CN102266757A - Methods for preparing modified biomass absorbent and removing heavy metal from beverage - Google Patents
Methods for preparing modified biomass absorbent and removing heavy metal from beverage Download PDFInfo
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- CN102266757A CN102266757A CN2011102683733A CN201110268373A CN102266757A CN 102266757 A CN102266757 A CN 102266757A CN 2011102683733 A CN2011102683733 A CN 2011102683733A CN 201110268373 A CN201110268373 A CN 201110268373A CN 102266757 A CN102266757 A CN 102266757A
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Abstract
The invention belongs to the field of foods and the technical field of beverage heavy metal removal and relates to methods for preparing a modified biomass absorbent and removing heavy metal from beverage. Biomass is subjected to pickling, washing and alkaline leaching sequentially first and immersed by using absolute ethanol or garlic oil ethanol solution so as to prepare an absorbent A in a modified manner; and during preparation of the absorbent A, the garlic oil ethanol solution or a mercaptan-containing substance is added into an acetic anhydride and acetic acid mixing system so as to prepare an absorbent B under sulfuric acid serving as a catalyst. The absorbents are proportionally added into seafood enzymolysis polysaccharide or beverage and can selectively remove heavy metal from the seafood or the beverage, and polysaccharide loss is low. The treated seafood enzymolysis polysaccharide or beverage can meet a requirement of a food industry on quantity limitation of heavy metal and keep the nutrition; therefore, the methods have a wide market prospect.
Description
Technical field
The invention belongs to field of food and drink heavy metal removal technology field, relate to the method for heavy metal in a kind of modified biomass preparation of adsorbent and the removal drink.
Background technology
Because various fruit juices, marine product hyperalimentation fluid, have characteristics such as nutritious, taste aquatic foods, people incline to this type of drink always and like to have to add.Their maximum characteristics are can be water-soluble, the local flavor, flavour and the nutritional labeling that effectively keep natural prodcuts, the protein content height, be rich in multiple protein, polypeptide and amino acid and polysaccharide, especially the hyperalimentation fluid of marine product is the high-quality low-cost local flavor base-material that used by the favor of famous brand name producer.
But in recent years because being on the rise of soil, river, ocean heavy metal pollution, the content of each heavy metal species also becomes the topic that people are concerned about in the product.Fruit juice, marine product enzymolysis liquid complicated component wherein may cause containing various heavy in a lot of products, as Cu, Zn, Cr, Pb, Cd, As etc. owing to being subjected to industrial pollution.The Cr of trace is one of metabolic indispensable element of human body, but just can cause damage, gastric ulcer even the death of kidney and liver when the Cr of excess intake in the human body; Cr forms chromium oxide after entering blood, causes hemoglobin to become ferrihemoglobin, causes suffocating in the cell etc.In the world the limit standard of Cr content also is not quite similar for different food products, wherein " pollutant is limited the quantity of in the GB-2762-2005 food " regulation: Cr content must not surpass 2.0mg/kg in the fish and shellfish.And in the present detected marine product enzymolysis polysaccharide Cr content at 3.0-4.0mg/kg, considerably beyond national limit standard.
Also do not have at present both at home and abroad a kind of method of comparatively perfect system both can remove heavy metal in the drink, can guarantee the method that polysaccharide is not suffered a loss again simultaneously.The domestic patent No. is the method for 200910012667 removing heavy metal ions from marine shellfish polysaccharide, utilize ion exchange resin that the heavy metal in the shellfish polysaccharide is removed, the ratio of polysaccharide and ion exchange resin is 1.0g: 0.6-4.8ml in the process, the heavy metal removing rate is 47.0-99.7%, the method of the heavy metal in the seashells has been removed in the proposition early of this method, utilize the resin of chemical synthesis, have potential Pollution by Chemicals problem.
And living beings such as wood chip, dry fruit shell and cornstalk etc. to heavy metal because of having abundant cellulosic structure, heavy metal is had certain coordination ability, can adsorb the binding heavy metal ion.The patent No.: 200,610,156,067 1 kinds of modified absorben cottons and preparation thereof, using method disclose a kind of modified absorben cotton and preparation thereof, using method.Its preparation method is that absorbent cotton is mixed with citric acid solution, stir, dry to constant weight, be warming up to 115-125 ℃ and insulation, be chilled to room temperature, use the distilled water cyclic washing, filter, add the capacity alkali metal soln in the filtered object, filter after stirring is not less than 60 minutes, filtered object is washed with distilled water to neutrality, is dried to constant weight; Its using method is regulated pH to 4-7 for containing cation waste water, adds the stirring of 1-20g/L modified absorben cotton and is not less than 30 minutes, can be used to handle cationic waste water.
In addition, the patent No. 200910186876 functionalized nano-fiber heavy metal ion adsorbing materials and preparation method thereof, disclosure of the Invention a kind of functionalized nano-fiber heavy metal ion adsorbing material and preparation method thereof, described material is prepared by following steps: (1) is dissolved polymeric substrate, functionalized reagent and is formed the polymer solution that has functionalized reagent in suitable solvent; (2) utilize electrospinning process that the polymer solution that has functionalized reagent of (1) preparation is made functionalized nano-fiber heavy metal ion adsorbing material.The fibre diameter of described functionalized nano-fiber heavy metal ion adsorbing material is in 10～1000nm scope.The fibrous material of this method handy and safe, preparation is of a size of nanometer grade diameter, specific area is big, absorption property is strong, the use amount of material is few during application, help the application in the few biological sample of sample size, but its used functionalized reagent is an organic compound, has certain potential chemical contamination for food and food service industry.
Heavy metal purification techniques in the existing food and drink utilizes the absorption of industrial chelating resin or chelate fibre, lacks the adsorbent of special food service industry.
Summary of the invention
The present invention proposes a kind of living beings of series methods modification of utilizing and remove heavy metal in the drink, the new method of as far as possible not losing polysaccharide again simultaneously.
For achieving the above object, the technical solution adopted in the present invention is:
Earlier living beings fragmentation, pickling, washing, alkali such as cotton, wood chip, buckwheat skin are soaked,, living beings are carried out modification then with alcohol solution dipping 1-8 hour of absolute ethyl alcohol or 0.5%-30% garlic oil; The concentration of modification alkali lye is 0.1-2M, soaks 0.3-3 hour, and temperature is 30-90 ℃, is washed to neutrality after soaking, and carries out drying then at low temperatures and obtains adsorbent A.Used alkali is nontoxic alkali (soil) the metal hydroxides aqueous solution.
For improving the wide spectrum effect, in preparation adsorbent A process, in acetic anhydride and acetate mixed system, add the ethanolic solution or the sulfur-bearing alcohols material of 0.5%-30% garlic oil, sulfuric acid is catalyst, carries out grafting; Be washed to neutrality, get adsorbent B under the low temperature after the drying.
Adsorbent A of preparing or B can pack into and be prepared into the fixed bed of serial or parallel connection in the Filter column.
Remove the heavy metal of marine product enzymolysis polysaccharide drink: at first, marine product enzymolysis polysaccharide and water in 1: the 40-60 ratio is mixed, after stirring dissolving in 1-5 hour then at normal temperatures fast, in the post that installs the adsorbent filler, add the enzymolysis liquid after water-soluble, it did not have the adsorbent filler and exceeded the about 10cm of packed height, began post after soaking half an hour, the control flow velocity is at 0.3-1.6ml/min.
Remove the heavy metal in the drink: is 1 with adsorbent by the ratio of beverage volume (L) and adsorbent mass (g): 0.2-50 (v/m) joins in the beverage and stirs, and constantly detects content of beary metal; When detecting content of beary metal behind the food limit standard, Separation of Solid and Liquid, the drink after promptly being purified.Drink after the processing, polysaccharide loss is few.
The adsorbent of the present invention's preparation can be selected to remove to the heavy metal in the drink, and polysaccharide loss is few; Route is simple, and non-secondary pollution, cost are low etc.Marine product enzymolysis polysaccharide or drink after the processing can satisfy food service industry for the heavy metal limit requirement, can keep the nutritive value of itself again, and market prospects are wide.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is described in further detail, but the present invention is not limited to embodiment 1:
With the cotton is example, after cotton is pulverized pickling, cleans up, and drying, nontoxic aqueous slkali soaking 0.3-3 hour of utilizing 0.1-2.0M, the control temperature is at 30-90 ℃.Used alkali is nontoxic alkali (soil) the metal hydroxides aqueous solution.Use soaked in absolute ethyl alcohol 1-8 hour then, and wash that low temperature drying promptly gets adsorbent A to the neutrality with water.For improving the wide spectrum effect, in preparation adsorbent A process, in acetic anhydride and acetate mixed system, add the ethanolic solution or the sulfur-bearing alcohols material of 0.5%-30% garlic oil, sulfuric acid is catalyst, carries out grafting, is washed to neutrality, gets adsorbent B after the low temperature drying.
Embodiment 2: adsorbent A is to the removal of marine product enzymolysis polysaccharide drink Cr
The first step: utilize absorbent cotton to be raw material, with soaking 1 hour in 0.5M NaOH 80 ℃ of water-baths, be washed to neutrality then after, place 35 ± 2 ℃ of baking ovens dry; Use soaked in absolute ethyl alcohol after 1 hour then, and after water cleans up, place 35 ± 2 ℃ of baking ovens to carry out dry adsorbent A.
Second step: marine product enzymolysis polysaccharide is mixed mixing time dissolving in 3 hours under the normal temperature with water according to 1: 40 ratio.
The 3rd step: the good adsorbent of modification packed into serve as filler in the post.In the post that installs the adsorbent filler, add the enzymolysis liquid after water-soluble, make it not have the adsorbent filler and exceed the about 10cm of packed height, immersion half an hour, began post.
The 4th step: will control the flow velocity of enzymolysis polysaccharide liquid when crossing post well, it is flowed out with 0.3dm/min.
The 5th step: the enzymolysis polysaccharide liquid of the intact post of above-mentioned mistake is cleared up processing, make it become colourless transparent liquid, detect.Average polysaccharide loss rate is below 10%, and heavy metal is lower than the state food limit standard.
Embodiment 3: adsorbent A is to the removal of marine product enzymolysis polysaccharide drink Cd
The first step: with absorbent cotton is raw material, with soaking 1 hour in 0.5M NaOH 80 ℃ of water-baths, be washed to neutrality after, place 35 ± 2 ℃ of baking ovens dry; Then with the alcohol solution dipping 1 hour that is dissolved with 1% garlic oil, and after water cleans up, place 35 ± 2 ℃ of baking ovens to carry out dry adsorbent A again.
Second step: marine product enzymolysis polysaccharide is mixed mixing time dissolving in 3 hours under the normal temperature with water according to 1: 40 ratio.
The 3rd step: in the good adsorbent of modification is packed post into, serving as filler.In the post that installs the adsorbent filler, add the enzymolysis liquid after water-soluble, make it not have the adsorbent filler and exceed the about 10cm of packed height, immersion half an hour, began post.
The 4th step: will control the flow velocity of enzymolysis polysaccharide liquid when crossing post well, it is flowed out with 0.6dm/min.
The 5th step: the enzymolysis polysaccharide liquid of the intact post of above-mentioned mistake is cleared up processing, be colourless transparent liquid, detect.The test result content of beary metal is lower than the state food limit standard.The loss late of polysaccharide is 20%.
Embodiment 4: the wide spectrum adsorbent B is to the removal of single heavy metal Pb in the simulation beverage
The first step: in wide-mouth bottle, add the 50mL TGA, the 30mL acetic anhydride, the 20mL glacial acetic acid and the 75 μ L concentrated sulfuric acids are cooled to room temperature after mixing, and add cotton (wood chip or buckwheat skin) and complete wetting that 7.5g shreds.Wide-mouth bottle sealing was placed in 38 ℃ the water-bath reaction 4 days, and stirred the primary first-order equation thing with glass bar every 20 hours.The reaction finish after water product is washed till neutrality, place 36 ℃ of baking ovens dry adsorbent B.
Second step: configuration contains the beverage simulated solution of glucose 500mg/L, and contains lead ion 25mg/L.
The 3rd step: get the above-mentioned beverage simulated solution of 50mL, regulating pH is about 6, adds the adsorbent (before the modification or after the modification) of 0.01g, stirring and adsorbing heavy metal under the room temperature condition.
The 4th step: stop concussion after 3 hours, detect in the above-mentioned simulated solution clear liquid content of sugar and heavy metal.The loss late of test result polysaccharide is almost nil, and the heavy metal adsorbance sees the following form:
The 5th step: continue to add adsorbent, concussion also constantly detects content of beary metal, till content of beary metal reaches the food limit standard, carries out Separation of Solid and Liquid then.
Embodiment 5: the wide spectrum adsorbent B is to the removal of various heavy in the simulation beverage
The first step: in wide-mouth bottle, add the 50mL TGA, the 30mL acetic anhydride, the 20mL glacial acetic acid and the 75 μ L concentrated sulfuric acids are cooled to room temperature after mixing, and add cotton and complete wetting that 7.5g shreds.Wide-mouth bottle sealing was placed in 38 ℃ the water-bath reaction 4 days, and stirred the primary first-order equation thing with glass bar every 20 hours.Water was washed till neutrality with product, the adsorbent B that places 36 ℃ of baking ovens to dry after reaction was finished.
Second step: configuration contains the beverage simulated solution of glucose 500mg/L, and cupric, lead, zinc ion concentration are 25mg/L.
The 3rd step: get the above-mentioned beverage simulated solution of 50mL, regulating pH is about 6, adds the adsorbent (before the modification or after the modification) of 0.01g, stirring and adsorbing heavy metal under the room temperature condition.
The 4th step: stop concussion after 3 hours, detect in the above-mentioned simulated solution clear liquid content of sugar and heavy metal.The loss late of test result polysaccharide is almost nil, and the heavy metal adsorbance sees the following form:
The 5th step: continue to add adsorbent, concussion absorption also constantly detects content of beary metal, till content of beary metal reaches the food limit standard, carries out Separation of Solid and Liquid then.
Claims (7)
1. a modified biomass preparation of adsorbent is characterized in that: adopt fragmentation, pickling, washing, alkali to soak, with alcohol solution dipping 1-8 hour of absolute ethyl alcohol or 0.5%-30% garlic oil, living beings are carried out modification then; The concentration of modification alkali lye is 0.1-2M, soaks 0.3-3 hour, and temperature is 30-90 ℃, is washed to neutrality after soaking, and carries out drying then at low temperatures and obtains adsorbent A; Used alkali is nontoxic alkali (soil) the metal hydroxides aqueous solution.
2. a kind of modified biomass preparation of adsorbent according to claim 1 is characterized in that: described living beings are cotton, wood chip, buckwheat skin.
3. a kind of modified biomass preparation of adsorbent according to claim 1 and 2, it is characterized in that: in preparation adsorbent A process, add the ethanolic solution or the sulfur-bearing alcohols material of 0.5%-30% garlic oil in acetic anhydride and acetate mixed system, sulfuric acid is catalyst, carries out grafting; Be washed to neutrality, get adsorbent B under the low temperature after the drying.
4. the modified biomass adsorbent of claim 1 or 2 described preparations is to the removal method of heavy metal in the marine product enzymolysis polysaccharide drink, it is characterized in that: at first, marine product enzymolysis polysaccharide and water in 1: the 40-60 ratio is mixed, after stirring dissolving in 1-5 hour then at normal temperatures, in the post that installs the adsorbent filler, add the enzymolysis liquid after water-soluble, it did not have the adsorbent filler and exceeded the about 10cm of packed height, and immersion began post after half an hour, and the control flow velocity is at 0.3-1.6ml/min.
5. the modified biomass adsorbent of claim 1 or 2 described preparations is to the removal method of heavy metal in the drink, it is characterized in that: is 1 with adsorbent in the ratio of beverage volume (L) and adsorbent mass (g): 0.2-50 joins in the beverage and stirs, and constantly detects content of beary metal; When detecting content of beary metal behind the food limit standard, Separation of Solid and Liquid, the drink after promptly being purified.
6. the modified biomass adsorbent of the described preparation of claim 3 is to the removal method of heavy metal in the marine product enzymolysis polysaccharide drink, it is characterized in that: at first, marine product enzymolysis polysaccharide and water in 1: the 40-60 ratio is mixed, after stirring dissolving in 1-5 hour then at normal temperatures, in the post that installs the adsorbent filler, add the enzymolysis liquid after water-soluble, it did not have the adsorbent filler and exceeded the about 10cm of packed height, and immersion began post after half an hour, and the control flow velocity is at 0.3-1.6ml/min.
7. the modified biomass adsorbent of the described preparation of claim 3 is to the removal method of heavy metal in the drink, it is characterized in that: is 1 with adsorbent in the ratio of beverage volume (L) and adsorbent mass (g): 0.2-50 joins in the beverage and stirs, and constantly detects content of beary metal; When detecting content of beary metal behind the food limit standard, Separation of Solid and Liquid, the drink after promptly being purified.
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Cited By (5)
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| CN102557181A (en) * | 2012-01-20 | 2012-07-11 | 北京科技大学 | Method for adsorption and removal of heavy metals and dye of waste water by garlic waste |
| CN104353430A (en) * | 2014-11-13 | 2015-02-18 | 中国烟草总公司郑州烟草研究院 | Plant adsorbing material capable of reducing lead content of tree moss extract and application thereof |
| CN105170098A (en) * | 2015-10-10 | 2015-12-23 | 常州大学 | Method for preparing hydrophobic silica gel through microwave-esterification modification |
| CN104046779B (en) * | 2014-06-23 | 2016-08-24 | 北京科技大学 | A kind of garlic waste is utilized to extract the method for noble metal in hydrochloric acid medium solution |
| CN107486161A (en) * | 2017-08-14 | 2017-12-19 | 中国烟草总公司郑州烟草研究院 | A kind of adsorbent for heavy metal and its application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557181A (en) * | 2012-01-20 | 2012-07-11 | 北京科技大学 | Method for adsorption and removal of heavy metals and dye of waste water by garlic waste |
| CN104046779B (en) * | 2014-06-23 | 2016-08-24 | 北京科技大学 | A kind of garlic waste is utilized to extract the method for noble metal in hydrochloric acid medium solution |
| CN104353430A (en) * | 2014-11-13 | 2015-02-18 | 中国烟草总公司郑州烟草研究院 | Plant adsorbing material capable of reducing lead content of tree moss extract and application thereof |
| CN105170098A (en) * | 2015-10-10 | 2015-12-23 | 常州大学 | Method for preparing hydrophobic silica gel through microwave-esterification modification |
| CN105170098B (en) * | 2015-10-10 | 2017-09-08 | 常州大学 | A kind of method that utilization microwave esterification modification prepares dewatering silica gel |
| CN107486161A (en) * | 2017-08-14 | 2017-12-19 | 中国烟草总公司郑州烟草研究院 | A kind of adsorbent for heavy metal and its application |
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| CN102266757B (en) | 2014-04-23 |
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