is polyvinyl chloride, polyurethane foam, phenol formaldehyde foam, polyolefins, Polymethacrylimide, polyethylene, polypropylene, tetrafluoroethylene, poly(vinylidene fluoride), polyvinyl chloride, polysulfones, polyethersulfone, polyacrylonitrile, polymeric amide, polyimide, polyamidoimide, polyetherimide, cellulose acetate, polyaniline, polypyrrole, polyether-ether-ketone, polybenzimidazole and composition thereof.
Described working medium is nitrogen, carbonic acid gas, methane, ethane, hexane, ammonia, hexanaphthene, heptane, water, methyl alcohol, ethanol, Virahol, butanols, benzene, toluene, chloroform, ethyl acetate, sec-butyl acetate, ethyl butyrate, vanay, methyl aceto acetate, ethyl acetate, isobutyl acetate, isopropyl acetate, Isoamyl Acetate FCC, pentyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, methyl acetate, jasmal, Phenylethyl ethanoate, butyl formate, propyl formate, formic acid n-pentyl ester, diethyl carbonate, methylcarbonate, phthalic acid two (2-ethylhexyl) ester, dinoctyl phthalate, diisononyl phthalate, acetone, ether, acetonitrile, dithiocarbonic anhydride, methyl-sulphoxide, formaldehyde, acetaldehyde, propionic aldehyde, at least one in butyraldehyde.Working medium is torpescence material, has in the volatile characteristic of Working environment, is convenient to realize the effect of carrying secretly of working medium, 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 triglyceride level, glycerine dibasic acid esters, monoglyceride, ethyl ester, phosphatide or its mixture.
Adopt said apparatus to remove a method for impurity in fluid, working medium is connected to working medium and blast mouth; Condensing works is started working; The pressure that controls the external region of porous material assembly is greater than 0.2 of the pressure of interior region more than normal atmosphere; Temperature in control tank body is in room temperature to 200 ℃; Fluid is added in tank body from oil-in; Impurity in fluid, under the effect of carrying secretly of working medium, condenses on condensing works; Fluid after purifying is discharged from oil outlet.
Generally, according to its temperature of the variety control of fluid, do not affecting under the prerequisite of Oil Quality, temperature is high, is conducive to pollutent and discharges.Those skilled in the art can select different working temperatures according to different fluid.
Further, the fluid after purified adds in tank body again, repeats purifying once.
Take fish oil 1050EE as raw material, take carbonic acid gas as working medium, and gas flow rate is 50ml/min, at the temperature of 120 ℃, speed with 200ml per hour adds material, then collected oil outlet material is processed again, and be take water as working medium, it is 20g/ hour that water adds speed, at the temperature of 120 ℃, speed with 200ml per hour adds material, collects oil outlet gained material and analyzes, and its analytical results 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 chloro-phenyl-trichloroethane { two (4-the chloro-phenyl-)-1,1,1-trichloroethane of 2,2-, neighbour, to ' dichlorodiphenyl trichloroethane, P, P '-dichlorodiphenyl trichloroethane, the chloro-2-[2 of 1-, the chloro-1-of 2-bis-(4-chloro-phenyl-) ethyl] benzene, 1,1-bis-is chloro-2, two (rubigan) ethane of 2-} |
μg/kg |
70 |
≤0.01 |
Perchlorobenzene |
μg/kg |
12 |
≤1 |
Lindane |
μg/kg |
5 |
≤1 |
Polychlorobiphenyl |
μg/kg |
10 |
≤1 |
Dioxin polychlorobiphenyl |
pg /g |
5.1 |
0.1 |
Many chloros Dioxins+phenyl polychloride furans |
pg /g |
35 |
0.5 |
Dioxins+furans+bis-dislike because of class polychlorobiphenyl |
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 |
St-yrax acid number |
? |
13 |
4 |
Take fish oil 1050TG as raw material, take carbonic acid gas as working medium, and gas flow rate is 50ml/min, at the temperature of 120 ℃, speed with 200ml per hour adds material, then collected discharge port material is processed again, and be take water as working medium, it is 20g/ hour that water adds speed, at the temperature of 120 ℃, speed with 200ml per hour adds material, collects discharge port gained material and analyzes, and its analytical results 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 chloro-phenyl-trichloroethane { two (4-the chloro-phenyl-)-1,1,1-trichloroethane of 2,2-, neighbour, to ' dichlorodiphenyl trichloroethane, P, P '-dichlorodiphenyl trichloroethane, the chloro-2-[2 of 1-, the chloro-1-of 2-bis-(4-chloro-phenyl-) ethyl] benzene, 1,1-bis-is chloro-2, two (rubigan) ethane of 2-} |
μg/kg |
47 |
≤0.01 |
Perchlorobenzene |
μg/kg |
10 |
≤1 |
Lindane |
μg/kg |
5 |
≤1 |
Polychlorobiphenyl |
μg/kg |
96 |
≤1 |
Dioxin polychlorobiphenyl |
pg /g |
4.3 |
0.1 |
Many chloros Dioxins+phenyl polychloride furans |
pg /g |
30 |
0.3 |
Dioxins+furans+bis-dislike because of class polychlorobiphenyl |
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 |
St-yrax acid number |
? |
31 |
3.5 |
Above two embodiment make while being short run experiment.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.