CN105195108A - Method for preparing modified natural fluoride adsorbent - Google Patents
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- CN105195108A CN105195108A CN201510625931.5A CN201510625931A CN105195108A CN 105195108 A CN105195108 A CN 105195108A CN 201510625931 A CN201510625931 A CN 201510625931A CN 105195108 A CN105195108 A CN 105195108A
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Abstract
The invention discloses a method for preparing modified natural fluoride adsorbent, which belongs to the technical field of adsorbents, and uses shell fragments as raw materials to prepare chitosan, and then the chitosan is calcined in high temperature to obtain adsorbent semi-finished products after being soaked chemically, grafted through formaldehyde and soaked in irons, thereby obtaining a modified natural fluoride adsorbent by polymerizing high molecules and combining magnetic polymers. The method for preparing modified natural fluoride adsorbent is simple and easy in operation, and the prepared modified natural fluoride adsorbent is obvious in adsorbing effect, can automatically degrade, achieves above 85.7% removal rate of fluorine in drinking water, is less in usage when being used, and reduces cost.
Description
Technical field
The invention discloses a kind of preparation method of modified natural de-fluoridation adsorbent, belong to absorbent preparation field.
Background technology
Fluorine is that in all elements, nonmetal character is the strongest, and at normal temperatures and pressures in gaseous state, its valence shell electronic structure is 2s
22p
5, atomic radius is 64pm, and fluorine is fluorite, ice crystal and fluor-apatite in natural main existence form.Fluorine is the necessary beneficial element of human body, and human body is respectively organized all fluorine-containing, maximum with the fluorinated volume of tooth, bone and hair.Within 1969, the 22nd WHA has made the resolution of " be recommended in running water and add fluoride caries prevention ".The supply and marketing of current toothpaste with fluoride is also the measure taked in order to caries prevention, but the harm that the too much absorption of fluorine produces animals and plants and human body, considerably beyond the not enough impact on health of fluorine.Oil repellent is too high, can affect the Ca,P metabolism of human body, makes the metabolism of human body and physiological function occur to wad a quilt with cotton disorderly, thus causes some fluorine poisoning symptoms such as fluorosis of bone, spot tooth.20 beginnings of the century, Late Cambrian mottled teeth near Italian Vesuvius, until nineteen thirty-seven, people just recognize that this is that in human body, Oil repellent has exceeded the slow poisoning caused by normal value, and this is that a kind of typical location is sick.Therefore, in environment, the harm of fluorine has become the problem that environmental science and health educational circles very pay close attention to, and general fluorine poisoning is mainly drunk caused by high-fluorine water, and the World Health Organization specifies that the upper limit of fluoride in drinking water is 1mg/L, exceedes this value and then can form harm to health.
Report that there is in more than 700,000,000 drinking water fluorine in China more than 1mg/L according to National survey, and traditional alumina adsorption method plays important large effect so far from the sixties, but the method fluoride removing rate is lower, consumption is large, and biodegradation can not be carried out voluntarily, in recent years all over the world because aluminium ion can cause neural disease to increase, in the drinking water quality standard of the execution of 2000, restriction aluminium content is 0.2mg/L, thus certain restriction of being subject to of alumina adsorption method.According to the present situation that I crosses, the World Health Organization, the World Bank and local government, carried out the poisoning study on prevention of fluoride in drinking water, especially for the removal of fluorine from water method being suitable for rural area and being suitable for, major requirement be that cost is low, place's fluorine rate improves, except water quality after fluorine do not change, simple to operate etc.In order to health, effectively removing the fluorine in drinking water, is a very important thing.
Summary of the invention
The technical problem that the present invention mainly solves: exceed standard for the fluorine in current drinking water and harm is constituted for human body, and although traditional alumina adsorption method plays a part great, but the method fluoride removing rate is lower, during use, amount ratio is larger, and cannot biodegradable problem voluntarily, provide a kind of preparation method of modified natural de-fluoridation adsorbent, the method is that raw material prepares shitosan with shell fragment, again chemical immersion is carried out to shitosan, formaldehyde grafting and leaching iron after, high-temperature calcination obtains adsorbent semi-finished product, combined by high molecular polymerization and magnetic high-molecular again, namely a kind of modified natural de-fluoridation adsorbent is obtained.The adsorbent made of the method not only adsorption effect is remarkable, can degrade voluntarily, make Oil repellent clearance in drinking water up to more than 85.7%, and when using, consumption is less, reduces cost.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
(1) collect the shell left over after the processing of scallop processing factory, with distilled water flushing 3 ~ 4 times, dry in its natural state, putting into that airslide disintegrating mill pulverizes is the fragment of 5 ~ 8mm;
(2) take 300 ~ 400g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 12 ~ 24h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier;
(3) continuation mass concentration is that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 110 ~ 120 DEG C, 1 ~ 2h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 90 ~ 100 DEG C, stirring reaction 1 ~ 2h, puts into baking oven and dries at 105 ~ 110 DEG C, obtain chitosan particle by filter residue after filtration;
(4) get the above-mentioned obtained chitosan particle of 10 ~ 20g and put into the formalin that 100 ~ 200mL mass concentration is 4%, add the sulfuric acid solution that 50 ~ 100mL concentration is 0.02mol/L again, be placed on vibration 60 ~ 90min on shaking table oscillator, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 4 ~ 5h under 60 ~ 70 DEG C of water bath condition, deionized water rinsing 2 ~ 3 times are used after taking out, put into baking oven to dry at 70 ~ 80 DEG C, obtained formaldehyde grafted chitosan;
(5) above-mentioned obtained formaldehyde grafted chitosan is put into ferric chloride solution immersion 12 ~ 24h that mass concentration is 80%, filter afterwards, by filter residue distilled water washing 2 ~ 3 times, put into thermostatic drying chamber dry 30 ~ 60min at 70 ~ 80 DEG C, armor aldehyde grafted chitosan must be soaked;
(6) above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 500 ~ 600 DEG C of high-temperature calcination 5 ~ 6h, obtain canescence adsorbent semi-finished product, for subsequent use;
(7) taking 10 ~ 13g iron chloride is dissolved in 85 ~ 90mL distilled water, stir obtained ferric ion solutions, taking 8 ~ 10g ferrous sulfate is again dissolved in 90 ~ 100mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 40 ~ 50mL mixed liquor afterwards, regulate pH to 9 ~ 10 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution;
(8) above-mentioned obtained adsorbent semi-finished product being dissolved in 100 ~ 200mL mass concentration is in the acetic acid solution of 80%, add 10 ~ 15g calcium chloride and 1 ~ 2g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 30 ~ 40min is stirred with the rotating speed of 300 ~ 400r/min, by 30 ~ 50mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 20 ~ 30min, filter after leaving standstill solidification 12 ~ 18h afterwards, filter residue deionized water rinsing 2 ~ 3 times, move into resistance furnace afterwards, calcine 2 ~ 3h at 300 ~ 400 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
Application process of the present invention is: a kind of modified natural de-fluoridation adsorbent got obtained by the present invention puts into pending drinking water, wherein add 10 ~ 20mg modified natural de-fluoridation adsorbent in every premium on currency, abundant mixing, after leaving standstill 15 ~ 25min, the fluorine-containing rate of water quality is measured with measuring instrument, the Oil repellent that contains in water can be made to be reduced to 0.1 ~ 0.2mg/L from 1.2 ~ 1.4mg/L, and clearance is up to more than 85.7%.
The invention has the beneficial effects as follows:
(1) a kind of modified natural de-fluoridation adsorbent made can carry out biodegradation voluntarily, and during each use, consumption is less, reduces cost;
(2) the adsorbent Be very effective made, makes Oil repellent clearance in drinking water up to more than 85.7%.
Detailed description of the invention
First collect the shell left over after the processing of scallop processing factory, with distilled water flushing 3 ~ 4 times, dry in its natural state, putting into that airslide disintegrating mill pulverizes is the fragment of 5 ~ 8mm, then take 300 ~ 400g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 12 ~ 24h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier, continuation mass concentration is subsequently that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 110 ~ 120 DEG C, 1 ~ 2h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 90 ~ 100 DEG C, stirring reaction 1 ~ 2h, puts into baking oven and dries at 105 ~ 110 DEG C, obtain chitosan particle by filter residue after filtration, get the above-mentioned obtained chitosan particle of 10 ~ 20g afterwards and put into the formalin that 100 ~ 200mL mass concentration is 4%, add the sulfuric acid solution that 50 ~ 100mL concentration is 0.02mol/L again, be placed on vibration 60 ~ 90min on shaking table oscillator, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 4 ~ 5h under 60 ~ 70 DEG C of water bath condition, deionized water rinsing 2 ~ 3 times are used after taking out, put into baking oven to dry at 70 ~ 80 DEG C, obtained formaldehyde grafted chitosan, next above-mentioned obtained formaldehyde grafted chitosan is put into ferric chloride solution immersion 12 ~ 24h that mass concentration is 80%, filter afterwards, by filter residue distilled water washing 2 ~ 3 times, put into thermostatic drying chamber dry 30 ~ 60min at 70 ~ 80 DEG C, armor aldehyde grafted chitosan must be soaked, again above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 500 ~ 600 DEG C of high-temperature calcination 5 ~ 6h, obtain canescence adsorbent semi-finished product, for subsequent use, taking 10 ~ 13g iron chloride is dissolved in 85 ~ 90mL distilled water, stir obtained ferric ion solutions, taking 8 ~ 10g ferrous sulfate is again dissolved in 90 ~ 100mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 40 ~ 50mL mixed liquor afterwards, regulate pH to 9 ~ 10 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution, finally above-mentioned obtained adsorbent semi-finished product being dissolved in 100 ~ 200mL mass concentration is in the acetic acid solution of 80%, add 10 ~ 15g calcium chloride and 1 ~ 2g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 30 ~ 40min is stirred with the rotating speed of 300 ~ 400r/min, by 30 ~ 50mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 20 ~ 30min, filter after leaving standstill solidification 12 ~ 18h afterwards, filter residue deionized water rinsing 2 ~ 3 times, move into resistance furnace afterwards, calcine 2 ~ 3h at 300 ~ 400 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
Example 1
First collect the shell left over after the processing of scallop processing factory, with distilled water flushing 3 times, dry in its natural state, put into airslide disintegrating mill and pulverize fragment for 5mm, then take 300g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 12h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier, continuation mass concentration is subsequently that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 110 DEG C, 1h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 90 DEG C, stirring reaction 1h, puts into baking oven and dries at 105 DEG C, obtain chitosan particle by filter residue after filtration, get the above-mentioned obtained chitosan particle of 10g afterwards and put into the formalin that 100mL mass concentration is 4%, add the sulfuric acid solution that 50mL concentration is 0.02mol/L again, be placed on 60min that shaking table oscillator vibrates, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 4h under 60 DEG C of water bath condition, uses deionized water rinsing 2 times after taking out, put into baking oven to dry at 70 DEG C, obtained formaldehyde grafted chitosan, next above-mentioned obtained formaldehyde grafted chitosan is put into mass concentration be 80% ferric chloride solution soak 12h, filter afterwards, filter residue distilled water washed 2 times, put into thermostatic drying chamber dry 30min at 70 DEG C, armor aldehyde grafted chitosan must be soaked, again above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 500 DEG C of high-temperature calcination 5h, obtain canescence adsorbent semi-finished product, for subsequent use, taking 10g iron chloride is dissolved in 85mL distilled water, stir obtained ferric ion solutions, taking 8g ferrous sulfate is again dissolved in 90mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 40mL mixed liquor afterwards, regulate pH to 9 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution, finally above-mentioned obtained adsorbent semi-finished product being dissolved in 100mL mass concentration is in the acetic acid solution of 80%, add 10g calcium chloride and 1g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 30min is stirred with the rotating speed of 300r/min, by 30mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 20min, filter after leaving standstill solidification 12h afterwards, filter residue deionized water rinsing 2 times, move into resistance furnace afterwards, calcine 2h at 300 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
This example operation is simple, a kind of modified natural de-fluoridation adsorbent got during use obtained by the present invention puts into pending drinking water, wherein add 10mg modified natural de-fluoridation adsorbent in every 1t water, abundant mixing, after leaving standstill 15min, measure the fluorine-containing rate of water quality with measuring instrument, the Oil repellent that contains in water can be made to be reduced to 0.2mg/L from 1.4mg/L, and clearance is up to 85.7%.
Example 2
First collect the shell left over after the processing of scallop processing factory, with distilled water flushing 3.5 times, dry in its natural state, put into airslide disintegrating mill and pulverize fragment for 7mm, then take 350g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 20h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier, continuation mass concentration is subsequently that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 115 DEG C, 1.5h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 95 DEG C, stirring reaction 1.5h, puts into baking oven and dries at 108 DEG C, obtain chitosan particle by filter residue after filtration, get the above-mentioned obtained chitosan particle of 15g afterwards and put into the formalin that 150mL mass concentration is 4%, add the sulfuric acid solution that 80mL concentration is 0.02mol/L again, be placed on 75min that shaking table oscillator vibrates, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 4.5h under 65 DEG C of water bath condition, uses deionized water rinsing 2.5 times after taking out, put into baking oven to dry at 75 DEG C, obtained formaldehyde grafted chitosan, next above-mentioned obtained formaldehyde grafted chitosan is put into mass concentration be 80% ferric chloride solution soak 20h, filter afterwards, filter residue distilled water washed 2.5 times, put into thermostatic drying chamber dry 50min at 75 DEG C, armor aldehyde grafted chitosan must be soaked, again above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 550 DEG C of high-temperature calcination 5.5h, obtain canescence adsorbent semi-finished product, for subsequent use, taking 12g iron chloride is dissolved in 88mL distilled water, stir obtained ferric ion solutions, taking 9g ferrous sulfate is again dissolved in 95mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 45mL mixed liquor afterwards, regulate pH to 9.5 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution, finally above-mentioned obtained adsorbent semi-finished product being dissolved in 115mL mass concentration is in the acetic acid solution of 80%, add 13g calcium chloride and 1.5g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 35min is stirred with the rotating speed of 350r/min, by 40mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 25min, filter after leaving standstill solidification 15h afterwards, filter residue deionized water rinsing 2.5 times, move into resistance furnace afterwards, calcine 2.5h at 350 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
This example operation is simple, a kind of modified natural de-fluoridation adsorbent got during use obtained by the present invention puts into pending drinking water, wherein add 15mg modified natural de-fluoridation adsorbent in every 1.5t water, abundant mixing, after leaving standstill 20min, measure the fluorine-containing rate of water quality with measuring instrument, the Oil repellent that contains in water can be made to be reduced to 0.15mg/L from 1.3mg/L, and clearance is up to 88.4%.
Example 3
First collect the shell left over after the processing of scallop processing factory, with distilled water flushing 4 times, dry in its natural state, put into airslide disintegrating mill and pulverize fragment for 8mm, then take 400g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 24h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier, continuation mass concentration is subsequently that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 120 DEG C, 2h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 100 DEG C, stirring reaction 2h, puts into baking oven and dries at 110 DEG C, obtain chitosan particle by filter residue after filtration, get the above-mentioned obtained chitosan particle of 20g afterwards and put into the formalin that 200mL mass concentration is 4%, add the sulfuric acid solution that 100mL concentration is 0.02mol/L again, be placed on 90min that shaking table oscillator vibrates, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 5h under 70 DEG C of water bath condition, uses deionized water rinsing 3 times after taking out, put into baking oven to dry at 80 DEG C, obtained formaldehyde grafted chitosan, next above-mentioned obtained formaldehyde grafted chitosan is put into mass concentration be 80% ferric chloride solution soak 24h, filter afterwards, filter residue distilled water washed 3 times, put into thermostatic drying chamber dry 60min at 80 DEG C, armor aldehyde grafted chitosan must be soaked, again above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 600 DEG C of high-temperature calcination 6h, obtain canescence adsorbent semi-finished product, for subsequent use, taking 13g iron chloride is dissolved in 90mL distilled water, stir obtained ferric ion solutions, taking 10g ferrous sulfate is again dissolved in 100mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 50mL mixed liquor afterwards, regulate pH to 10 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution, finally above-mentioned obtained adsorbent semi-finished product being dissolved in 200mL mass concentration is in the acetic acid solution of 80%, add 15g calcium chloride and 2g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 40min is stirred with the rotating speed of 400r/min, by 50mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 30min, filter after leaving standstill solidification 18h afterwards, filter residue deionized water rinsing 3 times, move into resistance furnace afterwards, calcine 3h at 400 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
This example operation is simple, a kind of modified natural de-fluoridation adsorbent got during use obtained by the present invention puts into pending drinking water, wherein add 20mg modified natural de-fluoridation adsorbent in every 2t water, abundant mixing, after leaving standstill 25min, measure the fluorine-containing rate of water quality with measuring instrument, the Oil repellent that contains in water can be made to be reduced to 0.1mg/L from 1.2mg/L, and clearance is up to 91.7%.
Claims (1)
1. a preparation method for modified natural de-fluoridation adsorbent, is characterized in that concrete preparation process is:
(1) collect the shell left over after the processing of scallop processing factory, with distilled water flushing 3 ~ 4 times, dry in its natural state, putting into that airslide disintegrating mill pulverizes is the fragment of 5 ~ 8mm;
(2) take 300 ~ 400g shell fragment and put into 2L beaker, add mass concentration be the hydrochloric acid of 10% by shell fragment submergence, shaking table oscillating reactions 12 ~ 24h, to remove the mineral compositions such as shell surface calcium carbonate and calcium phosphate, until raw material all softening after, dry with vacuum drier;
(3) continuation mass concentration is that the sodium hydroxide solution of 10% is by above-mentioned softening dried shell fragment submergence, move in oil bath pan, be warming up to 110 ~ 120 DEG C, 1 ~ 2h is boiled in stirring, obtains chitin with solubilising protein and degreasing, is that to be immersed in mass concentration be in the sodium hydroxide solution of 40% to 1:3 more afterwards by chitin by solid-to-liquid ratio, warming-in-water to 90 ~ 100 DEG C, stirring reaction 1 ~ 2h, puts into baking oven and dries at 105 ~ 110 DEG C, obtain chitosan particle by filter residue after filtration;
(4) get the above-mentioned obtained chitosan particle of 10 ~ 20g and put into the formalin that 100 ~ 200mL mass concentration is 4%, add the sulfuric acid solution that 50 ~ 100mL concentration is 0.02mol/L again, be placed on vibration 60 ~ 90min on shaking table oscillator, shitosan surface is fully contacted with formaldehyde sulfuric acid solution, move into reflux afterwards, reflux 4 ~ 5h under 60 ~ 70 DEG C of water bath condition, deionized water rinsing 2 ~ 3 times are used after taking out, put into baking oven to dry at 70 ~ 80 DEG C, obtained formaldehyde grafted chitosan;
(5) above-mentioned obtained formaldehyde grafted chitosan is put into ferric chloride solution immersion 12 ~ 24h that mass concentration is 80%, filter afterwards, by filter residue distilled water washing 2 ~ 3 times, put into thermostatic drying chamber dry 30 ~ 60min at 70 ~ 80 DEG C, armor aldehyde grafted chitosan must be soaked;
(6) above-mentioned leaching armor aldehyde grafted chitosan is put into Muffle furnace, be warming up to 500 ~ 600 DEG C of high-temperature calcination 5 ~ 6h, obtain canescence adsorbent semi-finished product, for subsequent use;
(7) taking 10 ~ 13g iron chloride is dissolved in 85 ~ 90mL distilled water, stir obtained ferric ion solutions, taking 8 ~ 10g ferrous sulfate is again dissolved in 90 ~ 100mL distilled water, stir preparation ferrous ions soln, by above-mentioned obtained iron ion and ferrous ions soln by volume for 3:2 mixes, get 40 ~ 50mL mixed liquor afterwards, regulate pH to 9 ~ 10 with the sodium hydroxide solution that mass concentration is 10%, obtained ferroferric oxide gel solution;
(8) above-mentioned obtained adsorbent semi-finished product being dissolved in 100 ~ 200mL mass concentration is in the acetic acid solution of 80%, add 10 ~ 15g calcium chloride and 1 ~ 2g calcium bicarbonate powder, stir and obtain mixed liquor, by mixed liquor by volume for 1:2 joins in ferroferric oxide gel solution, be placed on magnetic stirrer, 30 ~ 40min is stirred with the rotating speed of 300 ~ 400r/min, by 30 ~ 50mL mass concentration be while stirring afterwards 50% sodium alginate soln dropwise instill, controlling rate of addition makes it drip off in 20 ~ 30min, filter after leaving standstill solidification 12 ~ 18h afterwards, filter residue deionized water rinsing 2 ~ 3 times, move into resistance furnace afterwards, calcine 2 ~ 3h at 300 ~ 400 DEG C after, obtain a kind of modified natural de-fluoridation adsorbent.
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| CN108704616A (en) * | 2018-05-28 | 2018-10-26 | 苏州佑君环境科技有限公司 | A kind of preparation method of modification of chitosan fluorine ion absorber |
| CN110591316A (en) * | 2019-09-26 | 2019-12-20 | 深圳市氩氪新材料技术研究服务有限公司 | Shell powder modified polylactic acid composite material and preparation method and application thereof |
| CN113842871A (en) * | 2021-10-19 | 2021-12-28 | 山东建筑大学 | Anti-interference defluorination adsorbent and preparation method thereof |
| CN113896310A (en) * | 2021-11-16 | 2022-01-07 | 温州大学 | Preparation and application method of shell powder modified organic polymeric flocculant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108704616A (en) * | 2018-05-28 | 2018-10-26 | 苏州佑君环境科技有限公司 | A kind of preparation method of modification of chitosan fluorine ion absorber |
| CN110591316A (en) * | 2019-09-26 | 2019-12-20 | 深圳市氩氪新材料技术研究服务有限公司 | Shell powder modified polylactic acid composite material and preparation method and application thereof |
| CN113842871A (en) * | 2021-10-19 | 2021-12-28 | 山东建筑大学 | Anti-interference defluorination adsorbent and preparation method thereof |
| CN113896310A (en) * | 2021-11-16 | 2022-01-07 | 温州大学 | Preparation and application method of shell powder modified organic polymeric flocculant |
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Application publication date: 20151230 |