CN102311190A - Method for removing thallium from drinking water by enhanced conventional water treatment process - Google Patents
Method for removing thallium from drinking water by enhanced conventional water treatment process Download PDFInfo
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- CN102311190A CN102311190A CN201110239202A CN201110239202A CN102311190A CN 102311190 A CN102311190 A CN 102311190A CN 201110239202 A CN201110239202 A CN 201110239202A CN 201110239202 A CN201110239202 A CN 201110239202A CN 102311190 A CN102311190 A CN 102311190A
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Abstract
The invention discloses a method for removing thallium from drinking water by an enhanced conventional water treatment process, comprising the following steps of: adjusting the pH value of the drinking water to be processed to alkaline, adding potassium permanganate to oxidize positive monovalent thallium ions into positive trivalent thallium ions so as to generate a thallium hydroxide precipitate; adding a compound which can generate chloride ions so as to make residual free trivalent thallium ions to form a thallium chloride ligand complex, simultaneously adding polyaluminium chloride for coagulation to form floc particles, transferring thallium hydroxide and the thallium chloride ligand complex into the floc particles; removing a floc particle precipitate by precipitation; and further purifying through sand filtration. By the application of the method provided by the invention, thallium in drinking water can be effectively removed, and the concentration of thallium in the processed water is reduced to less than 0.1microgram/L. The method provided by the invention can also be conveniently combined with present water treatment processes at low operation cost, and is of great practicality.
Description
Technical field
The present invention relates to remove in a kind of water technology the method for heavy metal, especially a kind of method of strengthening thallium in the conventional water treatment process removal tap water.
Background technology
Since the reform and opening-up; China's economy grows continuously and fast; Expanding economy has brought very big pressure to water surrounding, and legislations of environmental protection is violated for the economic interests of pursuing short-term by some enterprises, and violation or criminal manipulation have caused the frequent generation of the pollution incident of China's water surrounding burst in recent years.The frequent generation of the water pollution incident and the regions of the world attack of terrorism causes serious threat for the water quality safety of drinking water source.Statistics shows that China's water surrounding burst pollution incident occurrence frequency and hazard rating all have the trend of rising in recent years.Drinking-water quality safety is directly connected to the healthy of the public, the Sustainable development of restriction economic society, the stable and long-term stability of influence society.
Thallium (Tl) is a kind of rare and scatter element, is present in iron, the zinc sulfides ore deposit with trace.In the smeltery of thallium, fuel-burning power plant and various contains the manufacturing processed of thallium material, medicament, have thallic waste gas, waste water, waste residue and get into environment.In a single day thallium gets into drinking water source, very easily causes the region chronic poisoning.Thallium can get into human body through tap water and food chain, and wherein thallium can be replaced potassium in the enzyme reaction process of human body, and produces very strong avidity with enzyme, thereby brings out the toxic effect of Tl.Therefore, effectively prevent and control the pollution of thallium to water surrounding, especially the thallium of tap water pollutes, and has important and positive meaning.
Thallium and compound thereof have been put into the monitoring index system of water body priority pollutants Black List and China's water environment quality standard (GB 3838-2002).About the removal of thallium, research and water treatment practice data are less both at home and abroad, comprise and utilize the active aluminum method of purification, ion exchange method and NaCl solution to remove the Tl in the tap water; Reduce the reactivity of Tl with sorbent materials such as sponge adsorbent, oxygenant and alkaline matter (like lime etc.), handle the water body that has been polluted by Tl.And to drinking water plant how to low thallium content for example the water of 0.1～0.5 μ g/L handle so that thallium content is reduced to the safer scope that meets GB 5749-2006 " the hygienic standard of living " regulation, still have no reported in literature or the disclosed feasible method of other modes.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the present invention provides a kind of method that conventional water treatment process is removed thallium in the tap water of strengthening, and using this method can be reduced to thallium content in the water below the 0.1 μ g/L.
The technical scheme that the present invention adopts is: a kind of method of strengthening thallium in the conventional water treatment process removal tap water comprises the following steps of carrying out successively:
B1, the pH value of pending tap water is adjusted to alkalescence, and adds potassium permanganate;
B2, adding can produce the compound of cl ions, add Poly aluminum Chloride (PAC) (PAC) coagulation simultaneously and form floc particle;
B3, remove after making the floc particle sedimentation through deposition;
B4, further purify through sand filtration.
Wherein can be earlier among the step B1 pH value of pending tap water be adjusted to alkalescence and adds potassium permanganate again, also can carry out simultaneously, promptly the one side pH value of regulating water simultaneously adds potassium permanganate oxidation monovalence thallium ion.
Preferably, among the said step B1, regulate the pH value of pending tap water and select sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), yellow soda ash (Na for use
2CO
3), calcium hydroxide (Ca (OH)
2) in one or more; Among the said step B2, the compound that can produce cl ions is selected from sodium-chlor (NaCl), Repone K (KCl), calcium chloride (CaCl
2), magnesium chloride (MgCl
2), bariumchloride (BaCl
2), aluminum chloride (AlCl
3), zinc chloride (ZnCl
2) in one or more.
Preferably, among the said step B1, regulate pH value to 8.5～10 of pending tap water.
Preferably, the add-on of potassium permanganate is every premium on currency 0.2～1mg among the said step B1.
Preferably, among the said step B2, the add-on that can produce the compound of cl ions is counted every premium on currency 2～10mg with cl ions.
Preferably, among the said step B2, the add-on of Poly aluminum Chloride (PAC) is every premium on currency 1～10mg.
Preferably, thallium content is 0.1～0.5 μ g/L in the said pending tap water.
Preferably, stir 1～3min among the said step B1 behind the adding potassium permanganate fast, the preferred stirring velocity of said quick stirring is 260～350rpm.
Preferably, add among the said step B2 to stir fast earlier behind the compound can produce cl ions, the Poly aluminum Chloride (PAC) again and stir at a slow speed, preferred churning time fast is 0.5～2min, stirs 10 ~ 20min at a slow speed.The preferred stirring velocity of said quick stirring is 260～350rpm, and said to stir preferred stirring velocity at a slow speed be 50～90rpm.
Preferably, the ST is 15～60min among the said step B3.
Beneficial technical effects of the present invention: use the inventive method and can remove the thallium in the tap water effectively, and the concentration of handling thallium in the water of back is reduced to below the 0.1 μ g/L; The inventive method can also combine with existing water technology easily, and working cost is low, has very high practicality.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Elaborate below in conjunction with accompanying drawing.
Referring to Fig. 1, the present invention strengthens the method for thallium in the conventional water treatment process removal tap water and removes the thallium in the water for the method for strengthening the PAC coagulation through pH regulator, potassium permanganate oxidation, cl ions co-ordination complex, specifically comprises several steps:
The first step adds alkaline matter pH value is adjusted to alkalescence in pending water, preferred pH value is 8～10, and alkaline matter is preferentially from sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), yellow soda ash (Na
2CO
3), calcium hydroxide (Ca (OH)
2) in select for use, more preferably sodium hydroxide, yellow soda ash, calcium hydroxide, can use separately or several kinds mix and use.Add potassium permanganate (KMnO then
4), fast (260～350 rev/mins) stir 1～3min, and the oxygenizement through potassium permanganate is with the positive monovalence thallium ion (Tl in the water
+) be oxidized to positive trivalent thallium ion (Tl
3+), potassium permanganate is reduced to mangaic acid radical ion (MnO
4 2-), mangaic acid radical ion hydrolysis reaction generates alkali formula manganese oxide (MnO (OH)
2), or be called hydrated manganese dioxide, be a kind of chocolate deposition.The positive trivalent thallium ion (Tl that generates
3+) and then with water in hydroxide ion (OH
-) reaction generation Tl (OH)
3Deposition.
Reactional equation is:
(1)
Also can in the pH value that adds alkaline matter adjusting water, add potassium permanganate.The dosage of potassium permanganate is good with the volumeter of pending water more than or equal to 0.2mg/L, and in order not influence the colourity of tap water, the upper limit is controlled in the 1mg/L, and preferred dosage is smaller or equal to 0.8mg/L more than or equal to 0.3mg/L.
In second step, Xiang Shuizhong adds the compound that can produce cl ions, adds Poly aluminum Chloride (PAC) (PAC) simultaneously, adds back earlier quick (260～350 rev/mins) and mixes 0.5～2min, and (50～90 rev/mins) stir 10 ~ 20min more at a slow speed.Cl ions (Cl
-) with the positive trivalent thallium ion (Tl of residual ionization
3+) form the thallium chloride co-ordination complex, for example: TlCl
2+, TlCl
2 +, TlCl
4 -, TlCl
6 3-Deng.Tl
3+The complex compound that forms with the cl ions ligand compares Tl
+Formed complex compound is more stable, and the formation of these stable co-ordination complexs makes Tl
+With Tl
3+Between redox potential significantly reduce Tl
+Be oxidized to Tl more easily
3+Thereby, make that above-mentioned chemical reaction (1) more is prone to carry out, positive monovalence thallium ion (Tl
+) oxidizing reaction more thorough.The Poly aluminum Chloride (PAC) that adds (PAC) coagulation forms floc particle, and thallic hydroxide and thallium chloride co-ordination complex are all transferred in the floc particle.The compound that can produce cl ions is selected from sodium-chlor (NaCl), Repone K (KCl), calcium chloride (CaCl
2), magnesium chloride (MgCl
2), bariumchloride (BaCl
2), aluminum chloride (AlCl
3), zinc chloride (ZnCl
2), preferred sodium-chlor, calcium chloride can use separately or several kinds of mixing are used; Its add-on is counted every premium on currency 2～10mg with cl ions.The add-on of Poly aluminum Chloride (PAC) (PAC) is every premium on currency 1～10mg.
The 3rd step, realize the sedimentation of floc particle forming the larger particles that is combined with thallic hydroxide and thallium chloride co-ordination complex after the flocculation reaction through deposition, in the flocculation sediment process, by the hydrated manganese dioxide of the first step reaction generation to Tl (OH)
3Stronger adsorption is arranged, can play the effect that thallium is removed in co-precipitation with the floc particle that PAC forms.Precipitate spoil disposal at settling tank, remove most floc particle.According to water factory's institute's adopting process and practical operation situation selective precipitation time, the ST is good with 15～60min, and the time, too short deposition was incomplete; Time is oversize; The thallium chloride co-ordination complex can produce desorb again, discharges from floc particle and returns water, is unfavorable for the removal of thallium.
The 4th step further purified through sand filtration, and unprecipitated small-particle is removed; Strengthen solid-liquid separation effect; Ensure in the water outlet total thallium content below GB, the hydrated state Manganse Dioxide that generates in the first step reaction in addition can be attached to the sand filtration filter material surface, and then forms manganese sand; It can ensure the removal of thallium to the still old certain adsorption of solvability thallium in the water.
Embodiment 1
Water factory strengthens conventional water treatment process, removes thallium in the tap water, implements following steps successively:
The pH value of a, adjusting water is to alkalescence and be oxidized to trivalent thallium to the monovalence thallium in the water: in former water distributing well or former water distributing pipe line, add sodium hydroxide and regulate former water pH value to 9.0; Amount by every premium on currency 0.8mg adds potassium permanganate simultaneously; Utilize the mixing effect that helps of mechanical stirring or pump and pipe network to make potassium permanganate and former water thorough mixing, the reaction mixing time is 1min.
B, the amount that in machinery or waterpower coagulation basin, adds sodium-chlor, every premium on currency 2mg by the amount of every premium on currency 3mg cl ions add PAC, and (300 rev/mins) stir 1min fast, and (70 rev/mins) stir 15min more at a slow speed.
C, get into settling tank, deposition 30min, sludge discharging period is by shortening to every day 2～3 times original every day for 1 time.In the sand filtration stage, the sand filter backwashing period is 24h, and the gas of combined water and air backwash is 54m towards intensity
3/ h/m
2, water is 10.2m towards intensity
3/ h/m
2, the combined water and air backwash time is 2-4min.
The check of thallium removal effect: the thallium content of former water is 0.43 μ g/L, and after the present embodiment method was handled, thallium content was reduced to below the 0.1 μ g/L.
Embodiment 2
Water factory strengthens conventional water treatment process, removes thallium in the tap water, implements following steps successively:
A, regulate water pH value to alkalescence and is oxidized to trivalent thallium to the monovalence thallium in the water: in former water distributing well or former water distributing pipe line, add after sodium hydroxide regulates former water pH value to 10.0; Amount by every premium on currency 0.9mg adds potassium permanganate again; Utilize mechanical stirring (300 rev/mins) to make potassium permanganate and former water thorough mixing, the reaction mixing time is 3min.
B, the amount that in machinery or waterpower coagulation basin, adds sodium-chlor, every premium on currency 10mg by the amount of every premium on currency 9mg cl ions add PAC, and (300 rev/mins) stir 1.5min fast, and (70 rev/mins) stir 20min more at a slow speed.
C, get into settling tank, deposition 50min, sludge discharging period is by shortening to every day 2～3 times original every day for 1 time.In the sand filtration stage, the sand filter backwashing period is 24h, and the gas of combined water and air backwash is 54m towards intensity
3/ h/m
2, water is 10.2m towards intensity
3/ h/m
2, the combined water and air backwash time is 2-4min.
The check of thallium removal effect: the thallium content of former water is 0.5 μ g/L, and after the present embodiment method was handled, thallium content was reduced to below the 0.1 μ g/L.
Embodiment 3
Water factory strengthens conventional water treatment process, removes thallium in the tap water, implements following steps successively:
The pH value of a, adjusting water is to alkalescence and be oxidized to trivalent thallium to the monovalence thallium in the water: in former water distributing well or former water distributing pipe line, add sodium hydroxide and regulate former water pH value to 8.5; Amount by every premium on currency 0.2mg adds potassium permanganate then; Utilize the mixing effect that helps of mechanical stirring or pump and pipe network to make potassium permanganate and former water thorough mixing, the reaction mixing time is 1min.
B, the amount that in machinery or waterpower coagulation basin, adds sodium-chlor, every premium on currency 1.5mg by the amount of every premium on currency 2.6mg cl ions add PAC, and (300 rev/mins) stir 1min fast, and (70 rev/mins) stir 10min more at a slow speed.
C, get into settling tank, deposition 20min, sludge discharging period is by shortening to every day 2～3 times original every day for 1 time.In the sand filtration stage, the sand filter backwashing period is 24h, and the gas of combined water and air backwash is 54m towards intensity
3/ h/m
2, water is 10.2m towards intensity
3/ h/m
2, the combined water and air backwash time is 2～4min.
The check of thallium removal effect: the thallium content of former water is 0.31 μ g/L, and after the present embodiment method was handled, thallium content was reduced to below the 0.1 μ g/L.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (10)
1. strengthen the method that conventional water treatment process is removed thallium in the tap water for one kind, comprise the following steps of carrying out successively:
B1, the pH value of pending tap water is adjusted to alkalescence, and adds potassium permanganate;
B2, adding can produce the compound of cl ions, add the Poly aluminum Chloride (PAC) coagulation simultaneously and form floc particle;
B3, remove after making the floc particle sedimentation through deposition;
B4, further purify through sand filtration.
2. reinforcement conventional water treatment process according to claim 1 is removed the method for thallium in the tap water; It is characterized in that: among the said step B1, the pH value of regulating pending tap water is selected one or more in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, the calcium hydroxide for use; The compound that can produce cl ions among the said step B2 is selected from one or more in sodium-chlor, Repone K, calcium chloride, magnesium chloride, bariumchloride, aluminum chloride, the zinc chloride.
3. reinforcement conventional water treatment process according to claim 2 is removed the method for thallium in the tap water, it is characterized in that: among the said step B1, regulate pH value to 8.5～10 of pending tap water.
4. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: the add-on of potassium permanganate is every premium on currency 0.2～1mg among the said step B1.
5. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: among the said step B2, the add-on that can produce the compound of cl ions is counted every premium on currency 2～10mg with cl ions.
6. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: among the said step B2, the add-on of Poly aluminum Chloride (PAC) is every premium on currency 1～10mg.
7. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: thallium content is 0.1～0.5 μ g/L in the said pending tap water.
8. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: add among the said step B1 that the speed with 260～350rpm stirs 1～3min fast behind the potassium permanganate.
9. remove the method for thallium in the tap water according to claim 1,2,3 or 8 described reinforcement conventional water treatment processes; It is characterized in that: the speed that adds among the said step B2 behind the compound can produce cl ions, the Poly aluminum Chloride (PAC) earlier with 260～350rpm stirs 0.5～2min fast, and the speed with 50～90rpm stirs 10 ~ 20min at a slow speed again.
10. remove the method for thallium in the tap water according to claim 1,2 or 3 described reinforcement conventional water treatment processes, it is characterized in that: the ST is 15～60min among the said step B3.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102768191A (en) * | 2012-07-31 | 2012-11-07 | 浙江中一检测研究院股份有限公司 | Method for easily detecting trace thallium in water |
| CN103693774A (en) * | 2013-11-27 | 2014-04-02 | 深圳市水务(集团)有限公司 | Method for simultaneous removal of cadmium and thallium in raw water |
| CN103991986A (en) * | 2014-05-30 | 2014-08-20 | 紫金矿业集团股份有限公司 | Method for removing thallium in copper effluent |
| CN105565451A (en) * | 2015-10-21 | 2016-05-11 | 刘锡峰 | Water treatment agent |
| CN108328800A (en) * | 2018-03-02 | 2018-07-27 | 中国大唐集团科学技术研究院有限公司西北分公司 | A kind of removal waste water of heat-engine plant heavy metal ion method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102768191A (en) * | 2012-07-31 | 2012-11-07 | 浙江中一检测研究院股份有限公司 | Method for easily detecting trace thallium in water |
| CN102768191B (en) * | 2012-07-31 | 2014-06-18 | 浙江中一检测研究院股份有限公司 | Method for easily detecting trace thallium in water |
| CN103693774A (en) * | 2013-11-27 | 2014-04-02 | 深圳市水务(集团)有限公司 | Method for simultaneous removal of cadmium and thallium in raw water |
| CN103693774B (en) * | 2013-11-27 | 2015-10-28 | 深圳市水务(集团)有限公司 | A kind of method simultaneously removing cadmium and thallium in former water |
| CN103991986A (en) * | 2014-05-30 | 2014-08-20 | 紫金矿业集团股份有限公司 | Method for removing thallium in copper effluent |
| CN105565451A (en) * | 2015-10-21 | 2016-05-11 | 刘锡峰 | Water treatment agent |
| CN108328800A (en) * | 2018-03-02 | 2018-07-27 | 中国大唐集团科学技术研究院有限公司西北分公司 | A kind of removal waste water of heat-engine plant heavy metal ion method |
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Application publication date: 20120111 |