CN103466742A - Method for removing bromate contained in drinking water - Google Patents
Method for removing bromate contained in drinking water Download PDFInfo
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- CN103466742A CN103466742A CN2013104391298A CN201310439129A CN103466742A CN 103466742 A CN103466742 A CN 103466742A CN 2013104391298 A CN2013104391298 A CN 2013104391298A CN 201310439129 A CN201310439129 A CN 201310439129A CN 103466742 A CN103466742 A CN 103466742A
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- organic polymer
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Abstract
The invention discloses a method for removing bromate contained in drinking water. The method comprises the following steps that: an absorption column filled with modified cross-linking chitosan organic high-molecular adsorbing materials is connected on the outflow position of the drinking water; after the drinking water is absorbed by the modified cross-linking chitosan organic high-molecular adsorbing materials inside the absorption column filled with the modified cross-linking chitosan organic high-molecular adsorbing materials, the bromate contained in the drinking water can be removed. The method for removing the bromate contained in the drinking water can be used for effectively removing the bromate contained in the drinking water and has the characteristics of no secondary pollution, nontoxicity, harmlessness, recycling, easiness for operation and low treatment cost.
Description
Technical field
The present invention relates to a kind of method of removing bromate in drinking water, particularly a kind of adsorption column of filling-modified cross-linked chitosan as sorbing material that utilize, remove the method for drinking the Bromide hydrochlorate produced after ozonization.
Background technology
Along with the development of giving water technology and the people attention to drinking-water quality, ozone disinfecting technology starts widespread use in the application of tap water.But, while in processing water body, containing bromide, after ozone Oxidation Treatment, can produce the by product bromate.Bromate is very large to harm, has carcinogenic and mutagenicity, is decided to be the potential carcinogen of 2B level (than high carcinogenic) by international cancer mechanism.(the World Health Organization of the World Health Organization, WHO) in up-to-date " drinking-water quality criterion ", by the bromate limit value, from 25 μ g/L revisions, be 10 μ g/L, " drinking water sanitary standard " of the new revision of China (GB5749-2006) also regulation bromate limit value be 10 μ g/L.Therefore, the research of control and removal ozone disinfection by-product bromate is very urgent.
Controlling bromate in drinking water has two large approach, and the one, in the generative process of bromate, control, the 2nd, the removal of the bromate after generating in water body.The technology of controlling at present bromate mainly contains ammonification, reduces pH value etc., and the technology of removing bromate has charcoal absorption to remove method, ion exchange method, ferrous ion reduction removal method, Zero-valent Iron reduction removal method, ultraviolet irradiation etc.But still have some drawbacks, as ammonification with reduce pH value to the too high former water of control bromide ion concentration, in effluent quality, bromate tends to exceed standard.Now more to the research of gac, but after using for some time, gac is removed the bromate decrease in efficiency, needs often regeneration and changes, and increases the drinking water treatment cost.The uviolizing power consumption is higher, and processing cost is high.The Zero-valent Iron method is subject to the impact of the factors such as DO, water intermediate ion larger, and cost is large, only limits to laboratory and can not drop into during a large amount of one-tenth produces.
Summary of the invention
The objective of the invention is the drawback for above-mentioned the whole bag of tricks, a kind of method that can effectively remove trace amounts of bromine hydrochlorate in tap water is provided, processing with low cost, capable of circulation, nontoxic that the method has.
Know-why of the present invention
Chitosan is by becoming larger molecular organics matter after cross-linking modified, the stability of physics and chemistry all strengthens greatly, thereby can be filled in adsorption column, bromate is removed, in the aqueous solution, a large amount of hydrolyzable aminosilanes generation hydrogen bonds of modified crosslinking chitosan and the larger chemical gravitation that the negatively charged ion bromate passes through adsorb bromate, thereby bromate is removed from tap water.
Technical scheme of the present invention
A kind of method of removing bromate in drinking water, be that tap water water outlet place connects an absorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, tap water, after the absorption of the modified crosslinking chitosan organic polymer sorbing material in the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, can be removed the bromate in tap water;
The absorption column that wherein is filled with modified crosslinking chitosan organic polymer sorbing material comprises packed column and sorbing material;
Described sorbing material is modified crosslinking chitosan organic polymer;
Described packed column is irony or quartziferous pipe;
Described modified crosslinking chitosan organic polymer sorbing material is filled in packed column, and the two ends of described packed column are provided with filter sieve, to guarantee water, pass through, and modified crosslinking chitosan organic polymer sorbing material is filtered and holds back;
Described packed column is irony or quartziferous pipe;
Described modified crosslinking chitosan organic polymer sorbing material is prepared by a method comprising the following steps:
At first, chitosan is dissolved in fully in the hydrochloric acid soln of 0.1mol/L, is heated to 50 ℃, the chitosan salt acid solution that to obtain concentration be 10g/L;
Then, controlling drop rate is 15ml/min
todrip the glutaraldehyde water solution that mass percent concentration is 25% in the chitosan salt acid solution of above-mentioned gained, drip post-heating and be warming up to 90 ℃, after stirring reaction 80min, obtain reaction solution;
The amount of the glutaraldehyde water solution that above-mentioned dropping mass percent concentration used is 25%, press glutaraldehyde: the mass ratio of the chitosan in the chitosan salt acid solution calculates, i.e. glutaraldehyde: chitosan is 1:1.2;
Then, the pH value of regulating the reaction solution of above-mentioned gained with the 6mol/L sodium hydroxide solution is 9, controlling temperature after yellow flocks occurring is that 45min is stirred in 90 ℃ of continuation, then filter, the filter cake of gained is washed with distilled water to the pH of effluent liquid to neutral, then use successively acetone and washing with alcohol 2 times, finally dry to constant weight under 45 ℃, obtain modified crosslinking chitosan organic polymer sorbing material.
A kind of above-mentioned method of removing bromate in drinking water, specifically comprise the steps:
(1), the preparation of modified crosslinking chitosan organic polymer sorbing material
At first, chitosan is dissolved in fully in the hydrochloric acid soln of 0.1mol/L, is heated to 50 ℃, the chitosan salt acid solution that to obtain concentration be 10g/L;
Then, controlling drop rate is 15ml/min
todrip the glutaraldehyde water solution that mass percent concentration is 25% in the chitosan salt acid solution of above-mentioned gained, drip post-heating and be warming up to 90 ℃, after stirring reaction 80min, obtain reaction solution;
The amount of the glutaraldehyde water solution that above-mentioned dropping mass percent concentration used is 25%, press glutaraldehyde: the mass ratio of the chitosan in the chitosan salt acid solution calculates, i.e. glutaraldehyde: chitosan is 1:1.2;
Then, the pH value of regulating the reaction solution of above-mentioned gained with the 6mol/L sodium hydroxide solution is 9, controlling temperature after yellow flocks occurring is that 45min is stirred in 90 ℃ of continuation, then filter, the filter cake of gained is washed with distilled water to the pH of effluent liquid to neutral, then use successively acetone and washing with alcohol 2 times, finally dry to constant weight under 45 ℃, obtain modified crosslinking chitosan organic polymer sorbing material;
(2), adsorption unit is installed
The modified crosslinking chitosan organic polymer sorbing material of step (1) gained is filled in packed column, obtain being filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, the adsorption column that then will be filled with modified crosslinking chitosan organic polymer sorbing material is installed on the outlet conduit of tap water or the water outlet of water container;
(3), remove bromate in water
After tap water is opened, the tap water water outlet is flowed through while being filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, modified crosslinking chitosan organic polymer sorbing material in packed column and the bromate negatively charged ion in tap water pass through hydrogen bond gravitation chemisorption, thereby bromate is removed from tap water.
After the above-mentioned adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material is used for some time, the adsorption effect variation, now will carry out activating and regenerating to the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, its concrete steps are as follows:
The adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material is disassembled from pipeline or container, first with the NaOH solution of 0.01mol/L, rinse immersion 30min, then extremely neutral with distilled water flushing, carry out activating and regenerating with the HCl solution flushing of 0.01mol/L again, final rinse water is to neutral, and 45 ℃ of oven drying at low temperatures get final product.
Beneficial effect of the present invention
A kind of method of removing bromate in drinking water of the present invention, connect an adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material owing to adopting in tap water water outlet place, tap water can effectively be removed bromate in drinking water after the absorption of the modified crosslinking chitosan organic polymer sorbing material in the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, and, modified crosslinking chitosan organic polymer sorbing material reusable edible used at least 5 times.
Further, a kind of method of removing bromate in drinking water of the present invention, due to sorbing material modified crosslinking chitosan organic polymer used, it has low production cost, wide material sources, nontoxic, and biodegradable, therefore method of the present invention has non-secondary pollution, nontoxic characteristics.
Further, a kind of method of removing bromate in drinking water of the present invention, because the used adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material is easy for installation, so the method has characteristics simple to operate.
Further, a kind of method of removing bromate in drinking water of the present invention, owing to adopting absorption method, processed, the energy consumption needed is little, and sorbing material modified crosslinking chitosan organic polymer is cheap and easy to get, saturated adsorption capacity to bromate is large, so processing cost is low, is suitable for promoting the use of.
Embodiment
Below by specific embodiment, the present invention is further set forth, but do not limit the present invention.
The selected all ingredients of the present invention is analytical pure.
embodiment 1
A kind of method of removing bromate in drinking water, connect an adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material in tap water water outlet place, tap water can be removed the bromate in tap water after the absorption of the modified crosslinking chitosan organic polymer sorbing material in the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, specifically comprises the steps:
(1), the preparation of modified crosslinking chitosan organic polymer sorbing material
The 1.0g chitosan is dissolved in the hydrochloric acid soln that 100ml concentration is 0.1mol/L fully, is heated to 50 ℃, the chitosan salt acid solution that to obtain concentration be 10g/L;
Then, controlling drop rate is 15ml/min
todrip the glutaraldehyde water solution that the 4.8ml mass percent concentration is 25% in the chitosan salt acid solution of above-mentioned gained, drip post-heating and be warming up to 90 ℃, after stirring reaction 80min, obtain reaction solution;
The amount of the glutaraldehyde water solution that above-mentioned dropping mass percent concentration used is 25%, press glutaraldehyde: the mass ratio of the chitosan in the chitosan salt acid solution calculates, i.e. glutaraldehyde: chitosan is 1:1.2;
Then, the pH value of regulating the reaction solution of above-mentioned gained with the 6mol/L sodium hydroxide solution is 9, controlling temperature after yellow flocks occurring is that 45min is stirred in 90 ℃ of continuation, then filter, the filter cake of gained is washed with distilled water to the pH of effluent liquid to neutral, then use successively acetone and washing with alcohol 2 times, finally dry to constant weight under 45 ℃, the reddish-brown powdery substance obtained is modified crosslinking chitosan organic polymer sorbing material;
(2), adsorption unit is installed
Get a diameter 8cm, the long transparent quartz tube for 0.5m is as packed column, the modified crosslinking chitosan organic polymer sorbing material that step (1) is obtained is filled in wherein, must be filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material of gained is installed on to the water outlet of sterilization outlet conduit or water container;
(3), remove bromate in water
The water outlet of tap water is flowed through while being filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, sorbing material modified crosslinking chitosan organic polymer wherein and the bromate negatively charged ion in tap water are by hydrogen bond gravitation chemisorption, thereby bromate is removed from tap water, through IC sulfate by ion chromatography (the drinking water standard method of inspection, the State Standard of the People's Republic of China, GB/T 5750.10-2006), water after the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material is processed, the content 50 μ g/L of the bromate before processing in tap water, the content of the bromate after processing in tap water is that the 0(inspection does not measure), its clearance reaches 100%.
Modified crosslinking chitosan organic polymer sorbing material sorbing material in above-mentioned packed column reach absorption saturated after, the adsorption effect variation, now to carry out rinsing desorption to the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material is disassembled from pipeline or container, first with the NaOH solution of 0.01mol/L, rinse immersion 30min, then extremely neutral with distilled water flushing, carry out activating and regenerating with the HCl solution flushing of 0.01mol/L again, final rinse water is to neutral, 45 ℃ of oven drying at low temperatures can utilize again.
Modified crosslinking chitosan organic polymer sorbing material in above-mentioned packed column through rinsing desorption repeatedly after, it is higher that adsorption rate still can keep.And experiment showed, that the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material of above-mentioned gained through utilizing after use in the drinking water treatment system circulates and regenerates for 5 times, its adsorption rate still can keep more than 80%.
In sum, a kind of method of removing bromate in drinking water of the present invention, can effectively remove bromate in drinking water, non-secondary pollution, and fitting operation is simple, with low cost, nontoxic, and reusable edible.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvement and modification, these improve and modification all should be considered as protection scope of the present invention.
Claims (2)
1. a method of removing bromate in drinking water, it is characterized in that connecing an absorption column that is filled with modified crosslinking chitosan organic polymer sorbing material in tap water water outlet place, tap water, after the absorption of the modified crosslinking chitosan organic polymer sorbing material in the adsorption column that is filled with modified crosslinking chitosan organic polymer sorbing material, can be removed the bromate in tap water;
The absorption column that wherein is filled with modified crosslinking chitosan organic polymer sorbing material comprises packed column and sorbing material;
Described sorbing material is modified crosslinking chitosan organic polymer;
Described packed column is irony or quartziferous pipe;
Sorbing material modified crosslinking chitosan organic polymer sorbing material is filled in packed column, and two of packed column is provided with filter sieve;
Described modified crosslinking chitosan organic polymer sorbing material is prepared by a method comprising the following steps:
At first, chitosan is dissolved in fully in the hydrochloric acid soln of 0.1mol/L, is heated to 45 ℃ and obtains the chitosan salt acid solution that concentration is 10g/L;
Then, controlling drop rate is that 15ml/min drips the glutaraldehyde water solution that mass percent concentration is 25% in the chitosan salt acid solution of above-mentioned gained, drips post-heating and is warming up to 90 ℃, after stirring reaction 80min, obtains reaction solution;
The amount of the glutaraldehyde water solution that above-mentioned dropping mass percent concentration used is 25%, press glutaraldehyde: the mass ratio of the chitosan in the chitosan salt acid solution calculates, i.e. glutaraldehyde: chitosan is 1:1.2;
Then, the pH value of regulating the reaction solution of above-mentioned gained with the 6mol/L sodium hydroxide solution is 9, controlling temperature after yellow flocks occurring is that 45min is stirred in 90 ℃ of continuation, then filter, the filter cake of gained is washed with distilled water to the pH of effluent liquid to neutral, then use successively acetone and washing with alcohol 2 times, finally dry to constant weight under 45 ℃, obtain modified crosslinking chitosan organic polymer.
2. a kind of method of removing bromate in drinking water as claimed in claim 1, is characterized in that specifically comprising the steps:
(1), the preparation of modified crosslinking chitosan organic polymer sorbing material
At first, chitosan is dissolved in fully in the hydrochloric acid soln of 0.1mol/L, is heated to 50 ℃, the chitosan salt acid solution that to obtain concentration be 10g/L;
Then, controlling drop rate is that 15ml/min drips the glutaraldehyde water solution that mass percent concentration is 25% in the chitosan salt acid solution of above-mentioned gained, drips post-heating and is warming up to 90 ℃, after stirring reaction 80min, obtains reaction solution;
The amount of the glutaraldehyde water solution that above-mentioned dropping mass percent concentration used is 25%, press glutaraldehyde: the mass ratio of the chitosan in the chitosan salt acid solution calculates, i.e. glutaraldehyde: chitosan is 1:1.2;
Then, the pH value of regulating the reaction solution of above-mentioned gained with the 6mol/L sodium hydroxide solution is 9, controlling temperature after yellow flocks occurring is that 45min is stirred in 90 ℃ of continuation, then filter, the filter cake of gained is washed with distilled water to the pH of effluent liquid to neutral, then use successively acetone and washing with alcohol 2 times, finally dry to constant weight under 45 ℃, obtain modified crosslinking chitosan organic polymer sorbing material;
(2), adsorption unit is installed
The modified crosslinking chitosan organic polymer sorbing material of step (1) gained is filled in packed column, obtain being filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, the adsorption column that then will be filled with modified crosslinking chitosan organic polymer sorbing material is installed on the outlet conduit of tap water or the water outlet of water container;
(3), remove bromate in water
After tap water is opened, the tap water water outlet is flowed through while being filled with the adsorption column of modified crosslinking chitosan organic polymer sorbing material, modified crosslinking chitosan organic polymer sorbing material in packed column and the bromate negatively charged ion in tap water pass through hydrogen bond gravitation chemisorption, thereby bromate is removed from tap water.
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| CN201310439129.8A CN103466742B (en) | 2013-09-25 | 2013-09-25 | Method for removing bromate contained in drinking water |
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| CN201310439129.8A CN103466742B (en) | 2013-09-25 | 2013-09-25 | Method for removing bromate contained in drinking water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993384A (en) * | 2018-07-18 | 2018-12-14 | 中国地质大学（北京） | A kind of load iron lotus charcoal and preparation method thereof removing bromate in water removal |
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| CN1765516A (en) * | 2005-09-13 | 2006-05-03 | 北京化工大学 | Laminated material for reclaiming bromine and bromine-containing water treatment method |
| JP2009045523A (en) * | 2007-08-16 | 2009-03-05 | National Institute Of Advanced Industrial & Technology | Adsorbent for bromic acid ion |
| CN102276008A (en) * | 2011-06-21 | 2011-12-14 | 中国科学院化学研究所 | Method for reducing bromate content of water |
| KR20120087678A (en) * | 2011-01-28 | 2012-08-07 | 재단법인 탄소순환형 차세대 바이오매스 생산전환 기술연구단 | Making method of bimetallic oxide adsorbent for bromate removal from drinking water |
| CN103041787A (en) * | 2013-01-08 | 2013-04-17 | 山东大学 | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material |
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2013
- 2013-09-25 CN CN201310439129.8A patent/CN103466742B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765516A (en) * | 2005-09-13 | 2006-05-03 | 北京化工大学 | Laminated material for reclaiming bromine and bromine-containing water treatment method |
| JP2009045523A (en) * | 2007-08-16 | 2009-03-05 | National Institute Of Advanced Industrial & Technology | Adsorbent for bromic acid ion |
| KR20120087678A (en) * | 2011-01-28 | 2012-08-07 | 재단법인 탄소순환형 차세대 바이오매스 생산전환 기술연구단 | Making method of bimetallic oxide adsorbent for bromate removal from drinking water |
| CN102276008A (en) * | 2011-06-21 | 2011-12-14 | 中国科学院化学研究所 | Method for reducing bromate content of water |
| CN103041787A (en) * | 2013-01-08 | 2013-04-17 | 山东大学 | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993384A (en) * | 2018-07-18 | 2018-12-14 | 中国地质大学（北京） | A kind of load iron lotus charcoal and preparation method thereof removing bromate in water removal |
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Inventor after: Gu Haixin Inventor after: Wen Huanhuan Inventor after: Shi Wenjian Inventor after: Wu Wei Inventor after: Wang Jingzhi Inventor after: Yin Xiaohang Inventor after: Ma Juntao Inventor after: Shen Cuan Inventor after: Liu Jianqing Inventor after: Feng Wenxuan Inventor after: Li Kuanyang Inventor before: Liu Jianqing Inventor before: Shi Wenjian Inventor before: Wen Huanhuan Inventor before: Feng Wenxuan Inventor before: Wu Wei Inventor before: Gu Haixin Inventor before: Wang Jingzhi |
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Free format text: CORRECT: INVENTOR; FROM: LIU JIANQING SHI WENJIAN WEN HUANHUAN FENG WENXUAN WU WEI GU HAIXIN WANG JINGZHI TO: GU HAIXIN WU WEI WANG JINGZHI YIN XIAOHANG MA JUNTAO SHEN XIN LIU JIANQING FENG WENXUAN LI KUANYANG WEN HUANHUAN SHI WENJIAN |
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