CN103693774B - A kind of method simultaneously removing cadmium and thallium in former water - Google Patents
A kind of method simultaneously removing cadmium and thallium in former water Download PDFInfo
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Abstract
The invention provides a kind of method simultaneously removing cadmium and thallium in former water, comprise following step: steps A: add sodium hydroxide at Yuan Shui, adjust ph, to weakly alkaline, then adds potassium permanganate 0.3 ~ 0.8mg/L; Step B: add clorox or liquid chlorine, adds concentration and counts 0.5 ~ 2.5mg/L with available chlorine, step C: add liming, adjust ph to 8.5 ~ 9.0 in the former water after oxidizing reaction is abundant; Step D: add flocculation agent, flocculation reaction, after 10 ~ 20 minutes, precipitates at least 0.5 hour, and the cadmium in former water, thallium and manganous hydroxide and ferric hydroxide colloid co-precipitation are removed, and after precipitation, the pH value of water is reduced within 7.0 ~ 8.5; Step e: the former water after precipitation is through quartz sand filtration.The invention has the beneficial effects as follows: the cadmium concentration after process in water can be low to moderate method detectability 0.02 μ g/L and following, the concentration of thallium can be low to moderate the detection limit 0.01 μ g/L or following of detection method, and the pH value of the rear water of process, mn ion, iron ion all can reach the requirement of water quality standard for drinking water.
Description
Technical field
The present invention relates to the emergency processing method of water factory when a kind of city water source is subject to polluting, particularly relate to a kind of method simultaneously removing cadmium and thallium when water source is subject to heavy metal cadmium and thallium pollution simultaneously.
Background technology
In recent years, frequently there is heavy metal contamination event in Drinking Water in China source, especially occurs the most frequent with cadmium pollution.Owing to there is the phenomenon of cadmium and thallium symbiosis at occurring in nature, while water source generation cadmium pollution, often with the appearance of thallium pollution.Very harmful to HUMAN HEALTH of cadmium, can produce irreversible damage to kidney after Excess free enthalpy and even cause renal tubular cell downright bad; Cadmium can affect the calcium metabolism of bone thus cause osteoporosis and richets, i.e. Japanese famous " itai-itai " once occurred; Meanwhile, cadmium also can produce infringement to reproductive system, affects the intelligent growth of children; The carcinogenic substance that cadmium or international cancer center (IARC) confirm.In Drinking Water in China standard, the limit value of cadmium is 5 μ g/L, and in contaminated source water, times of ultra standard may reach more than 10 times.Thallium is that occurring in nature disperses rare metal, due in Metal smelting process by enrichment and discharge contaminate environment, the toxicity of thallium is high, once sterilant and raticide was widely used as, all have infringement to neural system and Digestive tract, therefore, in Drinking Water in China standard, thallium is restricted to 0.1 μ g/L.Because this two heavy metal species pollution toxicity is high, occur frequent, it is extremely urgent that easy, efficient water factory emergency processing method is set up in research.
At present report is had no for the thallium removed in former water and cadmium pollution simultaneously, have some research reports about the technology removing cadmium and thallium respectively.In document, the removal of cadmium mainly adopts hydroxide precipitation method and sulphide precipitation.The report that thallium is removed is many, comprises potassium permanganate oxidation alkaline sedimentation method; Potassium permanganate+clorox+Ozonation; Iron trichloride is oxidized, polymerize aluminum chloride coagulating sedimentation, and about the investigation of materials etc. of Adsorption thallium.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that technique removes cadmium and thallium in former water simply simultaneously, comprises following step:
Steps A: add sodium hydroxide at Yuan Shui, adjust ph, to weakly alkaline, then adds potassium permanganate 0.3 ~ 0.8mg/L;
Step B: add clorox or liquid chlorine, adds concentration and counts 0.5 ~ 2.5mg/L with available chlorine,
Step C: add liming, adjust ph to 8.5 ~ 9.0 in the former water after oxidizing reaction is abundant;
Step D: add flocculation agent, flocculation reaction, after 10 ~ 20 minutes, precipitates at least 0.5 hour, and the cadmium in former water, thallium and manganous hydroxide and ferric hydroxide colloid co-precipitation are removed, and after precipitation, the pH value of water is reduced within 7.0 ~ 8.5;
Step e: the former water after precipitation is through quartz sand filtration.
The present invention adopts above technical characteristic, and its advantage is, the effect of steps A makes most of cadmium ion be converted into cadmium hydroxide, and most of divalence thallium ion initial oxidation is after trivalent thallium ion, under weak basic condition, be precipitated as thallic hydroxide; Step B makes divalence thallium be oxidized into trivalent thallium further, and is precipitated as thallic hydroxide; Step C and step D, makes the cadmium in former water, thallium and manganous hydroxide and ferric hydroxide colloid co-precipitation remove, and after precipitation, the pH value of water is reduced within 7.0 ~ 8.5; Step e: the former water after precipitation, through quartz sand filtration, removes the oxyhydroxide of cadmium and thallium further.
Preferably, in described steps A, the reaction times is at least 5 minutes, and pH value is 8.0 to 8.5.
Preferably, in described step B, the reaction times is at least 3 minutes.
Preferably, in described step C, the add-on of liming is that be 10 ~ 30mg/L, pH controls between 8.5-9.0 in calcium oxide.
Preferably, step D, described flocculation agent adopts bodied ferric sulfate, and add-on, in ferro element, is 3 ~ 10mg/L.
Present invention also offers a kind of processing method simultaneously removing cadmium and thallium in former water, adopt the device of the method to comprise the former water intake, mixing pit, flocculation basin, settling tank, sand filter and the clean water basin that set gradually, described method comprises following step:
Steps A ': add sodium hydroxide at the raw water pipeline of described former water intake, regulate pH between 8.0 ~ 8.5;
Step B ': add potassium permanganate in sodium hydroxide toss area raw water pipeline after a while, dosage controls at 0.4 ~ 0.8mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
Step C ': add clorox in described mixing pit, dosage controls at 1.5 ~ 2.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
Step D ': feeding lime water in described flocculation basin, in calcium oxide, dosage is 25 ~ 30mg/L;
Step e ': in described flocculation basin, add bodied ferric sulfate, in ferro element, dosage is 3.0-10.0 mg/L, and control ph is between 7.5 ~ 8.5;
Step F ': precipitate in settling tank;
Step G ': filter in sand filter.
Present invention also offers the processing method that another removes cadmium and thallium in former water simultaneously, be applicable to the simple and easy water factory that mixing pit is not set.Adopt the device of the method to comprise the former water intake, flocculation basin, settling tank, sand filter and the clean water basin that set gradually, method comprises following step:
1) add sodium hydroxide at the raw water pipeline of intake, dosage controls entering the former water pH of factory between 8.0 ~ 8.5;
2) add potassium permanganate in flocculation basin ingress of water factory, dosage controls at 0.4mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
3) add clorox at flocculation basin leading portion, dosage controls at 1.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
4) at flocculation basin leading portion feeding lime water, dosage is 25mg/L;
5) add bodied ferric sulfate at flocculation basin leading portion, dosage is 3.0 mg/L, and reacted pH value is between 7.5 ~ 8.5;
6) precipitate in settling tank;
7) filter in sand filter.
Wherein, the design of flocculation basin is generally fixed, and is divided into leading portion, stage casing and back segment.
Preferably, described step F ' and step 6) in sedimentation time be 1 to 3 hour.
Preferably, described step G ' is with in step 7), and the thickness filtering the quartz sand filtering layer adopted is at least 1.0m, and the particle diameter of quartz is between 0.6-1.0mm, and filtration velocity is not higher than 8m/ hour.
When adopting hydroxide precipitation method of the prior art to remove cadmium, pH value will reach more than 10 just can make cadmium concentration reach water quality standard requirement, flocculation agent is made with iron trichloride or poly-aluminium, flocculant dosage iron trichloride wants 10mg/L (in Fe) or poly-aluminium 10mg/L(in aluminium sesquioxide), after this method process, not only pH value exceedes water quality standard 8.5, need acid adding to regulate, and metallic iron or aluminium can be caused to exceed standard; When adopting sulphide precipitation to remove cadmium, sulfide and turbidity can be caused to exceed standard on the one hand, the more important thing is the peculiar smell that can make to have sulfide in water, be not suitable for adopting in drinking water treatment.When adopting basic potassium permanganate method of the prior art to remove thallium, if make thallium reach water quality standard for drinking water 0.1 μ g/L, the concentration of potassium permanganate must reach more than 1.5mg/L, and for general surface water, when potassium permanganate concentration is more than 0.8mg/L, namely can cause there is obvious redness in water, and under pH value reaches the condition of more than 9 in the literature, adopt poly-aluminium aluminium can be caused to exceed standard as flocculation agent.
And, when adopting potassium permanganate+clorox of the prior art+ozonization method to remove thallium, what do not possess ozone due to general common process water factory adds facility and condition, is difficult to realize in actually operating, and after adding potassium permanganate, need reaction more than 4 hours, be difficult to realize in general water factory.The method of iron(ic) chloride adsorption-flocculation is very low to the clearance of thallium in actual applications, and the thallium of water factory's water outlet is difficult to reach existing drinking water sanitary standard.
And the invention has the beneficial effects as follows: after above-mentioned steps process, cadmium concentration after process in water can be low to moderate method detectability 0.02 μ g/L and following, the concentration of thallium can be low to moderate the detection limit 0.01 μ g/L or following of detection method, the pH value of the rear water of process, mn ion, iron ion all can reach the requirement of water quality standard for drinking water, technique is simple, convenient enforcement.
Accompanying drawing explanation
Fig. 1 is the schema of an embodiment of the present invention.
Fig. 2 is the schema of an embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
Case study on implementation 1:
1) get the former water of 1L, adding sodium hydroxide adjust ph is 8.5;
2) add potassium permanganate 0.6mg/L, react 5 minutes;
3) add chlorine bleach liquor, adding effective chlorine density is 2.0mg/L, reacts 3 minutes:
4) add liming 25mg/L, react 1 minute;
5) add bodied ferric sulfate 5.0mg/L, react 20 minutes, precipitate 20 minutes, filter.
When the cadmium content in former water before process is 25 μ g/L, thallium content is 0.25 μ g/L, and after precipitation, in water, cadmium content is 2.7 μ g/L, and thallium content is 0.05 μ g/L, and the clearance in precipitation process is respectively cadmium 89.2%, 80%; After filter, in water, cadmium content is 0.08 μ g/L, and thallium content is 0.02 μ g/L, and total removal rate is respectively 99.7% and 92%.
Case study on implementation 2
1) get the former water of 1L, add sodium hydroxide and regulate pH to be 8.0;
2) add potassium permanganate 0.8mg/L, react 5 minutes;
3) add chlorine bleach liquor, the effective chlorine density added is 1.5mg/L, reacts 3 minutes;
4) add liming 30mg/L, react 1 minute;
5) add bodied ferric sulfate 5.0mg/L, react 20 minutes, precipitate 20 minutes, filter.
When in former water before process, cadmium content is 20 μ g/L, when thallium content is 0.18 μ g/L, after precipitation, in water, cadmium content is 1.8 μ g/L, and thallium content is 0.04 μ g/L, and clearance is respectively 91% and 77.8%; After filter, in water, cadmium content is 0.05 μ g/L, and thallium content is 0.02 μ g/L, and total removal rate is respectively 99.8% and 88.9%.
Embodiment 3
As Fig. 1 shows:
with
be respectively the toss area of sodium hydroxide and potassium permanganate, be generally located at intake or water intake pumping station, the two does not all possess the condition of adding, and can be located at mixing pit or the flocculation basin of water factory;
for clorox toss area, be located in mixing pit; If mixing pit needs to add other medicaments, flocculation basin leading portion can will be moved to after toss area;
liming toss area, is located at flocculation basin leading portion;
bodied ferric sulfate iron toss area, is located at flocculation basin leading portion, after liming toss area.
the horizontal sedimentation tank residence time should be not less than 1h, and the tube settler residence time should be not less than 0.5h.
sand filter adopts quartz sand filtering layer, and thickness is not less than 1.0m.
As shown in Figure 1, this assembling device comprises the former water intake, mixing pit, flocculation basin, settling tank, sand filter and the clean water basin that distribute successively
Method comprises following several step:
Steps A ': add sodium hydroxide at the raw water pipeline of described former water intake, regulate pH between 8.0 ~ 8.5;
Step B ': add potassium permanganate in sodium hydroxide toss area raw water pipeline after a while, dosage controls at 0.4 ~ 0.8mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
Step C ': add clorox in described mixing pit, dosage controls at 1.5 ~ 2.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
Step D ': feeding lime water in described flocculation basin, in calcium oxide, dosage is 25 ~ 30mg/L;
Step e ': in described flocculation basin, add bodied ferric sulfate, in ferro element, dosage is 3.0-10.0 mg/L, and control ph is between 7.5 ~ 8.5;
Step F ': in settling tank, carry out precipitation 3 hours after reaction.
Step G ': filter in sand filter.
In the former water of emergent period water factory, cadmium content is 6.5 μ g/L, and thallium content is 0.25 μ g/L, and after treatment, in output water, cadmium content is stabilized in≤0.02 μ g/L, and thallium stable content is at≤0.01 μ g/L.
Embodiment 4
As shown in Figure 2,
with
be respectively the toss area of sodium hydroxide and potassium permanganate, be generally located at intake or water intake pumping station, the two does not all possess the condition of adding, and can be located at mixing pit or the flocculation basin of water factory;
for clorox toss area, be located at flocculation basin leading portion;
liming toss area, is located at flocculation basin leading portion;
bodied ferric sulfate iron toss area, is located at flocculation basin leading portion, after liming toss area.
the horizontal sedimentation tank residence time should be not less than 1h, and the tube settler residence time should be not less than 0.5h.
sand filter adopts quartz sand filtering layer, and thickness is not less than 1.0m.
Implement the treatment scale 3.5 ten thousand tons/day of water factory.Adopt the device of the method to comprise the former water intake, flocculation basin, settling tank, sand filter and the clean water basin that set gradually, method comprises following step:
1) add sodium hydroxide at the raw water pipeline of intake, dosage controls entering the former water pH of factory between 8.0 ~ 8.5;
2) add potassium permanganate (this water factory is without mixing pit) in flocculation basin ingress of water factory, dosage controls at 0.4mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
3) add clorox at flocculation basin leading portion, dosage controls at 1.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
4) at flocculation basin leading portion feeding lime water, dosage is 25mg/L;
5) add bodied ferric sulfate at flocculation basin leading portion, dosage is 3.0 mg/L, and because bodied ferric sulfate is acid, reacted pH value is between 7.5 ~ 8.5;
6) the 20 minutes reaction times of water factory's flocculation basin
7) residence time of water factory's settling tank is 1 hour.
8) filter in sand filter.
In the former water of emergent period water factory, cadmium content is 6.5 μ g/L, and thallium content is 0.25 μ g/L, and after treatment, in output water, cadmium content is stabilized in≤0.02 μ g/L, and thallium stable content is at≤0.01 μ g/L.
The beneficial effect of embodiment 1 to 4 is:
(1) in embodiment, add alkali twice, be conducive to the cadmium hydroxide that promotes to be formed and the formation of thallic hydroxide, after add liming not only adjust ph, and have Coagulation aiding;
(2) owing to have employed potassium permanganate and clorox synergistic oxidation divalence thallium, the potassium permanganate concentration of employing is lower, and potassium permanganate is inexcessive, can not have an impact to the colourity of water quality; Adopt clorox supplemental, both served the effect of oxidation divalence thallium further, and also reduced the dosage of subsequent technique sterilizing agent;
(3) adopt polymeric ferric salt as flocculation agent, overcome due to the aluminium excessive problem that pH higher band is come when adopting polymerize aluminum chloride to make flocculation agent, simultaneously, because the acidity of bodied ferric sulfate is very strong, to high ph-values, there is very strong neutralizing effect, after not needing, add acid for adjusting pH value, simplify technique.
(4) calculate according to solubility product, make cadmium ion required pH value up to standard should more than 10, because the throwing out of bodied ferric sulfate to oxyhydroxide is better than the Manganse Dioxide of polymerize aluminum chloride and lime and formation and the co-precipitation of cadmium hydroxide, the pH value of precipitation is reduced greatly.
Practical application effect shows, when after this technique of employing, water outlet cadmium≤0.2 μ g/L after water factory's process, thallium≤≤ 0.01 μ g/L, far below the limit value of drinking water sanitary standard (GB5749-2006), significantly improve the security of tap water, and this technique is simple, application is convenient, does not need to increase new structures, greatly reduce processing cost, save the emergency response time.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (3)
1. remove a method for cadmium and thallium in former water simultaneously, it is characterized in that, comprise following step:
Steps A: add sodium hydroxide at Yuan Shui, adjust ph, to weakly alkaline, then adds potassium permanganate 0.3 ~ 0.8mg/L;
Step B: add clorox or liquid chlorine, adds concentration and counts 0.5 ~ 2.5mg/L with available chlorine;
Step C: add liming in the former water after oxidizing reaction is abundant, and adjust ph to 8.5 ~ 9.0;
Step D: add flocculation agent, flocculation reaction, after 10 ~ 20 minutes, precipitates at least 0.5 hour, and the cadmium in former water, thallium and manganous hydroxide and ferric hydroxide colloid co-precipitation are removed, and after precipitation, the pH value of water is reduced to 7.0 ~ 8.5;
Step e: the former water after precipitation removes residual cadmium and thallium further through quartz sand filtration;
In described steps A, the reaction times is at least 5 minutes, and pH value is 8.0 to 8.5;
In described step B, the reaction times is at least 3 minutes;
In described step C, the add-on of liming is in calcium oxide, is 10 ~ 30mg/L;
Described flocculation agent adopts bodied ferric sulfate, and add-on, in ferro element, is 3 ~ 10mg/L.
2. remove a processing method for cadmium and thallium in former water simultaneously, it is characterized in that, adopt the device of the method to comprise the former water intake, mixing pit, flocculation basin, settling tank, sand filter and the clean water basin that set gradually, described method comprises following step:
Steps A ': add sodium hydroxide at the raw water pipeline of described former water intake, regulate pH in 8.0 ~ 8.5;
Step B ': add potassium permanganate in sodium hydroxide toss area raw water pipeline after a while, dosage controls at 0.4 ~ 0.8mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
Step C ': add clorox in described mixing pit, dosage controls at 1.5 ~ 2.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
Step D ': feeding lime water in described flocculation basin, in calcium oxide, dosage is 25 ~ 30mg/L;
Step e ': in described flocculation basin, add bodied ferric sulfate, in ferro element, dosage is 3.0-10.0 mg/L, and control ph is 7.5 ~ 8.5;
Step F ': precipitate in settling tank;
Step G ': filter in sand filter;
Described step F ' in sedimentation time be 1 to 3 hour;
In described step G ', the thickness filtering the quartz sand filtering layer adopted is at least 1.0m, and the particle diameter of quartz is 0.6-1.0mm, and filtration velocity is not higher than 8m/ hour.
3. remove a processing method for cadmium and thallium in former water simultaneously, it is characterized in that, adopt the device of the method to comprise the former water intake, flocculation basin, settling tank, sand filter and the clean water basin that set gradually, method comprises following step:
1) add sodium hydroxide at the raw water pipeline of intake, dosage controls entering the former water pH of factory 8.0 ~ 8.5;
2) add potassium permanganate in flocculation basin ingress of water factory, dosage controls at 0.4mg/L, and by the potassium permanganate concentration of Monitoring and Controlling settling tank water outlet at below 0.2mg/L;
3) add clorox at flocculation basin, dosage controls at 1.5mg/L, and by Monitoring and Controlling settling tank water outlet chlorine residue at below 1.0mg/L;
4) at flocculation basin feeding lime water, dosage is 25mg/L;
5) add bodied ferric sulfate at flocculation basin, dosage is 3.0 mg/L, and reacted pH value is 7.5 ~ 8.5;
6) precipitate in settling tank;
7) filter in sand filter;
Sedimentation time in described step 6) is 1 to 3 hour;
In described step 7), the thickness filtering the quartz sand filtering layer adopted is at least 1.0m, and the particle diameter of quartz is 0.6-1.0mm, and filtration velocity is not higher than 8m/ hour.
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| CN103102026A (en) * | 2013-02-04 | 2013-05-15 | 华南理工大学 | Sudden raw water thallium pollution emergency treatment system and method |
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