CN1493393A - Adsorber for removing antiseptic byproduct in city water and its preparation and use method - Google Patents
Adsorber for removing antiseptic byproduct in city water and its preparation and use method Download PDFInfo
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- CN1493393A CN1493393A CNA031506496A CN03150649A CN1493393A CN 1493393 A CN1493393 A CN 1493393A CN A031506496 A CNA031506496 A CN A031506496A CN 03150649 A CN03150649 A CN 03150649A CN 1493393 A CN1493393 A CN 1493393A
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- water
- tap water
- dbp
- sorbent material
- disinfection byproduct
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Abstract
An adsorbent for removing the disinfecting by-products from running water is prepared from hydrotalcite and adhesive through proportionally mixing, granulating and calcining. Its advantages are strong selectively adsorptive power, a certain strangth, low cost and high effect.
Description
Technical field
The present invention relates to a kind of sorbent material and preparation and using method of removing disinfection byproduct (DBP) in the tap water.
Background technology
City tap-water need to add the chlorine agent in treating processes, cholorination can be killed microorganism in the water, the infection of the water disease that prevents to be situated between.But on the other hand, many by products of the sterilizing process formation of tap water that studies show that itself have carcinogenic and mutagenesis.Some organic chemicals effect meeting in chlorine and the processed water generates materials such as trichloromethane (THMs claims chloroform again), Mono Chloro Acetic Acid (HAAs) and chloromethyl cyanide (HANs) class.But trichloromethane and Mono Chloro Acetic Acid are classified as one of carcinogenic substance by EPA.EPA has announced that disinfection byproduct (DBP) trichloromethane (THMs) and the upper content limit of Mono Chloro Acetic Acid (HAAs) in tap water are respectively 0.080 and 0.060mg/L.How removing substance of disinfection by products is one of focus of studying to water treatment in the world at present, and China has also given great attention to this.
The disinfection byproduct (DBP) that produces for the prechlorination stage is mainly removed by water technology at present; For post chlorization and the living disinfection byproduct (DBP) of benefit chlorine special product, then remove its parent organism, to reduce the possibility that by product generates by technology.These organic chemistry materials mainly are the humic acid that exists in the former water.Humic acid is the product of soil ulmin degraded in the natural water, and as condensess such as carboxyl benzene, aromatic amine yl carboxylic acids, they all are anionic organic macromolecule materials.Present tap water treatment process adopts active carbon adsorption more.There are 2 deficiencies in this method: it is low to remove efficient, and the cycle of operation is short; The cost height, about 20,000 yuans per ton of activated carbon.Part water factory begins to adopt dioxide peroxide (ClO
2) replace chlorine, as the disinfection of tap water agent.Dioxide peroxide is strong oxidation punishment, does not contain the chlorination organic by-products substantially in the product of its institute's oxidation, but has produced new by product chlorite (ClO
2 -) and chlorate anions (ClO
3 -), these two kinds of materials can cause the health problem (as hemolytic anemia) of blood system, thereby also are put into the by product that needs removal.
In above-mentioned disinfection byproduct (DBP), chlorite, chlorate anions, Mono Chloro Acetic Acid, and the parent～humic acids of trichloromethane and chloromethyl cyanide all are negatively charged ion, complex anion or polymerization anionic form and exist in the aqueous solution.Therefore, the present invention is directed to and from tap water, remove disinfection byproduct (DBP) and parent material thereof, proposed a kind of preparation of adsorbent and using method.This sorbent material also has very strong removal effect to the poisonous and harmful component that is the anionic form existence in the open water supply, can be used for handling fluorine-containing, arsenic-containing water source, makes it to reach standard for drinking.
Summary of the invention
The purpose of this invention is to provide a kind of sorbent material and preparation and using method of removing disinfection byproduct (DBP) in the tap water.
The sorbent material that can remove disinfection byproduct (DBP) and parent material thereof from tap water is that hydrotalcite derivant and binding agent were by 20: 1 to 3: 1 weight ratio blended mixtures.
The step of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water is as follows:
1) hydrotalcite and binding agent dry respectively before use or are no more than under 80 ℃ of conditions in temperature and dry, and are milled to less than 200 orders;
2) hydrotalcite and the binding agent weight ratio by 20: 1 to 3: 1 is mixed, add 10～30% water, and stir kneading evenly;
3) said mixture being made diameter is 0.2～2 centimetre granular, dries or dries being lower than under 80 ℃ of temperature;
4) with above-mentioned particle 450～800 ℃ of temperature lower calcinations 1～4 hour, be cooled to preserve in the stopping property container of packing into after the room temperature stand-by.
The step of using method of sorbent material that can remove disinfection byproduct (DBP) and parent material thereof from tap water is as follows:
1) absorbent particles is filled in the cylindrical container, the diameter of cylindrical shell (3) is 2～8 times of running water pipe (1); The two ends of container are equipped with filter screen (2), and its mesh is less than the diameter of absorbent particles; Be provided with spirrillum baffle plate (4) in the container,, slow down its flow velocity to change the direction of a stream of water;
2) cylindrical container that fills sorbent material is installed in: the I) water-in of liquid chlorine, chlorinated lime sterilization process; II) liquid chlorine, chlorinated lime, ClO
2The water outlet of sterilization process; III) inlet at the tap water of resident family or other water source; When tap water flows I, sorbent material can remove the humic acid in anhydrating, and reduces the organic content of chlorination in the tap water; When tap water flows II and III, sorbent material can remove the disinfection byproduct (DBP) in anhydrating and be the unwanted component that anionic form exists;
3) the exhausted sorbent material is reusable after 2～4 hours through 450～600 ℃ of calcinings.
Sorbent material raw material sources provided by the present invention are extensive, and the preparation synthesis technique is simple, and cost is lower than existing gac.The sorbent material that is provided is easy-to-use, needn't change existing water treatment technological process.It promptly can be applicable to the waterworks, to remove by product or its parent material of chlorination, also can use for resident family, and water quality is done further to purify.This sorbent material also has very strong removal effect to the poisonous and harmful component that is the anionic form existence in the open water supply, can be used for handling fluorine-containing, arsenic-containing water source, makes it to reach standard for drinking.Sorbent material is reusable, has further reduced cost.
Description of drawings
Accompanying drawing is the cylindrical container structural representation that holds sorbent material, among the figure: running water pipe 1, filter screen 2, cylindrical shell 3, spirrillum baffle plate 4.
Embodiment
In view of being anionic form mostly, the disinfection byproduct (DBP) in the tap water and parent material thereof be dissolved in the water, the sorbent material main component that the present invention proposes is that negatively charged ion is had hydrotalcite derivant than the strong selectivity adsorptive power, claim bimetallic oxide again, for hydrotalcite at 450～800 ℃ of calcinates, its chemical structural formula is:
[M
x IIM
y IIIO
X+1.5y] M wherein
IIBe divalent metal; M
IIIBe trivalent metal cation.In the aqueous solution, the structure that bimetallic oxide can come the restoration and reconstruction hydrotalcite by the negatively charged ion in the absorption environment, therefore, it is to the disinfection byproduct (DBP) in the tap water, belong to chemisorption as chlorate anions, chlorite, chloroacetic absorption, loading capacity height, and tool non-reversibility.
Another component in the sorbent material is the molding bonded agent, can select a kind of in montmorillonite, kaolinite, illite, sepiolite, the polygorskite or several for use, and they all are natural bed flaky aluminum silicate mineralss, have stronger cohesive force and plasticity-.When being heated to 450～800 ℃, these components undergo phase transition because of dehydration, make absorbent particles have fixed shape and certain mechanical strength, are unlikely in use to disintegrate, run off.
Aluminium salt is a kind of of aluminum chloride, aluminum nitrate, Tai-Ace S 150 and hydrate thereof or several; Said magnesium salts is a kind of of magnesium chloride, magnesium nitrate, sal epsom and hydrate thereof or several; Said alkali is a kind of of sodium hydroxide, potassium hydroxide, ammoniacal liquor, and said carbonate is a kind of of yellow soda ash, salt of wormwood.
Hydrotalcite is the commercial goods, also can prepare according to the following steps:
1) is mixed with the solution that concentration is 0.1～0.4M with aluminium salt is soluble in water, in solution, adds 2～4 times of mole numbers, stir, make salts solution A until molten entirely to the magnesium salts of aluminium salt;
2) carbonate that mole number is equated with magnesium salts is soluble in water, is made into the solution that concentration is 0.6～0.9M, adds the alkali that mole number is three times in carbonate in solution, stirs until molten entirely, makes alkaline solution B;
3) adopt coprecipitation method that two kinds of solution of above-mentioned A, B are dropwise splashed in the water that violent stirring simultaneously; Perhaps with hydrothermal method with two solution short mix, obtain white suspension;
4) suspension is put into water-bath, under 70～95 ℃, stir crystallization; Perhaps suspension is placed pressure vessel, crystallization under 120～160 ℃ of conditions;
5) with step 4) products therefrom suction filtration, be washed to neutrality.Put into baking oven,, obtain hydrotalcite 60～80 ℃ of oven dry down.
The hydrotalcite that the present invention uses preferably uses the commercially available prod, can save initial investment on the one hand, and on the other hand, the commercially available prod has more price advantage, and quality is more stable.
Commercially available hydrotalcite is generally packed powder, can directly use.Mostly be massive ore as the clay mineral of binding agent, should dry and be milled to less than 200 orders after use.The ratio of the two can be grasped at 20: 1 to 3: 1.Water consumption is bigger to molding, granulating influence, should grasp in that pinch with hand can be agglomerating, is degree but be difficult for rheology.
After two kinds of raw materials add water and mix, can use routinely tablets press to make particulate state.Particle excessive and too small all being unfavorable for uses, and particle diameter should be controlled at 0.5～0.8 centimetre and be advisable.
The granular adsorption agent is filled in the tubular vessel uses, on the one hand current are fully contacted with sorbent material, be convenient to control reaction process simultaneously and detect adsorption effect.The diameter of tubular vessel and length can obtain according to flow velocity, flow rate calculation, generally should make tap water be no less than 5～8 minutes from the time that import flow to outlet and be advisable.
For the water factory that uses liquid chlorine and chlorinated lime, before and after sterilization, all need use sorbent material of the present invention.Use can remove the humic acids organic matter in anhydrating before the sterilization, suppresses the organic formation of chlorination such as chloroform, Mono Chloro Acetic Acid; Residual chlorate anions and chlorite can be further removed in sterilization back use.Use ClO
2As the water factory of sterilizing agent, only need after sterilization, to use.The sorbent material that the present invention proposes also can use for resident family, and water quality is done further to purify.This sorbent material also has very strong removal effect to the poisonous and harmful component that is the anionic form existence in the open water supply, can be used for handling fluorine-containing, arsenic-containing water source, makes it to reach standard for drinking.Used sorbent material can be reused after 2～4 hours at 450～600 ℃ of calcining and activatings.
Embodiment 1: the preparation of hydrotalcite.
1) with 0.225mol MgCl
2With 0.075mol AlCl
3Be dissolved in the 250mL water and be made into MgCl)
2And AlCl
3Salts solution A;
2) with 0.675mol NaOH and 0.225mol Na
2CO
3Be dissolved in and be made into NaOH and Na in the 250mL water
2CO
3Alkaline solution B;
3) saline solution and alkali lye are dropwise splashed into simultaneously in the 100mL distilled water that violent stirring, the dropping time is 4 hours;
4) suspension is put into water-bath, under 80 ℃ of temperature, stirred crystallization 24 hours;
5) with the product suction filtration, be washed to neutrality.
6) under 80 ℃ of temperature, dry, be ground to, place encloses container standby less than 200 orders.
Embodiment 2: preparation of adsorbent.
1) takes by weighing 8 kilograms of commercially available hydrotalcite powder, dry for 2 kilograms, and be milled to, mix, place container less than 200 purpose soft kaolins;
2) get 2 premium on currency, pour in the said vesse while stir, it is fast that mixture is rubbed into the plastic group of tool;
3) above-mentioned group being made soon diameter is 0.8 centimetre particle, dries under 80 ℃ of temperature;
4) particle after the oven dry moved in the muffle furnace, 550 ℃ of temperature lower calcinations 3 hours;
5) be cooled to room temperature after, place encloses container standby particle.
Embodiment 3: the use of sorbent material (I).
1) will fill the cylindrical container of absorbent particles as shown in Figure 1, be installed on the water-in and water outlet pipeline of waterworks liquid chlorine or chlorinated lime sterilization pool;
2) changed sorbent material every 10～20 days, to keep adsorption efficiency;
3) used sorbent material is reusable after two hours 550 ℃ of calcinings;
Embodiment 4: the use of sorbent material (II).
1) will fill the cylindrical container of absorbent particles as shown in Figure 1, be installed in waterworks ClO
2On the water outlet pipeline of sterilization pool;
2) changed sorbent material every 10～20 days, to keep adsorption efficiency;
3) used sorbent material is reusable after two hours 550 ℃ of calcinings;
Embodiment 5: the use of sorbent material (III).
1) will fill the cylindrical container of absorbent particles as shown in Figure 1, be installed on the tap water inlet duct of resident family;
2) changed sorbent material every 20～40 days, to keep adsorption efficiency;
3) used sorbent material is reusable after two hours 550 ℃ of calcinings;
Embodiment 6: the use of sorbent material (IV).
1) will fill the cylindrical container of absorbent particles as shown in Figure 1, be installed on the inlet duct at the fluorine-containing water source of resident family;
2) changed sorbent material every 20～40 days, to keep adsorption efficiency;
3) used sorbent material is reusable after two hours 550 ℃ of calcinings;
Embodiment 7: the use of sorbent material (V).
1) will fill the cylindrical container of absorbent particles as shown in Figure 1, be installed on the inlet duct in resident family arsenic-containing water source;
2) changed sorbent material every 20～40 days, to keep adsorption efficiency;
3) used sorbent material is reusable after two hours 550 ℃ of calcinings.
Claims (10)
1. an energy is removed the sorbent material of disinfection byproduct (DBP) and parent material thereof from tap water, it is characterized in that it is that hydrotalcite derivant and binding agent were by 20: 1 to 3: 1 weight ratio blended mixtures.
2. a kind of sorbent material that can from tap water, remove disinfection byproduct (DBP) and parent material thereof according to claim 1, it is characterized in that said hydrotalcite derivant has another name called bimetallic oxide, for hydrotalcite at 450～800 ℃ of calcinates, its chemical structural formula is:
[M
x IIM
y IIIO
X+1.5y] M wherein
IIBe divalent metal; M
IIIBe trivalent metal cation.
3. a kind of sorbent material that can from tap water, remove disinfection byproduct (DBP) and parent material thereof according to claim 1, it is characterized in that said binding agent is a kind of in montmorillonite, kaolinite, illite, sepiolite, the polygorskite or several, they all are natural bed flaky aluminum silicate mineralss.
4. energy is removed disinfection byproduct (DBP) and parent material thereof from tap water preparation of adsorbent method is characterized in that its step is as follows:
1) hydrotalcite and binding agent dry respectively before use or are no more than under 80 ℃ of conditions in temperature and dry, and are milled to less than 200 orders;
2) hydrotalcite and the binding agent weight ratio by 20: 1 to 3: 1 is mixed, add 10～30% water, and stir kneading evenly;
3) said mixture being made diameter is 0.2～2 centimetre granular, dries or dries being lower than under 80 ℃ of temperature;
4) with above-mentioned particle 450～800 ℃ of temperature lower calcinations 1～4 hour, be cooled to preserve in the stopping property container of packing into after the room temperature stand-by.
5. a kind of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water according to claim 4 is characterized in that preparation method's step of said hydrotalcite is as follows:
1) is mixed with the solution that concentration is 0.1～0.4M with aluminium salt is soluble in water, in solution, adds 2～4 times of mole numbers, stir, make salts solution A until molten entirely to the magnesium salts of aluminium salt;
2) carbonate that mole number is equated with magnesium salts is soluble in water, is made into the solution that concentration is 0.6～0.9M, adds the alkali that mole number is three times in carbonate in solution, stirs until molten entirely, makes alkaline solution B;
3) adopt coprecipitation method that two kinds of solution of above-mentioned A, B are dropwise splashed in the water that violent stirring simultaneously; Perhaps with hydrothermal method with two solution short mix, obtain white suspension;
4) suspension is put into water-bath, under 70～95 ℃, stir crystallization; Perhaps suspension is placed pressure vessel, crystallization under 120～160 ℃ of conditions;
5) with step 4) products therefrom suction filtration, be washed to neutrality.Put into baking oven,, obtain hydrotalcite 60～80 ℃ of oven dry down;
6. a kind of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water according to claim 5 is characterized in that said aluminium salt is a kind of of aluminum chloride, aluminum nitrate, Tai-Ace S 150 and hydrate thereof or several.
7. a kind of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water according to claim 5 is characterized in that said magnesium salts is a kind of of magnesium chloride, magnesium nitrate, sal epsom and hydrate thereof or several.
8. a kind of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water according to claim 5 is characterized in that said alkali is a kind of of sodium hydroxide, potassium hydroxide, ammoniacal liquor.
9. a kind of preparation of adsorbent method that can remove disinfection byproduct (DBP) and parent material thereof from tap water according to claim 5 is characterized in that said carbonate is a kind of of yellow soda ash, salt of wormwood.
10. energy is removed the sorbent material of disinfection byproduct (DBP) and parent material thereof from tap water using method is characterized in that its step is as follows:
1) absorbent particles is filled in the cylindrical container, the diameter of cylindrical shell (3) is 2～8 times of running water pipe (1); The two ends of container are equipped with filter screen (2), and its mesh is less than the diameter of absorbent particles; Be provided with spirrillum baffle plate (4) in the container,, slow down its flow velocity to change the direction of a stream of water;
2) cylindrical container that fills sorbent material is installed in: the I) water-in of liquid chlorine, chlorinated lime sterilization process; II) liquid chlorine, chlorinated lime, ClO
2The water outlet of sterilization process; III) inlet at the tap water of resident family or other water source; When tap water flows I, sorbent material can remove the humic acid in anhydrating, and reduces the organic content of chlorination in the tap water; When tap water flows II and III, sorbent material can remove the disinfection byproduct (DBP) in anhydrating and be the unwanted component that anionic form exists;
3) the exhausted sorbent material is reusable after 2～4 hours through 450～600 ℃ of calcinings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506496A CN1493393A (en) | 2003-08-25 | 2003-08-25 | Adsorber for removing antiseptic byproduct in city water and its preparation and use method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506496A CN1493393A (en) | 2003-08-25 | 2003-08-25 | Adsorber for removing antiseptic byproduct in city water and its preparation and use method |
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| Publication Number | Publication Date |
|---|---|
| CN1493393A true CN1493393A (en) | 2004-05-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031506496A Pending CN1493393A (en) | 2003-08-25 | 2003-08-25 | Adsorber for removing antiseptic byproduct in city water and its preparation and use method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413591C (en) * | 2005-09-01 | 2008-08-27 | 北京化工大学 | Laminated structure treatment compound and treatment method of of fluorinated water |
| CN102872794A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing bromate from water and preparation method for adsorption material |
| CN105061748A (en) * | 2015-07-17 | 2015-11-18 | 江苏斯德瑞克化工有限公司 | Attapulgite loaded hydrotalcite-like compound catalyst for polyether polyol synthesis and preparation method of hydrotalcite-like catalyst |
| CN105923683A (en) * | 2016-04-27 | 2016-09-07 | 陈书仁 | Drinking water purifier |
| CN106076246A (en) * | 2016-06-20 | 2016-11-09 | 江苏大学 | A kind of have the compound except iodine material and preparation method of micro-nano hierarchy |
| CN106215846A (en) * | 2016-09-21 | 2016-12-14 | 山东建筑大学 | A kind of magnalium silicon composite adsorbing material and its preparation method and application |
| CN108144577A (en) * | 2017-12-06 | 2018-06-12 | 常州杰轩纺织科技有限公司 | A kind of preparation method of heavy metal ion adsorbing material |
| CN109212050A (en) * | 2018-07-07 | 2019-01-15 | 丁立平 | The gas chromatography of nine kinds of trace halogen acetic acids in a kind of measurement barreled drinking water |
| CN112062204A (en) * | 2020-09-19 | 2020-12-11 | 邵阳天堂助剂化工有限公司 | Method for removing humic acid in water by adsorption of calcined hydrocalumite |
| CN114984977A (en) * | 2022-06-20 | 2022-09-02 | 重庆师范大学 | Hydrotalcite-like compound loaded PtM catalyst, and preparation method and application thereof |
-
2003
- 2003-08-25 CN CNA031506496A patent/CN1493393A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413591C (en) * | 2005-09-01 | 2008-08-27 | 北京化工大学 | Laminated structure treatment compound and treatment method of of fluorinated water |
| CN102872794A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing bromate from water and preparation method for adsorption material |
| CN105061748B (en) * | 2015-07-17 | 2017-03-29 | 江苏斯德瑞克化工有限公司 | PPG synthesis attapulgite loaded houghite catalyst and preparation method thereof |
| CN105061748A (en) * | 2015-07-17 | 2015-11-18 | 江苏斯德瑞克化工有限公司 | Attapulgite loaded hydrotalcite-like compound catalyst for polyether polyol synthesis and preparation method of hydrotalcite-like catalyst |
| CN105923683A (en) * | 2016-04-27 | 2016-09-07 | 陈书仁 | Drinking water purifier |
| CN106076246A (en) * | 2016-06-20 | 2016-11-09 | 江苏大学 | A kind of have the compound except iodine material and preparation method of micro-nano hierarchy |
| CN106076246B (en) * | 2016-06-20 | 2018-06-26 | 江苏大学 | It is a kind of compound except iodine material and preparation method with micro-nano hierarchical structure |
| CN106215846A (en) * | 2016-09-21 | 2016-12-14 | 山东建筑大学 | A kind of magnalium silicon composite adsorbing material and its preparation method and application |
| CN108144577A (en) * | 2017-12-06 | 2018-06-12 | 常州杰轩纺织科技有限公司 | A kind of preparation method of heavy metal ion adsorbing material |
| CN109212050A (en) * | 2018-07-07 | 2019-01-15 | 丁立平 | The gas chromatography of nine kinds of trace halogen acetic acids in a kind of measurement barreled drinking water |
| CN109212050B (en) * | 2018-07-07 | 2021-05-14 | 丁立平 | Gas chromatography for determining nine trace haloacetic acids in barreled drinking water |
| CN112062204A (en) * | 2020-09-19 | 2020-12-11 | 邵阳天堂助剂化工有限公司 | Method for removing humic acid in water by adsorption of calcined hydrocalumite |
| CN114984977A (en) * | 2022-06-20 | 2022-09-02 | 重庆师范大学 | Hydrotalcite-like compound loaded PtM catalyst, and preparation method and application thereof |
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