CN1868576B - Biological modification infusorial earth adsorbent, and its prepn. method - Google Patents
Biological modification infusorial earth adsorbent, and its prepn. method Download PDFInfo
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- CN1868576B CN1868576B CN2005100261252A CN200510026125A CN1868576B CN 1868576 B CN1868576 B CN 1868576B CN 2005100261252 A CN2005100261252 A CN 2005100261252A CN 200510026125 A CN200510026125 A CN 200510026125A CN 1868576 B CN1868576 B CN 1868576B
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Abstract
A biologically modified diatomite adsorbent for adsorbing the protein, heavy metal, Fe, residual agricultural chemical and antibiotics from specimen, or fixating enzyme, cell and biologic macro moleculae is composed of the tannin modified diatomite as carrier and the biologic cells or organic component fixed to said carrier. Its preparing process is also disclosed.
Description
Technical field
The present invention relates to biological adsorption agent and preparation method thereof.Be specifically related to a kind of biological modification infusorial earth adsorbent and preparation method thereof.
Background technology
Absorption is the important method of utility in impurity or the extracting liq in the separating liquid, is widely used in fields such as beverage preparation, Industrial Wastewater Treatment, oil product manufacturing, medical industry and chemical analysis.Existing adsorbent is divided into inorganic adsorbent, organic adsorbent and biological adsorption agent.The key of decision adsorbent application is its chemical composition and surface nature.
Inorganic adsorbent commonly used comprises silica gel, aluminium oxide, active carbon, diatomite, magnesia, calcium carbonate, calcium phosphate, clay, perlite, vermiculite, bloating shale and natural zeolite etc.Inorganic adsorbent can be used for adsorbing various types of hydrocarbon, acid and derivative thereof, alcohol, aldehyde, ketone, ester and nitro compound and is used for selectively adsorbing the molecule of different sizes or the ion of opposed polarity, wherein activated carbon is because of being easy to get and practical, is present decolouring, eliminates the unusual smell and handle water adsorbent commonly used.There is poor selectivity in inorganic adsorbent, and accumulation ability is not strong, and absorption property such as can't adjust at defective.
Organic adsorbent is divided into natural organic adsorbent and synthetic adsorbent.Advantages such as that natural organic adsorbent such as cellulose, starch, sucrose has is inexpensive, nontoxic, be easy to get have Many researchers it to be had at present and utilize and carried out modification, develop multiple adsorbent.Fanta etc. utilize no initator and different monomers that crosslinked starch is carried out glycerol polymerization, develop the different adsorbent of performance.Wang Yuting etc. are with Fe
2+,--H
2O
2Be initator, to the crosslinked starch skeleton, the carboxyl grafting starch of developing can effectively remove the Cd in anhydrating with acrylonitrile grafting
2+, Pb
2+, Cu
2+, Hg
2+, Cr
3+Deng (Liu Minghua etc., chemical industry environmental protection, 2001,21 (1): 1～5).But a big defective of right organic adsorbent is the regeneration difficulty.Synthetic adsorbent generally has bigger specific area and enough adsorption capacities; The different material that desire is separated has different adsorption capacities, and enough resolving powers are promptly arranged; With eluant, eluent, solvent and sample component chemical reaction can not take place; Absorbent particles is even.Can regeneration be a big advantage of synthetic adsorbent.Synthetic adsorbent commonly used has polyurethane, polypropylene and the resin of a large amount of meshes is arranged.The defective of synthetic adsorbent is to make difficulty, and cost is higher, and is aging easily, may bring residual chemical toxicity pollution etc. to food and medicine.
A lot of researchs are arranged aspect biological cell and the natural organic matter absorption utilizing both at home and abroad in recent years.The overseas utilization biosorption process is removed the heavy metal in the waste water.Greene uses gold (Geene Betal., Environ.Sci.Technol., 1986 in the algae removal water, 20:627～632), Tsezo/Maranon uses uranium (Tsezos Metal, the Biotechnol Bioeng. in the fungi adsorbed water, 1998,32:545～550).Mark Spint etc. are fixed on bog moss the Zn that successfully is applied to remove in the polymerization sulfuryl matter of porous in the acid mine water
2+, Cd
2+, Mg
2+Deng metal ion (Mark Spintietal., Water Environment Research., 1995,67 (6): 943～952).Biological adsorption agent is a kind of special ion-exchanger, and wherein microorganism is to be utilized object, and biological cell plays a major role.Discover that microorganisms such as bacterium, fungi, algae can adsorb or enriching heavy metal, and the microbial cell surface that can not only live, can also carry out on dead microbial cell surface, the microorganism Adsorption of Heavy Metal Ions is carried out ion-exchange with the active group on microbial cell surface and is mutually combined.The effect of using biological adsorption agent to remove heavy metal ion in the water is higher than the exchanger of common ion significantly.The preparation of biological adsorption agent is exactly that microorganism is fixed on the carrier by certain mode, and the mode of fixation of microbe cell commonly used comprises absorption method, covalent bond method, cross-linking method and investment.
Relevant biological modification infusorial earth adsorbent does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of biological modification infusorial earth adsorbent.This adsorbent is made of tannin modification infusorial earth carrier and biological cell or the biological organic principle fixed on it, be used for adsorbing harmful substances such as protein, heavy metal, irony, the farming of removing sample are residual, antibiotic, also can be used for fixed biologically enzyme, biological cell and large biological molecule.
Another object of the present invention is to provide this preparation of adsorbent method.
Biological modification infusorial earth adsorbent of the present invention is white or brown particle, slight fragrance is arranged, fineness is the 20-100 order, this adsorbent is made of tannin modification infusorial earth carrier and biological cell or the biological organic principle fixed on it, wherein tannin modification infusorial earth carrier is made of diatomite support particle and the tannin of fixing on it, and the usage ratio of diatomite support particle, tannin and biological cell or biological organic principle (by weight) is 10: 1～3: 1～4.
Among the present invention, the diatomite support particle is the single-size that diatomite obtains through 800 ℃ of calcinings, washing, drying, pulverizing, screening, and fineness is the 20-100 order.That diatomite should be selected for use is pure, light weight, grain are thin, the diatomite of porous, promptly selects SiO for use
2Content be 80-90% (butt, by weight), dry back density is 0.4～0.7g/cm
3, porosity reaches 85-95%, can absorb the diatomite of itself weight 1.5-4 times water, this diatomite has been removed complicated organic matter and soluble impurity after 800 ℃ of calcinings are cleaned, but has kept the structure and the unique shape of natural diatom anatomy, so diatomite support comes down to SiO
2Empty loose skeleton.
Tannin is the tannin composition that extracts from natural plants, and natural tannin employing molecular weight is hydrolyzable tannin or the condensed tannin of 500-1000 among the present invention, as five alkaloids, acorn cup tannin, larch tannin, black chaste tree tannin, theotannin etc.
Biological cell or biological organic principle are selected protein molecule, peptide quasi-molecule or the biological cell that the material of required absorption is had affinity interaction for use, as yeast cells, bioactive enzyme, antibody etc. are arranged.In the practical application, can select biological cell or biological organic principle targetedly for use according to the different order materials that is adsorbed.
The present invention is fixed on its diatomite with tannin, the present invention is fixed on tannin with biological enzyme technology and makes tannin modification infusorial earth carrier on the diatomite support particle, to there be the biological cell of affinity interaction or biological organic principle to be fixed on the tannin modification infusorial earth carrier then to the material of required absorption, make biological modification infusorial earth adsorbent.Its preparation method may further comprise the steps:
1, get diatomite through 800 ℃ of calcinings 1 hour, be cooled to wash after the room temperature, drying, pulverize through air-flow again, 20-100 purpose single-size is chosen in screening, makes the diatomite support particle;
2, the biological organic molecule aqueous solution with 5% (by weight) mixes with 3: 1 ratio (by weight) with the diatomite support particle, and 60-70 ℃ of drying crossed the 20-100 mesh sieve after 3 hours, make fine powder A;
3, the tannin aqueous solution with 5%-15% (by weight) adds in 40 ℃ of water of 5 times of amounts, and the oxidizing ferment that adds tannin dry weight 0.06%-0.2% is then made solution B;
4, fine powder A is added in the solution B, after be incubated 40 ℃ of reactions and fixing 1 hour, centrifugal removal reactant liquor, cleaning, dry sediment are made tannin modification infusorial earth carrier;
5, biological cell or biological organic principle are dissolved in 40 ℃ of water that 8-15 doubly measures, 5% the 50% glutaraldehyde (aqueous solution that adds vehicle weight then, volume ratio) and tannin modification infusorial earth carrier, after being incubated 40 ℃ of reactions and fixing 10 hours, centrifugal removal reactant liquor, cleaning, dry sediment are crossed the 20-100 mesh sieve and are made biological modification infusorial earth adsorbent;
Among the present invention, the usage ratio of diatomite support particle, tannin and biological cell or biological organic principle (in weight portion) is 10: 1～3: 1～4; Biological organic molecule refers to that molecular weight is the protein of 2000-8000 in the step 2, as the collagen of 2000-6000.
Beneficial effect
1, the present invention utilizes biological enzyme technology that natural tannin is fixed on the diatomite skeleton, equably the big molecule of tannin is combined on the diatomaceous absorption surface, its surface action relates to the multiple factors such as coupling of electrostatic interaction, Van der Waals force, hydrophobic effect power, hydrogen bond action, chelation and space size and shape, but not single physics chemical action, the peptide bond of protein can with the tannin generation multiple spot chelating crosslinked action that is combined in adsorbent surface, thereby have easily fixing, mass-transfer performance is good, stable in properties, intensity advantages of higher.
2, the present invention uses the diversity and the selectivity of protein molecule, to there be the suitable large biological molecule of affinity interaction to be fixed on the modification infusorial earth carrier to adsorbed material selectively, resulting adsorbent can adsorb target substance targetedly, the selectivity height, and accumulation ability is strong.
3, adsorbent of the present invention adopts natural material to make, and is cheap, pollution-free.
Description of drawings
Fig. 1 is preparation technology's flow chart of biological modification infusorial earth adsorbent of the present invention.
The specific embodiment
Below by embodiment the inventive method is further elaborated, but does not limit the present invention.
In the following preparation example, diatomaceous SiO
2Content is 80-90%, and dry back density is 0.5g/cm
3, porosity reaches 88%, can absorb the diatomite of 2.5 times of water of itself weight.
Embodiment 1
With 800 ℃ in diatomite calcining 1 hour, be cooled to room temperature after, wash, drying is pulverized through air-flow again, 20 purpose single-size 10Kg are chosen in screening; Get collagen 1.5Kg and mixes with diatomite with the dissolving of 10 times of water gagings and after adding water to 30Kg, 65 ℃ of dryings 3 hours, mistake 20 mesh sieves are made fine powder A; Get 2Kg larch tannin and use the 18Kg hot water dissolving, add in 40 ℃ of warm water of 100Kg, the polyphenol oxidase (polyhphenol oxidase is called for short PPO) that adds 2g is made solution B; Fine powder A is added solution B, and 40 ℃ were reacted 1 hour, and the centrifugal reactant liquor of removing cleans, and dry sediment obtains tannin modification infusorial earth carrier 13kg; In addition 3kg trypsase is dissolved in the 30kg40 ℃ of water, adds 50% glutaraldehyde and the 13kg tannin modification infusorial earth carrier of 650g, be incubated 40 ℃ and reacted 10 hours, centrifugal removal reactant liquor, washing, dry sediment are crossed 20 mesh sieves, obtain the JM immobilizing trypsinase.
Embodiment 2
With 800 ℃ in diatomite calcining 1 hour, be cooled to room temperature after, wash, drying is pulverized through air-flow again, 80 purpose single-size 10Kg are chosen in screening; Get collagen 1.5Kg and mixes with diatomite with the dissolving of 10 times of water gagings and after adding water to 30Kg, 65 ℃ of dryings 3 hours, mistake 80 mesh sieves are made fine powder A; Get the 1Kg theotannin and use the 19Kg hot water dissolving, add in the 100Kg40 ℃ of warm water, the polyphenol oxidase that adds 2g is made solution B; Fine powder A is added solution B, and 40 ℃ were reacted 1 hour, and the centrifugal reactant liquor of removing cleans, and dry sediment obtains tannin modification infusorial earth carrier 12 kg; There is the albumen of affinity interaction to be dissolved in 40 ℃ of water of 28kg 2kg and chlorogenic acid, add 50% the glutaraldehyde of 500g and the tannin modification infusorial earth carrier of the above-mentioned preparation of 10kg, be incubated 40 ℃ of cross-linking reactions 10 hours, centrifugal removal reactant liquor, washing, dry sediment, cross 80 mesh sieves, obtain JM-LY chlorogenic acid type adsorbent.
Embodiment 3
With 800 ℃ in diatomite calcining 1 hour, be cooled to room temperature after, wash, drying is pulverized through air-flow again, 100 purpose single-size 10Kg are chosen in screening; Get collagen 1.5Kg and mixes with diatomite with the dissolving of 10 times of water gagings and after adding water to 30Kg, 65 ℃ of dryings 3 hours, mistake 100 mesh sieves are made fine powder A; Get the 3Kg theotannin and use the 17Kg hot water dissolving, add in 40 ℃ of warm water of 100Kg, the polyphenol oxidase that adds 2g is made solution B; Fine powder A is added solution B, and 40 ℃ were reacted 1 hour, and the centrifugal reactant liquor of removing cleans, and dry sediment obtains tannin modification infusorial earth carrier 14kg; The 4kg gelatin protein is dissolved in 40 ℃ of water of 27kg, adds 50% the glutaraldehyde of 500g and the tannin modification infusorial earth carrier of the above-mentioned preparation of 10kg, be incubated 40 ℃ of cross-linking reactions 10 hours, centrifugal removal reactant liquor, washing, dry sediment, sieve obtains JM tannin adsorbent.
Comparative example
Get two parts of 5kg honeysuckles and add 40kg water respectively, 90-100 ℃ of lixiviate 20 minutes, leach leaching liquor and be cooled to 30 ℃, a copy of it leaching liquor is transferred pH to 7.5 and is added the prepared JM-LY chlorogenic acid type adsorbent of 1kg embodiment 2, and another portion leaching liquor transfers pH to 7 also to add 1kg D309 type macroporous absorbent resin, stirs respectively 40 minutes, the centrifugal stoste of removing, stir wash-out with the citric acid solution that adds 5Kg2% respectively, centrifugal collection filtrate, so wash-out is twice; Merge eluent respectively twice, concentrate, dry corresponding honeysuckle flower extract, JM-LY chlorogenic acid type adsorbents adsorb thing gets 223.5g, and D309 type macroporous absorbent resin adsorbate gets 434.5g; Detect the chlorogenic acid content of two kinds of powder respectively respectively with ultraviolet spectrometry light method.
The results are shown in Table 1.
Table 1
Table 1 shows, the effect of adsorbent chlorogenic acid extracting of the present invention comprises chlorogenic acid yield and content, all obviously is better than common macroporous absorbent resin, and visible adsorbent of the present invention has high accumulation rate, advantages such as high selectivity.
Claims (7)
1. biological modification infusorial earth adsorbent, it is characterized in that this biological modification infusorial earth adsorbent has the protein molecule of affinity interaction or biological cell to constitute by tannin modification infusorial earth carrier and the material of fixing on it to required absorption, wherein tannin modification infusorial earth carrier is made of diatomite support particle and the tannin that adopts biological enzyme technology to fix on it, and the usage ratio of diatomite support particle, tannin and protein molecule or biological cell is 10: 1～3: 1～4 by weight.
2. biological modification infusorial earth adsorbent according to claim 1 is characterized in that this biological modification infusorial earth adsorbent fineness is the 20-100 order.
3. biological modification infusorial earth adsorbent according to claim 1, the fineness that it is characterized in that the diatomite support particle is the 20-100 order.
4. biological modification infusorial earth adsorbent according to claim 1 is characterized in that tannin is that molecular weight is hydrolyzable tannin or the condensed tannin of 500-1000.
5. the preparation method of the described biological modification infusorial earth adsorbent of claim 1 comprises the steps:
(1) get diatomite through 800 ℃ of calcinings 1 hour, be cooled to wash after the room temperature, drying, pulverize through air-flow again, 20-100 purpose single-size is chosen in screening, makes the diatomite support particle;
(2) will be 5% the protein molecule aqueous solution by weight with the diatomite support particle be that 3: 1 ratio is mixed by weight, 60-70 ℃ of drying be crossed the 20-100 mesh sieve after 3 hours, make fine powder A;
(3) will be by weight for the tannin aqueous solution of 5%-15% add in 40 ℃ of water of 5 times of amounts, the oxidizing ferment that adds the 0.06%-0.2% of tannin dry weight is then made solution B;
(4) fine powder A is added in the solution B, after be incubated 40 ℃ of reactions and fixing 1 hour, centrifugal removal reactant liquor, cleaning, dry sediment are made tannin modification infusorial earth carrier;
(5) protein molecule or biological cell are dissolved in 40 ℃ of water that 8-15 doubly measures, add 5% 50 volume % glutaraldehyde water solutions of vehicle weight and the tannin modification infusorial earth carrier that step (4) is made then, after being incubated 40 ℃ of reactions and fixing 10 hours, centrifugal removal reactant liquor, cleaning, dry sediment are crossed the 20-100 mesh sieve and are made biological modification infusorial earth adsorbent.
6. the preparation method of biological modification infusorial earth adsorbent according to claim 5 is characterized in that diatomite is SiO in the step (1)
2Content is that 80-90 weight %, dry back density are 0.4～0.7g/cm
3, porosity reaches 85-95%, can absorb the diatomite of itself weight 1.5-4 times water, wherein SiO in the diatomite
2Content is in butt.
7. the preparation method of biological modification infusorial earth adsorbent according to claim 5 is characterized in that described protein molecule is that molecular weight is the protein molecule of 2000-8000.
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| CN101894597B (en) * | 2010-06-04 | 2013-04-03 | 清华大学 | Pretreatment method for radioactive wastewater |
| CN103316628B (en) * | 2013-06-27 | 2015-10-14 | 昆明理工大学 | A kind of preparation method and application of adsorbent |
| CN105598155A (en) * | 2015-12-31 | 2016-05-25 | 陕西清扬环境科技有限公司 | Remediation method for soil polluted by arsenic |
| CN105561943B (en) * | 2016-03-14 | 2017-12-15 | 武汉轻工大学 | A kind of preparation method and application of magnetic rape stalk sorbing material |
| CN106362704B (en) * | 2016-10-24 | 2021-04-02 | 青岛农业大学 | Composite filler for filling invisible anti-haze mask |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1431497A (en) * | 2003-01-28 | 2003-07-23 | 复旦大学 | Method of using nano zeolite molecular sieve assemble material as affinity chromatography filler to separate functional protein molecules |
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| CN1431497A (en) * | 2003-01-28 | 2003-07-23 | 复旦大学 | Method of using nano zeolite molecular sieve assemble material as affinity chromatography filler to separate functional protein molecules |
Non-Patent Citations (2)
| Title |
|---|
| 刘频 等.改性硅藻土对Pb(Ⅱ)的吸附作用. 云南化工30 5.2003,30(5),11-13. |
| 刘频等.改性硅藻土对Pb(Ⅱ)的吸附作用. 云南化工30 5.2003,30(5),11-13. * |
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