CN101607996B - Method for removing heavy metal ions from marine shellfish polysaccharide - Google Patents
Method for removing heavy metal ions from marine shellfish polysaccharide Download PDFInfo
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- CN101607996B CN101607996B CN2009100126672A CN200910012667A CN101607996B CN 101607996 B CN101607996 B CN 101607996B CN 2009100126672 A CN2009100126672 A CN 2009100126672A CN 200910012667 A CN200910012667 A CN 200910012667A CN 101607996 B CN101607996 B CN 101607996B
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- polysaccharide
- heavy metal
- shellfish
- exchange resin
- ion exchange
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- 150000004676 glycans Chemical class 0.000 title claims abstract description 140
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 140
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 140
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 74
- 235000015170 shellfish Nutrition 0.000 title claims abstract description 54
- 150000002500 ions Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 30
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 30
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- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 17
- 238000010612 desalination reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000012141 concentrate Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 238000000108 ultra-filtration Methods 0.000 claims description 11
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- 239000006210 lotion Substances 0.000 claims description 9
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- 230000008569 process Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
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- 150000003839 salts Chemical class 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
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- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 claims description 2
- 150000007528 brønsted-lowry bases Chemical class 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- 230000001172 regenerating effect Effects 0.000 claims 1
- 238000009418 renovation Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 11
- 235000013305 food Nutrition 0.000 abstract description 4
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- AILDTIZEPVHXBF-UHFFFAOYSA-N Argentine Natural products C1C(C2)C3=CC=CC(=O)N3CC1CN2C(=O)N1CC(C=2N(C(=O)C=CC=2)C2)CC2C1 AILDTIZEPVHXBF-UHFFFAOYSA-N 0.000 abstract 1
- 235000016594 Potentilla anserina Nutrition 0.000 abstract 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000013019 agitation Methods 0.000 description 13
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- Meat, Egg Or Seafood Products (AREA)
Abstract
The invention relates to a method for removing heavy metal ions from marine shellfish polysaccharide. The ratio of shellfish to ion exchange resin is 1.0g: 0.6-4.8ml, deionized water with 1-3 times of weight of shellfish polysaccharide is taken to prepare solution for carrying out ion exchange for 0.5-6.0 hours, obtained marine shellfish polysaccharide solution is collected for desalination, concentration and drying to obtain shellfish polysaccharide with heavy metal being removed. The heavy metal removing ratio of the marine shellfish polysaccharide is 47.0-99.7 percent. The removed heavy metal ions include the metal ions of cadmium, barium, vanadium, plumbum, thallium, molybdenum, uranium, strontium, aluminium, titanium, chromium, manganese, ferrum, cobalt, nickel, cuprum, zinc and argentine and nonmetal ions of arsenic and selenium. The invention solves the problem that marine food product is easy to enrich heavy metal to affect nutritive value thereof, improves the safe and quality of the product, has wide range of ion removal, simple processing technique and is easy to operate. The ion exchange resin can be regenerated for recycling use, so that the cost is greatly reduced.
Description
Technical field
The present invention relates to remove the technical field of heavy metal ion in the shellfish polysaccharide, also relate to technical fields such as enzymic hydrolysis, IX, lyophilize simultaneously with the method for IX.
Background technology
Fishery products and processed products thereof are just becoming one of first-selected food of domestic and international human consumer with its health, nutrition, advantage such as delicious, fishery products year production output and processing variety the more and more trend of expansion is also arranged; Along with the development of coastal waters culture fishery and mankind's activity aggravation to the coastal ocean environmental influence; The quality of fishery products and safety-problems also more and more receive domestic and international human consumer's concern, and simultaneously developed country has the trend that improves year by year to force us to strengthen this type of research from the purpose of trade protection to the detection threshold of China's exported product.
Even to detect concentration at aqueous phase very low because industrial and agricultural wastewater discharging gets into heavy metal element in the ocean environment, also enrichment and reach deleterious concentration in vivo.The edible health that receives the ocean food entail dangers to human body of heavy metal contamination of people.Therefore, carrying out the research of heavy metal removing method in the marine animal nutritive food, is very necessary to edible safety and the expansion products export that guarantees the human consumer.
Summary of the invention
To the defective that prior art exists, the present invention provides a kind of method that effectively removes heavy metal ion in the marine shellfish polysaccharide.
Technical scheme of the present invention is: adopt shellfish polysaccharide and ion exchange resin to carry out IX; Make the heavy metal ion in its absorption shellfish polysaccharide; Reaching the purpose of removing harmful heavy metal in the polysaccharide, and the ion exchange resin that has a heavy metal ion carries out activation and can reuse.Its method is:
1. the selection of raw material: (1) shellfish polysaccharide: by abalone, scallop etc. or/and polysaccharide crude or highly finished product that its internal organs extract all can.(2) ion exchange resin: comprise that any positively charged ion, anionite-exchange resin all can use.Leading ion exchange resin type is: strongly acidic cation-exchange, resin anion(R.A), 201 * 7 resin anion(R.A)s, weak base type anionite-exchange resin; Four types; Like Nankai's board 001 * 14.5 resin cation(R.C.), Nankai's board weak anion resin; Nankai's board, scape China board, green precious board, Austronesia board 201 * 7 resin anion(R.A)s, import resin cation(R.C.) U.S. Amberlite brand, U.S. Dowex brand, Britain Purolie brand, Britain Zeokarb brand, German Lewatit brand Zeo-karb or the like are selected for a post the use of meaning brand and all can.
2. removal methods: the ratio with shellfish polysaccharide and ion exchange resin is 1.0 (g): 0.6～4.8 (ml); Process with the vaal water of 1～3 times of quality of shellfish polysaccharide and to carry out hybrid ionic exchange 0.5～6.0h under the solution normal temperature, collect that resulting shellfish polysaccharide soln carries out aftertreatment and the shellfish polysaccharide that obtained removing heavy metal.Wherein carry out with following two kinds of methods:
(1) mixes stirring exchange 1～3 time.The steps include: ion exchange resin, shellfish polysaccharide soln are mixed stirring 2～3h, remove by filter ion exchange resin, solution carries out desalination, concentrates and the dry shellfish polysaccharide that has obtained removing heavy metal ion.Perhaps the above-mentioned solution that removes by filter behind the ion exchange resin is transferred required pH value with 1Mol/LNaOH or hydrochloric acid soln; Add identical or different ion exchange resin and repeat aforesaid operations again 1～2 time; The solution that then obtains removes by filter ion exchange resin, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion again.
(2) with ion exchange column the solution circulated of shellfish polysaccharide is exchanged 1～3 time.The steps include: ion exchange resin is adorned post; The solution of shellfish polysaccharide makes its absorption exchange 0.5～3.0h that in post, circulates with pump; Pick out the solution of shellfish polysaccharide; Wash post with deionized water (quite ion exchange resin capacity 0.15～1.00%), washing lotion merges with the solution that picks out the shellfish polysaccharide, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion.The solution that perhaps will pick out the shellfish polysaccharide again with activation same or different ion exchange column carry out repeating like this 1～2 time with the pump circulation.Washing lotion merges with the solution that picks out the shellfish polysaccharide, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion.
3. aftertreatment: comprise desalination, concentrated and dry.
(1) desalination:, remove the miscellaneous salts substances and promptly get the polysaccharide soln that removes behind the heavy metal with filtering 1-10K dalton's pore size semi-permeable membranes ultrafiltration or dialysis 1-12h with the polysaccharide soln of above-mentioned collection gained.
(2) concentrate: adopt the method for vacuum concentration to concentrate.
(3) drying: adopt lyophilize or spray drying process.
4. the activation of resin and regeneration:
(1) activation of new resin: new resin should be earlier with 95% ethanol bubble 30min, and washing removes ethanol again, soaks 1h by 2 times of volume 1-10%NaCl, is washed till neutral back again and uses.
(2) be used to the regeneration of resin that exchanged: Zeo-karb adopts the mode of acid-alkali-acid to clean, and each step should continue to be no less than 10min, and step will be washed pH neutrality with deionized water at interval.Anionite-exchange resin takes the mode of alkali-acid-alkali to clean, and each step should continue to be no less than 10min, and it is neutral that step will be washed pH with deionized water at interval.Employed bronsted lowry acids and bases bronsted lowry is 1-10%HCl and 1-10%NaOH.
Heavy metal removing situation:, use method involving of the present invention to handle after atomic absorption spectrum identifies that heavy metal content obviously reduces because the difference of season, the place of production, growth year, kind causes shellfish not the same to the enrichment condition of heavy metal.Especially the high more removal effect of contents of heavy metal elements is remarkable more.For example being example with the cadmium metal, is ppm in content in the shellfish polysaccharide, if content is tens, can make it reduce more than 98% after the IX; After if content is decimal place, can make it reduce by 50～85% after the IX.Exchange removal effect often is better.The shellfish heavy metal ion that removes according to the invention; Except metals ions such as cadmium, barium, vanadium, lead, thallium, molybdenum, uranium, strontium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver; Also comprise nonmetallic ions such as arsenic, selenium, its removal effect is all fine.
The advantage that the present invention gives prominence to is: 1. adopt the method for ion exchange resin the harmful heavy metal in the shellfish polysaccharide is removed, solved that sea-food is prone to enriching heavy metal and the problem that influences its nutritive value, thereby improved safety of products and quality.2. the ionic of deviating from is wide, and not only heavy metal ion, light metal ion can remove, and nonmetal example also can remove smoothly.
3. treatment process is simple, easy handling.Because ion exchange resin can regenerate, recycle, its cost greatly reduces simultaneously.
Embodiment
Embodiment one
With the homogenate of 50g abalone internal organs, be 1.0% with damping fluid to concentration of substrate (S), add Sumizyme MP, regulate pH to 10,43 ℃ of enzymolysis 3h, 90 ℃ of enzyme 10min postcooling that go out are to room temperature.Regulate pH to neutral, 4000r/min, centrifugal 10min.Supernatant concentration adds long-pending 95% ethanol of triploid, and alcohol precipitation 12h is centrifugal, removes supernatant.Deposition washing back recentrifuge, the dry abalone Crude polysaccharides that gets of alcohol precipitation once more.
Abalone internal organs Crude polysaccharides 100mg is added deionized water 200ml dissolving, add strong acid type Zeo-karb 100ml (Nankai's board), magnetic agitation 2h after-filtration, removing resin, to stay clear liquid be polysaccharide soln.Polysaccharide soln after the processing is through the abalone polysaccharide lyophilized powder of dialysing, concentrating, lyophilize having obtained removing heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.25ppm by the 0.72ppm before handling and reduced by 64%
Embodiment two
Producing of abalone Crude polysaccharides like embodiment one.
Abalone internal organs Crude polysaccharides 150mg is added deionized water 300ml dissolving, add 201 * 7 anionite-exchange resin 200mg (Nankai's board), magnetic agitation 2h after-filtration, removing resin, to stay clear liquid be polysaccharide soln.Polysaccharide soln after the processing through dialysis, concentrate and lyophilize has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.069ppm by the 0.11ppm before handling, and has reduced by 37.3%.
Embodiment three
Producing of abalone Crude polysaccharides like embodiment one.
Abalone internal organs Crude polysaccharides 300mg is added deionized water 500ml, add weak base type anionite-exchange resin 200ml (Nankai's board), magnetic agitation 3h after-filtration, removing resin, to stay clear liquid be polysaccharide soln.Polysaccharide soln after the processing through dialysis, concentrate and lyophilize has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.05ppm by the 0.11ppm before handling, and has reduced by 54.5%.
Embodiment four
Producing of abalone Crude polysaccharides like embodiment one.
200mg is dissolved in the 200ml deionized water with abalone internal organs Crude polysaccharides; Add strongly acidic cation-exchange 200ml (U.S. Dowex board), magnetic agitation 3h after-filtration, gained liquid is transferred pH to 10 with 1Mol/L NaOH; Add same resin 200ml once more, magnetic agitation 1h after-filtration.Polysaccharide soln after the processing through dialysis, concentrate and lyophilize has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.35ppm by the 12.76ppm before handling, and has reduced by 97.7%.
Embodiment five
Producing of abalone Crude polysaccharides like embodiment one.
100mg is dissolved in the 100ml deionized water with abalone internal organs Crude polysaccharides, adds 201 * 7 resin anion(R.A) 80ml (Nankai's board), magnetic agitation 3h after-filtration, and gained liquid is transferred pH to 9 with 1Mol/L NaOH, adds same resin 80ml once more, magnetic agitation 3h after-filtration.Polysaccharide soln after the processing through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Each 200mg of lyophilized powder sample carries out atomic absorption spectrum heavy metal content test analysis before and after getting processing, and its result shows that wherein cadmium content reduces to 0.048ppm by the 0.11ppm before handling, and has reduced by 56.4%.
Embodiment six
With the homogenate of 1kg scallop internal organs, be 3.0% with damping fluid to concentration of substrate (S), add the Sumizyme MP of dry weight massfraction 2%, regulate pH to 10,45 ℃ of enzymolysis 2h, 90 ℃ of enzyme 10min postcooling that go out are to room temperature.Regulate pH to neutral, 4000r/min, centrifugal 10min.Supernatant concentration adds long-pending 95% ethanol of triploid, and alcohol precipitation 12h is centrifugal, removes supernatant.Deposition washing back recentrifuge, the dry scallop Crude polysaccharides that gets of alcohol precipitation once more.
200mg is dissolved in the 400ml deionized water with scallop internal organs Crude polysaccharides; Add weak base type anionite-exchange resin 250ml (Nankai's board), magnetic agitation 2h after-filtration, gained liquid is transferred pH to 10 with 1Mol/L NaOH; Add same resin 250ml once more, magnetic agitation 1h after-filtration.Polysaccharide dialysis after the processing concentrates, and the alcohol precipitation drying has obtained removing the scallop polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.38ppm by the 60.39ppm before handling and reduced by 99.37%.
Embodiment seven
Producing of abalone Crude polysaccharides like embodiment one.
Strongly acidic cation-exchange (Nankai's board; Or other brands all can) 100ml records resin displacement chromatography post; The concentration of 20mg/ml installs polysaccharide 20ml additional, goes up current downflow 2h with the pump circulation and exchanges absorption, picks out polysaccharide liquid; Ion column goes out to remain polysaccharide with the 100ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid comes again with ion exchange column after another activation.The polysaccharide soln of collecting through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.09ppm by the 0.72ppm before handling and reduced by 87.5%.
Embodiment eight
Producing of abalone Crude polysaccharides like embodiment one.
Resin anion(R.A) (Nankai's board) 300ml records resin displacement chromatography post; The concentration of 50mg/ml installs polysaccharide 10ml additional; Go up current downflow 1h with the pump circulation and exchange absorption; Pick out polysaccharide liquid, ion column goes out to remain polysaccharide with the 100ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid comes again with ion exchange column after another activation.Collecting abalone polysaccharide liquid and washing lotion after exchanging for twice merges through the ultrafiltration desalination, concentrates and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.032ppm by the 0.11ppm before handling, and has reduced by 70.9%.
Embodiment nine
Producing of abalone Crude polysaccharides like embodiment one.
Weak base type anionite-exchange resin (Nankai's board; Or other brands all can) 400ml records resin displacement chromatography post; The concentration of 80mg/ml installs polysaccharide 10ml additional, goes up current downflow 3h with the pump circulation and exchanges absorption, picks out polysaccharide liquid; Ion column goes out to remain polysaccharide with the 80ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid comes again with ion exchange column after another activation.Abalone polysaccharide liquid and the washing lotion of collecting after exchanging for twice merge, through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.012ppm by the 0.11ppm before handling and reduced by 89.1%.
Embodiment picks up
Producing of abalone Crude polysaccharides like embodiment one.
201 * 7 resin anion(R.A)s (Nankai's board; Or other brands all can) 300ml records resin displacement chromatography post; The concentration of 40mg/ml installs polysaccharide 10ml additional, goes up current downflow 0.5h with the pump circulation and exchanges absorption, picks out polysaccharide liquid; Ion column goes out the surplus solution polysaccharide with the 90ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid exchanges 2h again with strong-acid type cation exchange column after another activation.Abalone polysaccharide liquid and the washing lotion of collecting after exchanging for twice merge, through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.056ppm by the 0.11ppm before handling, and has reduced by 49.1%.
Embodiment 11
Producing of abalone Crude polysaccharides like embodiment one.
Weak base type anionite-exchange resin (Nankai's board) 200ml records resin displacement chromatography post; The concentration of 70mg/ml installs polysaccharide 10ml additional; Go up current downflow 1h with the pump circulation and exchange absorption; Pick out polysaccharide liquid, ion column goes out the surplus solution polysaccharide with the 30ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid exchanges 2h again with strong-acid type cation exchange column after another activation.Abalone polysaccharide liquid and the washing lotion of collecting after exchanging for twice merge, through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 0.013ppm by the 0.11ppm before handling, and has reduced by 88.2%.
Embodiment 12
Producing of abalone Crude polysaccharides like embodiment one.
Weak base type anionite-exchange resin (Nankai's board) 100ml records resin displacement chromatography post; The concentration of 100mg/ml installs polysaccharide 10ml additional; Go up current downflow 1h with the pump circulation and exchange absorption; Pick out polysaccharide liquid, ion column goes out the surplus solution polysaccharide with the 60ml deionized water rinsing again, and the merging of twice collection polysaccharide liquid exchanges 1h again with anion column after another activation.Abalone polysaccharide liquid and the washing lotion of collecting after exchanging for twice merge, through the ultrafiltration desalination, concentrate and spraying drying has obtained removing the abalone polysaccharide lyophilized powder of heavy metal.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.023ppm by the 0.11ppm before handling and reduced by 79.1%.
Embodiment 13
Producing of scallop Crude polysaccharides like embodiment six.
300mg is dissolved in the 400ml deionized water with scallop internal organs Crude polysaccharides; Add strongly acidic cation-exchange 400ml (U.S. Dowex board), magnetic agitation 3h after-filtration, gained liquid is transferred pH to 10 with 1Mol/LNaOH; Add same resin 400ml once more, magnetic agitation 2h after-filtration.Polysaccharide after the processing through dialysis, concentrate and lyophilize must remove heavy metal and gets scallop polysaccharide.
Atomic absorption spectrum heavy metal content test analysis, its result shows that cadmium content wherein reduces to 0.20ppm by the 60.39ppm before handling and reduced by 99.7%.
Embodiment 14
Producing of scallop Crude polysaccharides like embodiment six.
250mg is dissolved in the 400ml deionized water with scallop internal organs Crude polysaccharides; Add 201 * 7 resin anion(R.A) 300ml (Nankai's board), magnetic agitation 2h after-filtration, gained liquid is transferred pH to 10 with 1Mol/L NaOH; Add same resin 300ml once more, magnetic agitation 1h after-filtration.Polysaccharide after the processing through dialysis, concentrate and lyophilize must remove heavy metal and gets scallop polysaccharide.
Atomic absorption spectrum heavy metal content test analysis, its result shows that wherein cadmium content reduces to 1.78ppm by the 60.39ppm before handling, and has reduced by 97.0%.
Embodiment 15
Producing of abalone Crude polysaccharides like embodiment one.
IX removes the heavy metal operation with embodiment four.
The content that removes front and back for the various heavy element that contains in the abalone polysaccharide (comprising some non-heavy metal elements) contrasts like following table in an embodiment;
Element contrast table (data unit: ppm) before and after shellfish polysaccharide heavy metal is removed
| Element | Al | Ti | V | Cr | Mn | Fe | Pb |
| After the removing | 68.02 | 8.88 | 0.75 | 0.84 | 10.88 | 107.51 | 40.56 |
| Before the removing | 812.86 | 232.17 | 14.45 | 20.72 | 27.09 | 3649.29 | 42.28 |
| Element | Co | Ni | Cu | Zn | As | Se | U |
| After the removing | 0.79 | 12.99 | 34.64 | 109.39 | 3.39 | 0.17 | 0.17 |
| Before the removing | 25.98 | 318.32 | 703.86 | 903.08 | 83.63 | 5.05 | 3.22 |
| Element | Sr | Mo | Ag | Cd | Ba | Tl | |
| After the removing | 202.37 | 0.6 | 0.41 | 0.35 | 45.41 | 0.00 | |
| Before the removing | 2181.04 | 9.34 | 4.37 | 12.76 | 495.93 | 0.00 |
Claims (4)
1. the method for removing heavy metal ions from marine shellfish polysaccharide is characterized in that adopting shellfish polysaccharide and ion exchange resin to carry out IX, makes the heavy metal ion in its absorption shellfish polysaccharide; The ion exchange resin that has carried out the absorption exchange back reuse of regenerating;
Removal methods is: the ratio with shellfish polysaccharide and ion exchange resin is 1.0g: 0.6～4.8ml; Process with the deionized water of 1～3 times of quality of shellfish polysaccharide and to carry out hybrid ionic exchange 0.5～6.0h under the solution normal temperature, collect that resulting shellfish polysaccharide soln carries out aftertreatment and the shellfish polysaccharide that obtained removing heavy metal:
Said aftertreatment comprises desalination, concentrated and dry:
(1) desalination:, remove the miscellaneous salts substances and promptly get the polysaccharide soln that removes behind the heavy metal with filtering 1-10K dalton's pore size semi-permeable membranes ultrafiltration or dialysis 1-12h with the polysaccharide soln of above-mentioned collection gained;
(2) concentrate: adopt the method for vacuum concentration to concentrate;
(3) drying: adopt lyophilize or spray drying process;
Said heavy metal ion of deviating from comprises: cadmium, barium, vanadium, lead, thallium, molybdenum, uranium, strontium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver metal ion also comprise arsenic, selenium nonmetallic ion.
2. according to the method for the said removing heavy metal ions from marine shellfish polysaccharide of claim 1, it is characterized in that described hybrid ionic exchange 1～3 time; The steps include: ion exchange resin, shellfish polysaccharide soln are mixed stirring 2～3h, remove by filter ion exchange resin, solution carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion;
The step of repeated exchanged is: NaOH or hydrochloric acid soln that the above-mentioned solution that removes by filter behind the ion exchange resin is 1mol/L with concentration are transferred required pH value; Add identical or different ion exchange resin and repeat aforesaid operations again 1～2 time; The solution that then obtains removes by filter ion exchange resin, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion again;
Said aftertreatment comprises desalination, concentrated and dry:
(1) desalination:, remove the miscellaneous salts substances and promptly get the polysaccharide soln that removes behind the heavy metal with filtering 1-10K dalton's pore size semi-permeable membranes ultrafiltration or dialysis 1-12h with the polysaccharide soln of above-mentioned collection gained;
(2) concentrate: adopt the method for vacuum concentration to concentrate;
(3) drying: adopt lyophilize or spray drying process.
3. according to the method for the said removing heavy metal ions from marine shellfish polysaccharide of claim 2, it is characterized in that described hybrid ionic is exchanged for the solution circulated exchange 1～3 time that makes the shellfish polysaccharide with ion exchange column; The steps include: ion exchange resin is adorned post; The solution of shellfish polysaccharide makes its absorption exchange 0.5～3.0h that in post, circulates with pump; Pick out the solution of shellfish polysaccharide; With 0.15～1.00% the de-ionized washing post of suitable ion exchange resin capacity, washing lotion merges with the solution that picks out the shellfish polysaccharide, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion;
The step of repeated exchanged is: the solution that will pick out the shellfish polysaccharide again with activation same or different ion exchange resin column carry out repeating aforesaid operations 1～2 time with the pump circulation; Washing lotion merges with the solution that picks out the shellfish polysaccharide, carries out the shellfish polysaccharide that aftertreatment has obtained removing heavy metal ion;
Said aftertreatment comprises desalination, concentrated and dry:
(1) desalination:, remove the miscellaneous salts substances and promptly get the polysaccharide soln that removes behind the heavy metal with filtering 1-10K dalton's pore size semi-permeable membranes ultrafiltration or dialysis 1-12h with the polysaccharide soln of above-mentioned collection gained;
(2) concentrate: adopt the method for vacuum concentration to concentrate;
(3) drying: adopt lyophilize or spray drying process.
4. according to the method for the said removing heavy metal ions from marine shellfish polysaccharide of claim 1, it is characterized in that said regeneration of ion-exchange resin of adsorbing exchange after owing to use different ion exchange resin, its renovation process is respectively:
The ion exchange resin that uses is that Zeo-karb adopts the mode of acid-alkali-acid to clean, and each step should continue to be no less than 10min, and it is neutral that step will be washed pH with deionized water at interval;
What use is that anionite-exchange resin takes the mode of alkali-acid-alkali to clean, and each step should continue to be no less than 10min, and it is neutral that step will be washed pH with deionized water at interval;
Employed bronsted lowry acids and bases bronsted lowry is respectively 1-10%HCl and 1-10%NaOH.
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| CN102242172B (en) * | 2010-05-10 | 2014-07-16 | 上海海健堂集团有限公司 | Method for extracting fish collagen from fish skin |
| CN103120275B (en) * | 2012-04-17 | 2014-07-02 | 杭州百山祖生物科技有限公司 | Method for removing heavy metals in edible fungi polysaccharide |
| CN105077382A (en) * | 2015-05-18 | 2015-11-25 | 浙江海洋学院 | Method for removing metal ions in shrimp products |
| JP6875973B2 (en) * | 2017-10-04 | 2021-05-26 | 株式会社神戸製鋼所 | How to treat marine biological resources |
| CN109929049B (en) * | 2019-03-29 | 2021-03-30 | 大连工业大学 | Method for removing heavy metal in acidic polysaccharide |
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