CN105688865A - Bio-adsorbent prepared by modifying ball-milled tea residues and preparation method and application of bio-adsorbent - Google Patents
Bio-adsorbent prepared by modifying ball-milled tea residues and preparation method and application of bio-adsorbent Download PDFInfo
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- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a bio-adsorbent prepared by modifying ball-milled tea residues and a preparation method and application of the bio-adsorbent. The method includes the steps of removing dissoluble pigments and other substances in tea residues through sulfuric acid to obtain pigment-removed tea residues, ball-milling pigment-removed tea residues to obtain superfine tea residues, soaking superfine tea residues in a mixed solution of metal ions of zirconium, iron, lanthanum, cerium, titanium and the like, loading generated hydroxide in tea residues under the alkaline conditions, conducting high-temperature drying to ensure that hydroxide can be sufficiently loaded in superfine tea residues, and finally conducting washing and drying to prepare the defluorination bio-adsorbent. Tea residues serve as the main raw material of the bio-adsorbent, the resource is wide and the price is low; not only can tea residue waste and pollution caused by tea residue waste be eliminated, but also a new approach is provided for high-value utilization of tea residues, and the problem that it is difficult to dispose tea residues in the industrial production process is solved. The bio-adsorbent is mild in reaction condition in the preparation process, the process route is simple and easy to implement, and industrial operation is easy.
Description
Technical field
The present invention relates to the application in a kind of biological adsorption agent, the preparation method of this biological adsorption agent and this biological adsorption agent fluorine removal at the same time prepared by tea grounds ball milling post-modification and metal。
Background technology
Fluorine (Fluoride) as trace element necessary to human body, a small amount of absorption can anti-caries in advance, promote the calcium metabolism of skeleton, but if the fluorine that Excess free enthalpy exceedes safe level can cause fluorosis。World Health Organization (WHO) specifies, the suitable concentration 0.5mg/L～1.0mg/L of content of fluoride in drinking water。It is reported, the whole world has people more than 200,000,000 to drink the water that Oil repellent exceeds standard。China is one of country that Water fluorosis is popular the most in the world, harm is the heaviest, and there is 1135 drinking water type Endemic Fluorosis county in the whole nation, and affected fluorine lesion village total number of people reaches 8851.7 ten thousand people。And up to the present, endemic fluorosis there is no effective Therapeutic Method, therefore prevent fluorosis by reduction fluorine content of drinking water, be the Main Means controlling Water fluorosis。
In recent years, produced by industry, the leachate of waste water and solid waste is directly discharged into water body, the unreasonable landfill such as civilian solid waste and stacking, and the using of a large amount of chemical fertilizer, pesticide so that in drinking-water, the Oil repellent heavy metal pollution simultaneously that exceeds standard is also comparatively serious。It addition, Camellia sinensis is the enriching plant of a kind of fluorine and aluminum, its Leaf is main enrichment positions, particularly postfermented tea, its composition is thick old blade mainly, and Oil repellent is up to thousands of mg/kg, exceeding well over national standard 300mg/kg, aluminum content also reaches tens mg/kg, and its health risk can not be ignored。
The method of fluorine and metal in water that processes both at home and abroad at present mainly has absorption method, coagulant sedimentation, ion exchange, membrane separation process, electricity flocculence and electroosmose process etc., and the de-fluoridation adsorbent that wherein absorption method is the most frequently used is also conventional in most efficient method drinking water includes agricultural by product, clay, activated bentonite, brucite, bone black, zeolite and activated alumina etc.。Wherein activated alumina is one of adsorbent of being most widely used in the world, but alumina adsorption capacity is on the low side and has residual can cause secondary pollution after adsorbing, and absorption optimum pH scope is narrower and only just has good adsorption effect in acid condition。Therefore, developing adsorbent efficient, applied widely is the key removing fluorine and metal。
Tea grounds (teawaste) refer to produce in Tea planting, processing, deep processing and the circulation process such as consumption based on the general name of the garbage of Folium Camelliae sinensis biomass, be an important component part of agricultural solid residue。World's tea yield in 2013 481.9 ten thousand tons according to statistics, wherein Chinese tea yield 1,850,000 tons, these Folium Camelliae sinensis can produce substantial amounts of tea grounds in productive consumption process, and having catered to the current living habit of people along with instant tea, tea beverage and tea polyphenol health products etc., a large amount of exploitations of tea comprehensive processing product and production also create a large amount of Folium Camelliae sinensis garbage。And tea grounds offal treatment is increasingly becoming an ecological environment problem。Any disposal of tea grounds not only causes environmental pollution, and wastes huge living resources。In recent years, tea grounds garbage how is developed, it has also become study hotspot in recent years。Therefore, how tea grounds is modified, prepares novel biological adsorption agent, thus not only biomass castoff can have been utilized but also can purify fluorine and drinking water that metal exceeds standard, be that those skilled in the art make great efforts to solve the technical problem that always。
Summary of the invention
For above-mentioned deficiency, the invention provides and a kind of will be modified fluorine removal, metal biological adsorption agent of preparing and its preparation method and application after tea grounds ball milling。Preparation method in the present invention is with tea grounds for raw material, and preparation process is few and preparation efficiency is high；In the biological adsorption agent prepared by this method can be widely applied to fluorine and metal exceeds standard drinking water, brick tea and instant tea, there is the remarkable advantages such as low cost, high efficiency, simple, the non-secondary pollution of process。
A kind of preparation method that will be modified after tea grounds ball milling and prepare fluorine removal, metal biological adsorption agent is provided one of for achieving the above object, present invention employs techniques below scheme:
A kind of method that prepared by tea grounds ball milling post-modification biological adsorption agent, comprises the steps:
S1, putting in dilution heat of sulfuric acid by tea grounds, under 70～80 DEG C of warm water, water-bath 1～3h removes the pigment in tea grounds；In 70～100 DEG C of baking ovens, dry 3～4h with deionized water wash after for several times after water-bath, after drying, obtain treating the tea grounds of ball milling；
S2, the tea grounds treating ball milling is carried out ball milling, prepare ultra micro tea grounds to be modified；
S3, ultra micro tea grounds to be modified is joined in the metal ion solution of one or more mixing in zirconium, ferrum, lanthanum, cerium, titanium, stir at 50～80 DEG C and add alkaline compound solution the pH value of mixed solution is adjusted to 4.0～7.0；Then proceeding to stirring 0.5～2h, taking-up precipitate puts into dry 2～4h in 70～150 DEG C of baking ovens makes the abundant load of hydroxide of metal ion on tea grounds, obtains modified ultra micro tea grounds；
S4, modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dry in 70～100 DEG C of baking ovens and can obtain biological adsorption agent。
Preferably, in step S1, the concentration of described dilution heat of sulfuric acid is 0.02M。
Preferably, in step S2, the ultra micro tea grounds particle diameter obtained by ball milling is less than 76 μm
Preferably, in step S3, the total concentration of described metal ion is 0.01～1.0M。
Further, in step S3, described metal ion adopts zirconium ion, and the concentration of zirconium ion solution is 0.4M。
Meanwhile, the invention provides the biological adsorption agent prepared according to above-mentioned preparation method。
Further, present invention also offers above-mentioned biological adsorption agent in drinking water, brick tea, instant tea, remove the application of fluorine and metal simultaneously。
Preferably, after this biological adsorption agent inorganic pollution in absorption drinking water, brick tea, instant tea, it is immersed in alkaline compound solution by biological adsorption agent 1～5h, namely renewable and repeat to use。
Further, described alkaline compound solution is the sodium hydroxide solution of 1～5wt%。
The beneficial effects of the present invention is:
1), the present invention first passes through the materials such as the soluble pigment that sulphuric acid removes in tea grounds and obtains discoloring the tea grounds of element, then the tea grounds of the element that discolors is carried out ball milling and obtain ultra micro tea grounds, again ultra micro tea grounds is immersed in the mixed solution of the metal ions such as zirconium, aluminum, ferrum, lanthanum, titanium, the hydroxide making generation in the basic conditions is carried in tea grounds, high temperature drying is to guarantee that hydroxide can fully load be in ultra micro tea grounds subsequently, and last washing and drying prepares fluorine removal biological adsorption agent。
This adsorbent primary raw material is tea grounds, wide material sources and cheap, therefore the present invention is while eliminating tea grounds garbage and the pollution that brings thereof, provides new approach for tea grounds higher value application, solves the intractable problem of tea grounds in industrial processes。
2), the preparation process reaction condition of this biological adsorption agent gentle, process route is simple, it is easy to industrial operation, therefore possesses the potentiality of large-scale promotion application。
3), in this biological adsorption agent can be widely applied to fluorine and metal exceeds standard drinking water and brick tea, instant tea, there is the advantages such as low cost, high efficiency, process be simple。
4), this biological adsorption agent by the alkaline compound solution zeolite regeneration of certain mass concentration, use can be continued cycling through, environmentally friendly。
Accompanying drawing explanation
Fig. 1 a, 1b respectively amplify the unmodified tea grounds SEM figure of 2000 times, ultra micro tea grounds (i.e. UTP) SEM to be modified after ball milling schemes。
Fig. 1 c is the SEM figure amplifying 100000 times of lower ultra micro tea grounds。
Fig. 1 d is the SEM figure of UTP-Zr system metal ion-modified through zirconium under amplifying 100000 times, the hydroxide of load zirconium in modified tea grounds。
Fig. 1 e is the SEM figure of UTP-Zr system Adsorption of fluoride metal ion-modified through zirconium under amplifying 100000 times。
Fig. 1 f is the SEM figure of UTP-Zr system Adsorption of fluoride metal ion-modified through zirconium under amplifying 100000 times and aluminum。
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are better understood from, below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not restricted to the present embodiment。
Adsorption capacity in embodiment is that biological adsorption agent is to the index of fluorion absorption in water, wherein in water, fluorinion concentration is measured by fluoride ion selective electrode, zirconium ion and aluminum ions concentration use Inductively coupled plasma optical emission spectrometer (ICP) to measure, and caffeine and catechin content use high performance liquid chromatography (HPLC) to measure。
Embodiment 1
Being put into by 2.5g ultra micro tea grounds in 0.02M (i.e. 0.02mol/L) sulfuric acid solution of 100mL, under 70 DEG C of warm water, water-bath 3h removes pigment in tea grounds；In 70 DEG C of baking ovens, dry 3h with deionized water wash after for several times after water-bath, carry out ball milling after drying and obtain ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is joined in the solution of basic zirconium chloride (0.4M, 100mL), stir at 60 DEG C and add sodium hydroxide solution (2M) pH value of mixed solution is adjusted to 7.0；Then proceed to stirring 0.5h, take out precipitate and put into dry 2h in 110 DEG C of baking ovens, obtain modified ultra micro tea grounds；Modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dries in 70 DEG C of baking ovens and can obtain ultra micro tea grounds biological adsorption agent。
Take the above-mentioned 0.08g ultra micro tea grounds adsorbent prepared put into equipped with pH be 7.0, fluorinion concentration is 10mg/L, aluminium ion concentration be 2mg/L 25mL simulation drinking water in centrifuge tube, it it is 25 ± 2 DEG C in temperature, rotating speed be 300r/min constant-temperature table in concussion 2h after, filter after the absorption surveyed fluorion and aluminium ion concentration in solution, test three times parallel。
Under this condition of calculating, the clearance of fluorine is 94.1% by adsorbent, and in the solution after absorption, the fluorinion concentration of residual is 0.59mg/L, lower than national standard。The clearance of aluminum is 99.5% by adsorbent, and in solution, the concentration of zirconium limits (LOD lower than ICP detection；0.01mg/L)。
Embodiment 2
Being put into by 2.5g ultra micro tea grounds in the 0.02M sulfuric acid solution of 100mL, under 70 DEG C of warm water, water-bath 3h removes pigment in tea grounds；In 70 DEG C of baking ovens, dry 3h with deionized water wash after for several times after water-bath, carry out ball milling after drying and obtain ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is joined in the solution of basic zirconium chloride (0.4M, 100mL), stir at 60 DEG C and add sodium hydroxide solution (2M) pH value of mixed solution is adjusted to 7.0；Then proceed to stirring 0.5h, take out precipitate and put into dry 2h in 110 DEG C of baking ovens, obtain modified ultra micro tea grounds；Modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dries in 70 DEG C of baking ovens and can obtain ultra micro tea grounds biological adsorption agent。
Take the above-mentioned 0.08g ultra micro tea grounds adsorbent prepared put into equipped with pH be 6.0, fluorinion concentration is 10mg/L, aluminium ion concentration be 4mg/L 25mL simulation drinking water in centrifuge tube, it it is 25 ± 2 DEG C in temperature, rotating speed be 300r/min constant-temperature table in concussion 2h after, filter after the absorption surveyed fluorion and aluminium ion concentration in solution, test three times parallel。
Under this condition of calculating, the clearance of fluorine is 92.8% by adsorbent, and in the solution after absorption, the fluorinion concentration of residual is 0.72mg/L, lower than national standard。The clearance of aluminum is 89.7% by adsorbent, and in solution, the concentration of zirconium limits (LOD lower than ICP detection；0.01mg/L)。
Embodiment 3
Being put into by 2.5g ultra micro tea grounds in the 0.02M sulfuric acid solution of 100mL, under 70 DEG C of warm water, water-bath 3h removes pigment in tea grounds；In 70 DEG C of baking ovens, dry 3h with deionized water wash after for several times after water-bath, carry out ball milling after drying and obtain ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is joined in the solution of basic zirconium chloride (0.4M, 100mL), stir at 60 DEG C and add sodium hydroxide solution (2M) pH value of mixed solution is adjusted to 7.0；Then proceed to stirring 0.5h, take out precipitate and put into dry 2h in 110 DEG C of baking ovens, obtain modified ultra micro tea grounds；Modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dries in 70 DEG C of baking ovens and can obtain ultra micro tea grounds biological adsorption agent。
Take the above-mentioned 0.08g ultra micro tea grounds adsorbent prepared put into equipped with pH be 5.0, fluorinion concentration is 10mg/L, aluminium ion concentration be 10mg/L 25mL simulation drinking water in centrifuge tube, it it is 25 ± 2 DEG C in temperature, rotating speed be 300r/min constant-temperature table in concussion 2h after, filter after the absorption surveyed fluorion and aluminium ion concentration in solution, test three times parallel。
Under this condition of calculating, the clearance of fluorine is 91.0% by adsorbent, and in the solution after absorption, the fluorinion concentration of residual is 0.90mg/L, lower than national standard。The clearance of aluminum is 50% by adsorbent, and in solution, the concentration of zirconium limits (LOD lower than ICP detection；0.01mg/L)。
Embodiment 4
Being put into by 2.5g ultra micro tea grounds in the 0.02M sulfuric acid solution of 100mL, under 70 DEG C of warm water, water-bath 3h removes pigment in tea grounds；In 70 DEG C of baking ovens, dry 3h with deionized water wash after for several times after water-bath, carry out ball milling after drying and obtain ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is joined in the solution of basic zirconium chloride (0.4M, 100mL), stir at 60 DEG C and add sodium hydroxide solution (2M) pH value of mixed solution is adjusted to 7.0；Then proceed to stirring 0.5h, take out precipitate and put into dry 2h in 110 DEG C of baking ovens, obtain modified ultra micro tea grounds；Modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dries in 70 DEG C of baking ovens and can obtain ultra micro tea grounds biological adsorption agent。
Take the above-mentioned 0.05g biological adsorption agent prepared put into equipped with pH be 5.3, concentration be the centrifuge tube of Fu-brick tea millet paste (prepared by 1:50m/v) of 25mL of 9.4mg/L, after temperature is 30 ± 1 DEG C of boiling 30min, filter after the absorption surveyed fluorinion concentration, aluminium ion concentration, caffeine, catechin and pH value in solution, test three times parallel。
Being 28% through calculating adsorbent under this condition to the clearance of fluorine, the clearance to aluminum is 15%, and after absorption, the caffeine content in millet paste and pH are substantially free of change, and catechin loss only has 5%, is substantially free of change before and after the process of millet paste color and luster。
Embodiment 5
Being put into by 2.5g ultra micro tea grounds in the 0.02M sulfuric acid solution of 100mL, under 70 DEG C of warm water, water-bath 3h removes pigment in tea grounds；In 70 DEG C of baking ovens, dry 3h with deionized water wash after for several times after water-bath, carry out ball milling after drying and obtain ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is joined in the solution of basic zirconium chloride (0.4M, 100mL), stir at 60 DEG C and add sodium hydroxide solution (2M) pH value of mixed solution is adjusted to 7.0；Then proceed to stirring 0.5h, take out precipitate and put into dry 2h in 110 DEG C of baking ovens, obtain modified ultra micro tea grounds；Modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dries in 70 DEG C of baking ovens and can obtain ultra micro tea grounds biological adsorption agent。
Take the above-mentioned 0.05g biological adsorption agent prepared put into equipped with pH be 5.2, concentration be the centrifuge tube of instant tea millet paste (prepared by 1:50m/v) of 25mL of 52.4mg/L, after temperature is 30 ± 1 DEG C of boiling 30min, filter after the absorption surveyed fluorinion concentration, aluminium ion concentration, caffeine, catechin and pH value in solution, test three times parallel。
Being 43% through calculating adsorbent under this condition to the clearance of fluorine, the clearance to aluminum is 25%, and after absorption, the caffeine content in millet paste and pH are substantially free of change, and catechin loss only has 8%, is substantially free of change before and after the process of millet paste color and luster。
Claims (9)
1. the method that tea grounds ball milling post-modification is prepared biological adsorption agent, it is characterised in that comprise the steps:
S1, putting in dilution heat of sulfuric acid by tea grounds, under 70～80 DEG C of warm water, water-bath 1～3h removes the pigment in tea grounds；In 70～100 DEG C of baking ovens, dry 3～4h with deionized water wash after for several times after water-bath, after drying, obtain treating the tea grounds of ball milling；
S2, the tea grounds treating ball milling is carried out ball milling, prepare ultra micro tea grounds to be modified；
S3, ultra micro tea grounds to be modified is joined in the metal ion solution of one or more mixing in zirconium, ferrum, lanthanum, cerium, titanium, stir at 50～80 DEG C and add alkaline compound solution the pH value of mixed solution is adjusted to 4.0～7.0；Then proceeding to stirring 0.5～2h, taking-up precipitate puts into dry 2～4h in 70～150 DEG C of baking ovens makes the abundant load of hydroxide of metal ion on tea grounds, obtains modified ultra micro tea grounds；
S4, modified ultra micro tea grounds deionized water wash is removed soluble-salt for several times, dry in 70～100 DEG C of baking ovens and can obtain biological adsorption agent。
2. a kind of method that tea grounds ball milling post-modification is prepared biological adsorption agent according to claim 1, it is characterised in that: in step S1, the concentration of described dilution heat of sulfuric acid is 0.02M。
3. a kind of method that tea grounds ball milling post-modification is prepared biological adsorption agent according to claim 1, it is characterised in that: in step S2, the ultra micro tea grounds particle diameter obtained by ball milling is less than 76 μm。
4. a kind of method that tea grounds ball milling post-modification is prepared biological adsorption agent according to claim 1, it is characterised in that: in step S3, the total concentration of described metal ion is 0.01～1.0M。
5. a kind of method that tea grounds ball milling post-modification is prepared biological adsorption agent according to claim 4, it is characterised in that: in step S3, described metal ion adopts zirconium ion, and the concentration of zirconium ion solution is 0.4M。
6. the biological adsorption agent that preparation method according to any one of Claims 1 to 5 prepares。
7. biological adsorption agent according to claim 6 removes the application of fluorine and metal in drinking water, brick tea, instant tea。
8. the application of biological adsorption agent according to claim 7, it is characterized in that: after this biological adsorption agent inorganic pollution in absorption drinking water, brick tea and instant tea, it is immersed in alkaline compound solution by biological adsorption agent 1～5h, namely renewable and repeat to use。
9. the application of biological adsorption agent according to claim 8, it is characterised in that: described alkaline compound solution is the sodium hydroxide solution of 1～5wt%。
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| CN114392722A (en) * | 2022-01-28 | 2022-04-26 | 湖南烯富环保科技有限公司 | Biochar @ five-membered metal oxide composite defluorination material and preparation and application thereof |
| CN114653341A (en) * | 2022-04-12 | 2022-06-24 | 四川文理学院 | Modified tea residue biochar, preparation method and application thereof |
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| CN104525137A (en) * | 2014-12-04 | 2015-04-22 | 安徽农业大学 | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof |
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| CN101507913A (en) * | 2009-02-10 | 2009-08-19 | 浙江大学 | Preparation method of tea-leaf power capable of cleaning organic waste gas and use method thereof |
| CN103506087A (en) * | 2013-09-27 | 2014-01-15 | 华南农业大学 | Method for preparing heavy metal ion adsorbent using maleic acylation wood fibers at room temperature |
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| CN114392722A (en) * | 2022-01-28 | 2022-04-26 | 湖南烯富环保科技有限公司 | Biochar @ five-membered metal oxide composite defluorination material and preparation and application thereof |
| CN114653341A (en) * | 2022-04-12 | 2022-06-24 | 四川文理学院 | Modified tea residue biochar, preparation method and application thereof |
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| CN105688865B (en) | 2018-07-06 |
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