CN102861553A - Composite adsorbing material for removing aluminium ions in natural water body and preparation method of composite adsorbing material - Google Patents
Composite adsorbing material for removing aluminium ions in natural water body and preparation method of composite adsorbing material Download PDFInfo
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Abstract
The invention belongs to the field of water purification treatment and in particular relates to a composite adsorbing material for removing aluminium ions in a natural water body and a composite adsorbing material of the composite adsorbing material. The preparation method is characterized in that a nanobacteria cellulose-modified starch microsphere composite adsorbing material is added in the natural water body of which the aluminium ion content is more than 0.2mg/L so that the aluminium ion content of the water body is reduced to below 0.2mg/L. The composite adsorbing material is used for treating the natural water body polluted by the aluminium ions. Compared with the prior art, the composite adsorbing material is renewable and reusable, does not have secondary pollution and has good social benefits and economic benefits. By utilizing the composite adsorbing material and the preparation method, materials are easy to get, the process is simple, the treatment effect is good, and recycling of wastes is realized.
Description
Technical field
The present invention relates to aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body, be specifically related to utilize nanometer bacteria cellulose to load on a kind of novel material that makes at the modified starch microballoon, belong to the purifying water process field.
Background technology
Aluminium, one of metal that a kind of people are the most frequently used, though its harm known by most people institute heat, be not subject to enough attention.Studies confirm that aluminum content is too high in the food, will cause people's early stage aging, aluminium is put aside in brain can cause cerebral neural degeneration, is losing one's memory, and intelligence and personality also can be affected, even present senile dementia.Therefore, aspect environmental protection and the health, tool has very important significance to aluminum ions detection.The World Health Organization studies show that, the aluminium that the human body per kilogram of body weight allows to take in can not surpass 1mg.Aluminum content must not be higher than 0.2mg/L in China's regulation drinking water.
The aluminum ions method that is used at present the removal natural water body mainly contains enhanced coagulation, ozone oxidation, charcoal absorption, film processing.Enhanced coagulation is to react the generation precipitation by add coagulant and aluminium ion in water, thereby reaches the purpose of removal.Although this method clearance is good, operating process is complicated, produces easily secondary pollution.Ozonation also has the shortcoming of said method.Active carbon adsorption is to utilize active carbon that the Selective adsorption of ion is reached aluminum ions removal purpose, and clearance is also fine, but its process is complicated, and expense is very high, and material is difficult for regeneration.And the method that film is processed also has above-mentioned shortcoming.
Compare the characteristics such as the present invention has that material is easy to get, reproducible utilization, process are simple, non-secondary pollution with the method that traditional aluminium ion is removed.Realize the comprehensive utilization of house refuse, protected environment, widened the range of choice of composite in the water adsorption treatment process, realized the resource of discarded object, had good Social benefit and economic benefit.
Summary of the invention
The objective of the invention is in order to overcome existing technology in the deficiency of the aspects such as material regeneration utilization and generation secondary pollution, aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body is provided, the present invention is a kind of novel composite adsorption material section, has the adsorption efficiency height, material is easy to get, simple to operate, cost is few, the characteristics such as non-secondary pollution.
The objective of the invention is to be achieved through the following technical solutions:
(1) presses green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 85～90 ℃ and keeps 20～30min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add 0.3%～0.5% peptone, 0.5%～1% ethanol stirring, mixing, cooling again;
(2) the fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution among 5～10ml above-mentioned (1), static cultivation is 7～10 days under 30 ℃ of constant temperatures;
(3) take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 3～5 times, 90～100 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 20～30min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 120～130 ℃ of autoclave sterilization 20～30min;
(4) get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 50～60 ℃ is that dispersant dissolves fully, stand-by;
(5) take by weighing 5～10g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets 10～15ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving;
(6) water for preparing in (5) is dropwise joined in (4), the maintenance mixing speed is 450～500r/min, add 0.1～0.3g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 8～9 behind reaction 1～2h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind dry 20～24h;
(7) the spherex powder is soluble in water, add again 3%～5% polyvinyl alcohol, in the situation that adds thermal agitation 3～4h so that polyvinyl alcohol dissolving, adding an amount of nanometer bacteria cellulose floods again, again in 60～80 ℃ of oven dry, can obtain this novel composite adsorbing material behind stirring 3～4h.
Described dispersant is one or more in triethyl group hexyl phosphoric acid, upper sodium dialkyl sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, sorbester p18, polysorbate60, the fatty acid polyethylene glycol ester.
Principle of the present invention is: contain the network structure that a large amount of functional groups are unified into around the spherex of modification, by chelatropic reaction or ion-exchange aluminium ion is adsorbed on the surface, and a large amount of bacteria celluloses is intertwined to form irregular loose network structure, strengthen the specific area of adsorbent, thereby reached larger adsorption effect.
Concrete application process of the present invention is: at room temperature, get pH=6～7, concentration is containing of 50mg/L of aluminum ions sewage 50ml, in sewage, add 5g nanometer bacteria cellulose-spherex sorbing material, behind the absorption 30min, record that aluminium ion concentration is less than 0.2mg/L in the sewage, clearance can reach more than 99.9%.
The invention has the beneficial effects as follows:
(1) spherolite of the present invention is directly very little, has huge Free Surface, makes nano particle have higher colloidal stability and excellent absorption property, can reach faster adsorption equilibrium;
(2) the present invention can carry out the physics desorption, realizes the recycling of spherex and bacteria cellulose, and can not produce secondary pollution.
The specific embodiment
The technical solution used in the present invention is as follows:
(1) presses green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 85～90 ℃ and keeps 20～30min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add 0.3%～0.5% peptone, 0.5%～1% ethanol stirring, mixing, cooling again;
(2) the fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution among 5～10ml above-mentioned (1), static cultivation is 7～10 days under 30 ℃ of constant temperatures;
(3) take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 3～5 times, 90～100 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 20～30min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 120～130 ℃ of autoclave sterilization 20～30min;
(4) get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 50～60 ℃ is that dispersant dissolves fully, stand-by;
(5) take by weighing 5～10g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets 10～15ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving;
(6) water for preparing in (5) is dropwise joined in (4), the maintenance mixing speed is 450～500r/min, add 0.1～0.3g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 8～9 behind reaction 1～2h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind dry 20～24h;
(7) the spherex powder is soluble in water, add again 3%～5% polyvinyl alcohol, in the situation that adds thermal agitation 3～4h so that polyvinyl alcohol dissolving, adding an amount of nanometer bacteria cellulose floods again, again in 60～80 ℃ of oven dry, can obtain this novel composite adsorbing material behind stirring 3～4h.
Described dispersant is one or more in triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, sorbester p18, polysorbate60, the fatty acid polyethylene glycol ester.
Example 1
Press green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 85 ℃ and keeps 20min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add 0.3% peptone, 0.5% ethanol stirring, mixing, cooling again.The fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution of the above-mentioned gained of 5ml, static cultivation is 7 days under 30 ℃ of constant temperatures.Take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 3 times, 90 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 20min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 120 ℃ of autoclave sterilization 20min.Get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 50 ℃ is that dispersant dissolves fully, stand-by.Take by weighing the 5g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets the 10ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving.Dropwise join the water for preparing in above-mentioned in the oil phase, the maintenance mixing speed is 450r/min, add the 0.1g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 8 behind the reaction 1h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind the dry 20h.The spherex powder is soluble in water, add 3% polyvinyl alcohol again, in the situation that adds thermal agitation 3h so that polyvinyl alcohol dissolving, add again an amount of nanometer bacteria cellulose and flood, again in 60 ℃ of oven dry, can obtain this novel composite adsorbing material behind the stirring 3h.
Example 2 is pressed green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 90 ℃ and keeps 30min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add 0.5% peptone, 1% ethanol stirring, mixing, cooling again.The fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution of the above-mentioned gained of 10ml, static cultivation is 10 days under 30 ℃ of constant temperatures.Take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 5 times, 100 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 30min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 130 ℃ of autoclave sterilization 30min.Get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 60 ℃ is that dispersant dissolves fully, stand-by.Take by weighing the 10g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets the 15ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving.Dropwise join the water for preparing in above-mentioned in the oil phase, the maintenance mixing speed is 500r/min, add the 0.3g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 9 behind the reaction 2h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind the dry 24h.The spherex powder is soluble in water. add again 5% polyvinyl alcohol, in the situation that adds thermal agitation 4h so that polyvinyl alcohol dissolving, add again an amount of nanometer bacteria cellulose and flood, again in 80 ℃ of oven dry, can obtain this novel composite adsorbing material behind the stirring 4h.
Example 3
Press green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 88 ℃ and keeps 25min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add the 0.8% ethanol stirring of 0.4% peptone, mixing, cooling again.The fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution of the above-mentioned gained of 8ml, static cultivation is 9 days under 30 ℃ of constant temperatures.Take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 4 times, 95 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 25min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 125 ℃ of autoclave sterilization 25min.Get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 55 ℃ is that dispersant dissolves fully, stand-by.Take by weighing the 8g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets the 12ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving.Dropwise join the water for preparing in above-mentioned in the oil phase, the maintenance mixing speed is 470r/min, add the 0.2g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 9 behind the reaction 1.5h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind the dry 23h.The spherex powder is soluble in water, add again 4% polyvinyl alcohol, in the situation that adds thermal agitation 3.5h, so that polyvinyl alcohol dissolving, add again an amount of nanometer bacteria cellulose and flood, again in 70 ℃ of oven dry, can obtain this novel composite adsorbing material behind the stirring 3.5h.
Claims (5)
1. remove aluminum ions composite adsorbing material in the natural water body for one kind, it is characterized in that: this composite adsorbing material is nanometer bacteria cellulose to be loaded on the modified starch microballoon make.
2. aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body according to claim 1 is characterized in that the preparation method of nanometer bacteria cellulose:
(1) presses green tea (butt): sugar: behind the mass ratio weighing above-mentioned substance of water=0.5: 100: 1000, first with water boil, adding green tea is soaked in 85～90 ℃ and keeps 20～30min, the elimination tealeaf residue, add the ratio in dextrose plus saccharose dissolve and be 1: 1 syrup, it is for subsequent use to add 0.3%～0.5% peptone, 0.5%～1% ethanol stirring, mixing, cooling again;
(2) the fermented tea bacterial classification is put in the sterile tray, poured into the nutrient solution among 5～10ml above-mentioned (1), static cultivation is 7～10 days under 30 ℃ of constant temperatures;
(3) take out the bacteria cellulose film that static cultivation generates afterwards, with distilled water flushing 3～5 times, 90～100 ℃ of NaOH solution that again it are soaked in 0.1mol/L boil 20～30min after it becomes milky translucent, be placed on again in the physiological saline, can make nanometer bacteria cellulose behind 120～130 ℃ of autoclave sterilization 20～30min.
3. aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body according to claim 1 is characterized in that the preparation method of modified starch microballoon:
(1) get cyclohexane 40ml and chloroform 10ml is mixed into oil phase in flask, add 2g dispersant (m (Span60): m (Tween60)=3: 2) again, adding thermal agitation under 50～60 ℃ is that dispersant dissolves fully, stand-by;
(2) take by weighing 5～10g soluble starch and add in the distilled water, heating for dissolving is made into 10% starch solution, gets 10～15ml starch solution and adds 0.2gN, N '-methylene-bisacrylamide, fully dissolving;
(3) water for preparing in (2) is dropwise joined in (1), the maintenance mixing speed is 450～500r/min, add 0.1～0.3g ammonium ceric nitrate after forming symmetrical liquid drop, regulate pH to 8～9 behind reaction 1～2h, leave standstill, centrifugal, remove upper oil phase, lower floor's cross-linked polymer is used ethyl acetate successively, and absolute ethanol washing obtains pulverous spherex behind dry 20～24h.
4. aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body according to claim 1 is characterized in that nanometer bacteria cellulose loads on the method for modified starch microballoon:
(1) the spherex powder is soluble in water, add again 3%～5% polyvinyl alcohol, in the situation that adds thermal agitation 3～4h so that polyvinyl alcohol dissolving, adding an amount of nanometer bacteria cellulose floods again, stir behind 3～4h again in 60～80 ℃ dry by the fire in, can obtain this novel composite adsorbing material.
5. aluminum ions composite adsorbing material and preparation method thereof in a kind of removal natural water body described in according to claim 3, it is characterized in that: described dispersant is one or more in triethyl group hexyl phosphoric acid, upper sodium dialkyl sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, sorbester p18, polysorbate60, the fatty acid polyethylene glycol ester.
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Cited By (5)
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| CN103896389A (en) * | 2014-03-26 | 2014-07-02 | 华南师范大学 | Controlled release type potassium ferrate composite as well as preparation method and application thereof |
| CN105126791A (en) * | 2015-09-07 | 2015-12-09 | 天津工业大学 | Preparation method of self-assembled microsphere-containing non-woven cloth for adsorbing volatile organic compound |
| CN108975440A (en) * | 2017-05-31 | 2018-12-11 | 南京博络金环保科技有限公司 | A kind of method of soluble residual aluminum in deep removal water |
| CN109225170A (en) * | 2018-09-27 | 2019-01-18 | 陕西科技大学 | A kind of cellulose base adsorbent material and its preparation method and application of casein crosslinking |
| CN110872385A (en) * | 2018-08-31 | 2020-03-10 | 南京理工大学 | Preparation method of starch/bacterial cellulose composite material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896389A (en) * | 2014-03-26 | 2014-07-02 | 华南师范大学 | Controlled release type potassium ferrate composite as well as preparation method and application thereof |
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| CN105126791A (en) * | 2015-09-07 | 2015-12-09 | 天津工业大学 | Preparation method of self-assembled microsphere-containing non-woven cloth for adsorbing volatile organic compound |
| CN105126791B (en) * | 2015-09-07 | 2017-11-28 | 天津工业大学 | A kind of preparation method for the non-woven cloth containing self-assembly microspheres for adsorbing volatile organic matter |
| CN108975440A (en) * | 2017-05-31 | 2018-12-11 | 南京博络金环保科技有限公司 | A kind of method of soluble residual aluminum in deep removal water |
| CN110872385A (en) * | 2018-08-31 | 2020-03-10 | 南京理工大学 | Preparation method of starch/bacterial cellulose composite material |
| CN110872385B (en) * | 2018-08-31 | 2021-12-10 | 南京理工大学 | Preparation method of starch/bacterial cellulose composite material |
| CN109225170A (en) * | 2018-09-27 | 2019-01-18 | 陕西科技大学 | A kind of cellulose base adsorbent material and its preparation method and application of casein crosslinking |
| CN109225170B (en) * | 2018-09-27 | 2021-06-29 | 陕西科技大学 | Casein crosslinked cellulose-based adsorption material and preparation method and application thereof |
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Application publication date: 20130109 |