CN102266757B - 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 PDF

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CN102266757B
CN102266757B CN201110268373.3A CN201110268373A CN102266757B CN 102266757 B CN102266757 B CN 102266757B CN 201110268373 A CN201110268373 A CN 201110268373A CN 102266757 B CN102266757 B CN 102266757B
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adsorbent
heavy metal
beverage
polysaccharide
hour
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CN102266757A (en
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马伟
吴志敏
程子洪
王刃
宋晓燕
吕腾飞
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Dalian University of Technology
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Dalian University of Technology
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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

A kind of method of heavy metal in preparation of modified biomass adsorbent and removal drink
Technical field
The invention belongs to field of food and drink heavy metal removal technology field, relate to a kind of preparation of modified biomass adsorbent and remove the method for heavy metal in drink.
Background technology
Due to various fruit juices, marine product hyperalimentation fluid, there is the features such as nutritious, taste is fresh, people incline always and like to have to add this type of drink.Their maximum feature is can be water-soluble, effectively retain local flavor, flavour and the nutritional labeling of natural prodcuts, protein content is high, 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 the favor of Shou famous brand name producer is used in the world at present.
But due to being on the rise of soil, river, marine sediment, in product, the content of each heavy metal species also becomes the topic that people are concerned about in recent years.Fruit juice, marine product enzymolysis liquid complicated component, wherein may cause containing various heavy in a lot of products owing to being subject to industrial pollution, as Cu, Zn, Cr, Pb, Cd, As etc.The Cr of trace is one of metabolic indispensable element of human body, but when human body in, just can cause damage, the even death of gastric ulcer of kidney and liver during the Cr of excess intake; Cr forms chromium oxide after entering blood, causes hemoglobin to become ferrihemoglobin, causes suffocating etc. in cell.For different food products, in the world the limit standard of Cr content is also not quite similar, wherein limit the quantity of > > regulation of < < GB-2762-2005 pollutants in food: in fish and shellfish, Cr content must not surpass 2.0mg/kg.And in the marine product enzymolysis polysaccharide detecting at present Cr content at 3.0-4.0mg/kg, considerably beyond national limit standard.
At present also do not have a kind of method of comparatively perfect system both can remove the heavy metal in drink both at home and abroad, 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 to remove the heavy metal in Shellfish polysaccharide, in process, the ratio of polysaccharide and ion exchange resin is 1.0g: 0.6-4.8ml, heavy metal removing rate is 47.0-99.7%, the method of the heavy metal in seashells has been removed in the proposition early of this method, utilize the resin of chemical synthesis, there is potential Pollution by Chemicals problem.
And living beings are as the counterweight because of metals such as wood chip, dry fruit shell and cornstalk have abundant cellulosic structure, heavy metal is had to certain coordination ability, can adsorb 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 distilled water cyclic washing, filter, in filtered object, add enough alkali metal solns, after stirring is not less than 60 minutes, filter, filtered object is washed with distilled water to neutrality, is dried to constant weight; Its using method regulates pH to 4-7 for containing cation waste water, adds 1-20g/L modified absorben cotton to stir and is not less than 30 minutes, can be for the treatment of 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) dissolves polymeric substrate, functionalized reagent the polymer solution forming with functionalized reagent in suitable solvent; (2) utilize the polymer solution with functionalized reagent that electrospinning process is prepared (1) to make functionalized nano-fiber heavy metal ion adsorbing material.The fibre diameter of described functionalized nano-fiber heavy metal ion adsorbing material is within the scope of 10~1000nm.The fibrous material of the method handy and safe, preparation is of a size of nanometer grade diameter, specific area is large, absorption property is strong, during application, the use amount of material is few, be conducive to the application in the few biological sample of sample size, but its functionalized reagent used is organic compound, for food and food service industry, there is certain potential chemical contamination.
Heavy metal purification techniques in existing food and drink, utilizes industrial chelating resin or chelate fibre absorption, 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 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:
First living beings fragmentation, pickling, washing, the alkali such as cotton, wood chip, buckwheat skin are soaked, then with the alcohol solution dipping 1-8 hour of absolute ethyl alcohol or 0.5%-30% garlic oil, living beings are carried out to modification; The concentration of modification alkali lye is 0.1-2M, soaks 0.3-3 hour, and temperature is 30-90 ℃, after soaking, is washed to neutrality, is then dried at low temperatures and obtains adsorbent A.Alkali used is nontoxic alkali (soil) the metal hydroxides aqueous solution.
For improving wide spectrum effect, in preparation adsorbent A process, in acetic anhydride and acetic acid mixed system, add 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, after being dried under low temperature, obtain adsorbent B.
The adsorbent A of preparing or B can pack the fixed bed that is prepared into serial or parallel connection in Filter column into.
Remove the heavy metal of marine product enzymolysis polysaccharide drink: first, marine product enzymolysis polysaccharide with water in 1: 40-60 ratio is mixed, then after within rapid stirring 1-5 hour at normal temperatures, dissolving, to installing the enzymolysis liquid adding in the post of adsorbent filler after water-soluble, it did not have adsorbent filler and exceeded the about 10cm of packed height, after soaking half an hour, started post, coutroi velocity is at 0.3-1.6ml/min.
Remove the heavy metal in drink: by adsorbent, in beverage volume (L), be 1 with the ratio of adsorbent mass (g): 0.2-50 (v/m) joins in beverage and stirs, and constantly detects content of beary metal; When detecting content of beary metal after food limit standard, Separation of Solid and Liquid, the drink after being purified.Drink after processing, polysaccharide loss is few.
Adsorbent prepared by the present invention can be selected to remove to the heavy metal in drink, and polysaccharide loss is few; Route is simple, and non-secondary pollution, cost are low etc.Marine product enzymolysis polysaccharide or drink after processing, can meet food service industry for 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:
Take cotton as example, after cotton is pulverized to pickling, cleans up, dry, utilize the nontoxic aqueous slkali soaking 0.3-3 hour of 0.1-2.0M, control temperature at 30-90 ℃.Alkali used is nontoxic alkali (soil) the metal hydroxides aqueous solution.Then use soaked in absolute ethyl alcohol 1-8 hour, and wash with water to low temperature drying after neutrality and obtain adsorbent A.For improving wide spectrum effect, in preparation adsorbent A process, in acetic anhydride and acetic acid mixed system, add 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, obtains adsorbent B after low temperature drying.
Embodiment 2: the removal of adsorbent A to marine product enzymolysis polysaccharide drink Cr
The first step: utilize absorbent cotton for raw material, with soaking 1 hour in 80 ℃ of water-baths of 0.5M NaOH, be then washed to after neutrality, be placed in 35 ± 2 ℃ of baking ovens dry; Then use soaked in absolute ethyl alcohol after 1 hour, and after water cleans up, be placed in 35 ± 2 ℃ of baking ovens and be dried to obtain adsorbent A.
Second step: marine product enzymolysis polysaccharide is mixed according to 1: 40 ratio with water, and under normal temperature, mixing time is dissolved for 3 hours.
The 3rd step: the good adsorbent of modification is packed into and serves as filler in post.To installing the enzymolysis liquid adding in the post of adsorbent filler after water-soluble, make it not have adsorbent filler and exceed the about 10cm of packed height, soak half an hour, started post.
The 4th step: will control the flow velocity of enzymolysis polysaccharide liquid while crossing post well, it is flowed out with 0.3dm/min.
The 5th step: the enzymolysis polysaccharide liquid of the complete post of above-mentioned mistake is cleared up to processing, become colourless transparent liquid, detect.Average polysaccharide loss rate is below 10%, and heavy metal is lower than state food limit standard.
Embodiment 3: the removal of adsorbent A to marine product enzymolysis polysaccharide drink Cd
The first step: take absorbent cotton as raw material, with soaking 1 hour in 80 ℃ of water-baths of 0.5M NaOH, be washed to after neutrality, be placed in 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, then be placed in 35 ± 2 ℃ of baking ovens and be dried to obtain adsorbent A.
Second step: marine product enzymolysis polysaccharide is mixed according to 1: 40 ratio with water, and under normal temperature, mixing time is dissolved for 3 hours.
The 3rd step: serve as filler in post packing into through the good adsorbent of modification.To installing the enzymolysis liquid adding in the post of adsorbent filler after water-soluble, make it not have adsorbent filler and exceed the about 10cm of packed height, soak half an hour, started post.
The 4th step: will control the flow velocity of enzymolysis polysaccharide liquid while crossing post well, it is flowed out with 0.6dm/min.
The 5th step: the enzymolysis polysaccharide liquid of the complete post of above-mentioned mistake is cleared up to processing, be colourless transparent liquid, detect.Test result content of beary metal is lower than state food limit standard.The loss late of polysaccharide is 20%.
Embodiment 4: the removal of wide spectrum adsorbent B to single heavy metal Pb in simulation beverage
The first step: in wide-mouth bottle, add 50mL TGA, 30mL acetic anhydride, 20mL glacial acetic acid and the 75 μ L concentrated sulfuric acids, be cooled to room temperature after mixing, and adds cotton (wood chip or buckwheat skin) complete wetting that 7.5g shreds.Wide-mouth bottle is sealed in the water-bath that is placed on 38 ℃ and reacted 4 days, every 20 hours, with glass bar, stir primary first-order equation thing.Reacted rear water product has been washed till to neutrality, be placed in 36 ℃ of baking ovens and dry to obtain adsorbent B.
Second step: configuration contains the beverage simulated solution of glucose 500mg/L, and containing lead ion 25mg/L.
The 3rd step: get the above-mentioned beverage simulated solution of 50mL, regulating pH is 6 left and right, adds the adsorbent (before modification or after modification) of 0.01g, stirring and adsorbing heavy metal under room temperature condition.
The 4th step: stop concussion after 3 hours, detect the content of sugared in above-mentioned simulated solution clear liquid and heavy metal.The loss late of test result polysaccharide is almost nil, and heavy metal adsorption amount sees the following form:
The 5th step: continue to add adsorbent, concussion also constantly detects content of beary metal, until content of beary metal reaches food limit standard, then carries out Separation of Solid and Liquid.
Embodiment 5: the removal of wide spectrum adsorbent B to various heavy in simulation beverage
The first step: in wide-mouth bottle, add 50mL TGA, 30mL acetic anhydride, 20mL glacial acetic acid and the 75 μ L concentrated sulfuric acids, be cooled to room temperature after mixing, and adds cotton complete wetting that 7.5g shreds.Wide-mouth bottle is sealed in the water-bath that is placed on 38 ℃ and reacted 4 days, every 20 hours, with glass bar, stir primary first-order equation thing.React rear water product has been washed till to neutrality, be placed in the adsorbent B that 36 ℃ of baking ovens are dried.
Second step: configuration is containing 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 6 left and right, adds the adsorbent (before modification or after modification) of 0.01g, stirring and adsorbing heavy metal under room temperature condition.
The 4th step: stop concussion after 3 hours, detect the content of sugared in above-mentioned simulated solution clear liquid and heavy metal.The loss late of test result polysaccharide is almost nil, and heavy metal adsorption amount sees the following form:
The 5th step: continue to add adsorbent, concussion absorption also constantly detects content of beary metal, until content of beary metal reaches food limit standard, then carries out Separation of Solid and Liquid.

Claims (3)

1. a preparation method for modified biomass adsorbent, is characterized in that: after cotton is pulverized to pickling, cleans up, dry, utilize the nontoxic aqueous slkali soaking 0.3-3 hour of 0.1-2.0M, and control temperature at 30-90 ℃; Alkali used is nontoxic alkali metal hydroxide aqueous solution; Then use soaked in absolute ethyl alcohol 1-8 hour, and wash with water to low temperature drying after neutrality and obtain adsorbent.
2. the removal method of the modified biomass adsorbent that described in claim 1 prepared by preparation method to heavy metal in marine product enzymolysis polysaccharide drink, it is characterized in that: first, marine product enzymolysis polysaccharide is mixed in 1:40-60 ratio with water, then stir at normal temperatures after dissolving in 1-5 hour, to installing the enzymolysis liquid adding in the post of adsorbent filler after water-soluble, it did not have adsorbent filler and exceeded packed height 10cm, and immersion started post after half an hour, and coutroi velocity is at 0.3-1.6ml/min.
3. the removal method of the modified biomass adsorbent that described in claim 1 prepared by preparation method to heavy metal in drink, it is characterized in that: by adsorbent, in the ratio of beverage volume and adsorbent mass, be that 1:0.2-50v/m joins in beverage and stirs, and constantly detect content of beary metal; When detecting content of beary metal after food limit standard, Separation of Solid and Liquid, the drink after being purified.
CN201110268373.3A 2011-09-10 2011-09-10 Methods for preparing modified biomass absorbent and removing heavy metal from beverage Active CN102266757B (en)

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CN102557181B (en) * 2012-01-20 2013-06-12 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
CN104353430B (en) * 2014-11-13 2016-08-17 中国烟草总公司郑州烟草研究院 A kind of plant absorptive material reducing lead content in tree moss extract and application thereof
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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