CN110818128A - Method for deeply removing thallium from high-ammonia-nitrogen and high-COD wastewater - Google Patents
Method for deeply removing thallium from high-ammonia-nitrogen and high-COD wastewater Download PDFInfo
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- CN110818128A CN110818128A CN201911060723.XA CN201911060723A CN110818128A CN 110818128 A CN110818128 A CN 110818128A CN 201911060723 A CN201911060723 A CN 201911060723A CN 110818128 A CN110818128 A CN 110818128A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 80
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 36
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- CGOSIVYNVKVZBK-UHFFFAOYSA-K sodium cobalt(2+) trinitrite Chemical compound [Na+].[Co++].[O-]N=O.[O-]N=O.[O-]N=O CGOSIVYNVKVZBK-UHFFFAOYSA-K 0.000 claims abstract description 20
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 15
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 15
- 239000004571 lime Substances 0.000 claims abstract description 15
- 239000008267 milk Substances 0.000 claims abstract description 15
- 210000004080 milk Anatomy 0.000 claims abstract description 15
- 235000013336 milk Nutrition 0.000 claims abstract description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 14
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000008394 flocculating agent Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000005189 flocculation Methods 0.000 claims abstract description 6
- 230000016615 flocculation Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910008649 Tl2O3 Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical compound O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 thallium ions Chemical class 0.000 description 1
- BXJGLLKRUQQYTC-UHFFFAOYSA-N thallium(1+);sulfide Chemical compound [S-2].[Tl+].[Tl+] BXJGLLKRUQQYTC-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a method for deeply removing thallium from high ammonia nitrogen and high COD wastewater, which comprises the following steps: s1, adjusting the pH value of the wastewater by using lime milk or sulfuric acid, adding potassium ferrate for reaction, adding a flocculating agent, and standing; s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes; s3, recovering valuable metals in the first-stage and second-stage slag rotary kilns after liquid-solid separation, feeding the treated liquid into a clean water tank, and discharging the treated liquid out.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a thallium deep removal method for high ammonia nitrogen and high COD wastewater.
Background
With the increasing shortage of concentrate resources in recent years, ores, slags or fly ash containing various impurities have become an important source of raw materials for many smelters. Besides some impurities which are usually concerned, thallium and salts thereof are water pollutants with strong toxicity and have strong mobility so as to be concerned by people, and how to deeply treat thallium in various smelting wastewater is a big problem in the industry;
studies on thallium treatment in wastewater have been reported, and can be roughly classified into the following categories: the method comprises the following steps of (1) a precipitation method, an adsorption method, an ion exchange method, a membrane method, a biological method, an electrochemical separation method and the like, wherein the adsorption method and the ion exchange method are small in adsorption capacity and difficult to regenerate, so that the adsorption method and the ion exchange method cannot be widely used, the membrane method and the biological method have high requirements on water quality and are not wide in universality and difficult to popularize, the electrochemical separation method is easy to be interfered by other metal ions such as Pb, Cd, Cu, Ti, Fe and the like in actual use and is difficult to play a role, the precipitation method is the most widely used method with the strongest applicability at present, and the number of people is;
the most studied precipitation method is a chemical oxidation precipitation method, monovalent thallium is stable, thallium often exists in a monovalent thallium form in a liquid and is difficult to naturally settle, trivalent thallium is easy to form Tl2O3 or Tl (OH)3, and trivalent thallium is easy to form coprecipitation with hydroxide precipitates of various heavy metals, so that the trivalent thallium is oxidized by using an oxidant to form the monovalent thallium, and then the trivalent thallium is coagulated and precipitated to form a main path for removing thallium from wastewater. In actual operation, thallium is often difficult to treat qualified discharge, especially, thallium is difficult to continue to descend after being treated to 15-50ug/L, especially for high ammonia nitrogen and high COD wastewater, ammonia nitrogen and organic matter exist in a complex state with metal ions, the metal ions are difficult to remove in the complex state of being wrapped up, so that the wastewater is difficult to be discharged after being treated for several sections, the requirements of the wastewater on ammonia nitrogen and COD discharge indexes are more and more strict at present, and how to treat heavy metal in the wastewater and reduce ammonia nitrogen and COD in the wastewater form a great trouble of various smelting enterprises.
Disclosure of Invention
The invention provides a thallium deep removal method for high ammonia nitrogen and high COD wastewater, which can effectively solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a thallium deep removal method for high ammonia nitrogen and high COD wastewater comprises the following steps:
s1, adjusting the pH value of the wastewater by using lime milk or sulfuric acid, adding potassium ferrate for reaction, adding a flocculating agent, and standing;
s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes;
s3, recovering valuable metals from the first-stage slag and the second-stage slag in the rotary kiln after liquid-solid separation, and discharging the treated liquid in a clean water tank.
According to the technical scheme, the wastewater in the step S1 has ammonia nitrogen content of more than 30mg/L, COD content of more than 120mg/L and thallium content of 20ug/L-10 mg/L.
According to the technical scheme, the initial pH of the wastewater in the step S1 is adjusted to be 6.0-8.0.
According to the technical scheme, the adding amount of the potassium ferrate in the step S1 is one thousandth to five thousandth of the volume of the wastewater, and the reaction time is 15-25 minutes.
According to the technical scheme, the supernatant in the step S2 is adjusted to the initial pH value of 4.0-5.0.
According to the technical scheme, the addition amount of the sodium cobalt nitrite in the step S2 is one thousandth to two thousandth of the volume of the wastewater;
the adding amount of the sodium sulfide is one thousandth to four thousandth of the volume of the wastewater;
the reaction time is 15-25 minutes.
According to the technical scheme, the end point pH value of the wastewater in the step S2 is adjusted to 7-9.
According to the technical scheme, the total thallium removal rate of the wastewater treated in the step S4 is more than 98%, and ammonia nitrogen and COD are discharged after reaching the standard.
Compared with the prior art, the invention has the beneficial effects that: the invention has scientific and reasonable structure and safe and convenient use, three medicaments of potassium ferrate, sodium cobalt nitrite and sodium sulfide are matched for use under specific conditions, one section of potassium ferrate is used, most metal ions, ammonia nitrogen and COD indexes can reach qualification or approach qualification, the matching of the two sections of sodium cobalt nitrite and sodium sulfide is the most important for treating trace thallium with excessive liquid after one section of treatment except other unqualified indexes, 15-50ug/L of thallium is difficult to continuously descend by adopting a conventional method, and the method is crucial for ensuring qualified treatment of trace thallium while treating other metal ions;
the sodium cobalt nitrite is commonly used as an identification reagent of potassium ions, the potassium ions and the sodium cobalt nitrite generate yellow crystal-shaped precipitates, and the main product is K2Na[Co(NO2)6]Ammonium ion is the main interfering cation in the identification of potassium ion, and it can also form yellow (NH) with sodium cobalt nitrite4)2Na[Co(NO2)6]Precipitation, in which sodium cobalt nitrite can also play a role in removing ammonia nitrogen in wastewater, has been shown according to the data that thallium precipitation by chemical oxidation precipitation is more difficult to remove than trivalent thallium, and thallium precipitation by chemical oxidation precipitation has been studied, while thallium oxidation from monovalent thallium in wastewater is often difficult to complete to trivalent thallium, so complete removal of thallium from wastewater is difficult to achieve, and sodium cobalt nitrite can react with monovalent thallium to form Tl3[Co(NO2)6]Precipitation can further remove incompletely oxidized monovalent thallium, thallium ions can replace potassium ions in certain specific environments, and the precipitation can be more easily combined with cobalt sodium nitrite, so that part of ammonia nitrogen can be reduced by the cobalt sodium nitrite, monovalent thallium can be precipitated, the important effect is achieved in deep thallium removal, the addition of sodium sulfide not only ensures complete precipitation of other metal ions, but also reacts with thallium to generate thallium sulfide precipitation, trace thallium in wastewater is further removed, and the generation of various precipitates can also achieve mixed precipitationThe effect of coagulation and precipitation, and the matching use of two medicaments for secondary treatment can ensure that the thallium-containing wastewater with high ammonia nitrogen and high COD is qualified in treatment:
2K++Na++[Co(NO2)6]3-→K2Na[Co(NO2)6]↓；
2NH4 ++Na++[Co(NO2)6]3-→(NH4)2Na[Co(NO2)6]↓；
Tl++[Co(NO2)6]3-→Tl3[Co(NO2)6]↓；
in conclusion, the method can treat conventional wastewater, is more suitable for treating wastewater containing thallium and high ammonia nitrogen and COD, has the thallium removal rate of more than 98 percent, ensures that the wastewater containing thallium and high ammonia nitrogen and COD are qualified after being treated together, reaches the external drainage standard, does not produce waste residues and waste gases, does not discharge wastewater, and has the advantages of simple and convenient operation process and environmental friendliness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1: as shown in figure 1, the invention provides a technical scheme, and the method for deeply removing thallium from high ammonia nitrogen and high COD wastewater comprises the following steps:
s1, adjusting the pH value of the wastewater by using lime milk, adding potassium ferrate for reaction, adding a flocculating agent, and standing;
s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes;
s3, recovering valuable metals from the first-stage slag and the second-stage slag in the rotary kiln after liquid-solid separation, and discharging the treated liquid in a clean water tank.
According to the technical scheme, the wastewater Pb in the step S1 is as follows: 2.57mg/L, Zn: 105mg/L, Cd: 1.64mg/L, As: 32mg/L, Tl: 128ug/L, COD: 426mg/L, ammonia nitrogen: 120mg/L, pH 10.
According to the technical scheme, the initial pH value of the wastewater in the step S1 is adjusted to 8.0.
According to the technical scheme, the adding amount of the potassium ferrate in the step S1 is three thousandth of the volume of the wastewater, and the reaction time is 25 minutes.
According to the above technical scheme, the supernatant is adjusted to an initial pH of 4.5 in step S2.
According to the technical scheme, the addition amount of the sodium cobalt nitrite in the step S2 is two thousandth of the volume of the wastewater;
the adding amount of the sodium sulfide is three thousandth of the volume of the wastewater;
the reaction time was 25 minutes.
According to the technical scheme, the pH of the end point of the wastewater is adjusted to 8 after the lime milk is added in the step S2.
According to the technical scheme, the total thallium removal rate of the wastewater treated in the step S4 is more than 98%, and ammonia nitrogen and COD are discharged after reaching the standard.
The specific effects are shown in the table:
after two-stage treatment, the heavy metal finally reaches the discharge standard, and COD and ammonia nitrogen also reach the discharge standard.
Example 2: as shown in figure 1, the invention provides a technical scheme, and the method for deeply removing thallium from high ammonia nitrogen and high COD wastewater comprises the following steps:
s1, adjusting the pH value of the wastewater by using lime milk, adding potassium ferrate for reaction, adding a flocculating agent, and standing;
s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes;
s3, recovering valuable metals from the first-stage slag and the second-stage slag in the rotary kiln after liquid-solid separation, and discharging the treated liquid in a clean water tank.
According to the technical scheme, the wastewater Pb in the step S1 is as follows: 1.86mg/L, Zn: 367mg/L, Cd: 2.12mg/L, As: 59mg/L, Tl: 722ug/L, COD: 378mg/L, ammonia nitrogen: 286mg/L, pH 5.
According to the technical scheme, after the lime milk is added into the wastewater in the step S1, the initial pH is adjusted to 7.0.
According to the technical scheme, the adding amount of the potassium ferrate in the step S1 is one thousandth to five thousandth of the volume of the wastewater, and the reaction time is 25 minutes.
According to the above technical scheme, the supernatant is adjusted to an initial pH of 4.5 in step S2.
According to the technical scheme, the addition amount of the sodium cobalt nitrite in the step S2 is one thousandth of the volume of the wastewater;
the adding amount of the sodium sulfide is three thousandth of the volume of the wastewater;
the reaction time was 25 minutes.
According to the technical scheme, the end point pH value of the wastewater in the step S2 is adjusted to 9.
According to the technical scheme, the total thallium removal rate of the wastewater treated in the step S4 is more than 98%, and ammonia nitrogen and COD are discharged after reaching the standard.
The specific parameters are shown in the following table:
after two-stage treatment, the heavy metal finally reaches the discharge standard, and COD and ammonia nitrogen also reach the discharge standard.
Example 3: as shown in figure 1, the invention provides a technical scheme, and the method for deeply removing thallium from high ammonia nitrogen and high COD wastewater comprises the following steps:
s1, adjusting the pH value of the wastewater by using lime milk, adding potassium ferrate for reaction, adding a flocculating agent, and standing;
s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes;
s3, recovering valuable metals from the first-stage slag and the second-stage slag in the rotary kiln after liquid-solid separation, and discharging the treated liquid in a clean water tank.
According to the technical scheme, the wastewater Pb in the step S1 is as follows: 4.02mg/L, Zn: 733mg/L, Cd: 3.65mg/L, As: 135mg/L, Tl: 1640ug/L, COD: 699mg/L, ammonia nitrogen: 467mg/L, pH 5.
According to the technical scheme, lime milk is added into the wastewater in the step S1 at the beginning to adjust the pH value to 8.0.
According to the technical scheme, the adding amount of the potassium ferrate in the step S1 is one thousandth of the volume of the waste water, and the reaction time is 15 minutes.
According to the above technical scheme, the supernatant is adjusted to an initial pH of 5.0 in step S2.
According to the technical scheme, the addition amount of the sodium cobalt nitrite in the step S2 is two thousandth of the volume of the wastewater;
the adding amount of the sodium sulfide is four thousandth of the volume of the wastewater;
the reaction time was 25 minutes.
According to the technical scheme, the end point pH value of the wastewater in the step S2 is adjusted to 9.
According to the technical scheme, the total thallium removal rate of the wastewater treated in the step S4 is more than 98%, and ammonia nitrogen and COD are discharged after reaching the standard.
The specific parameters are shown in the following table:
after two-stage treatment, the heavy metal finally reaches the discharge standard, and COD and ammonia nitrogen also reach the discharge standard.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A thallium deep removal method for high ammonia nitrogen and high COD wastewater is characterized in that: the method comprises the following steps:
s1, adjusting the pH value of the wastewater by using lime milk or sulfuric acid, adding potassium ferrate for reaction, adding a flocculating agent, and standing;
s2, taking the supernatant after standing, adding sodium cobalt nitrite and sodium sulfide for reaction, adding lime milk for wastewater adjustment, and adding a flocculating agent for flocculation and precipitation for 30 minutes;
s3, recovering valuable metals from the first-stage slag and the second-stage slag in the rotary kiln after liquid-solid separation, and discharging the treated liquid in a clean water tank.
2. The method of claim 1, wherein the wastewater in step S1 has an ammonia nitrogen content of 30mg/L or more, a COD content of 120mg/L or more, and a thallium content of 20ug/L to 10 mg/L.
3. The method for deeply removing thallium in the wastewater with high ammonia nitrogen and high COD in claim 1, wherein the initial pH of the wastewater in step S1 is adjusted to 6.0-8.0.
4. The method for deeply removing thallium from high ammonia nitrogen and high COD wastewater according to claim 1, wherein the amount of potassium ferrate added in step S1 is one thousandth to five thousandth of the volume of the wastewater, and the reaction time is 15-25 minutes.
5. The method for deeply removing thallium in the wastewater with high ammonia nitrogen and high COD in the claim 1, wherein the supernatant in the step S2 is adjusted to an initial pH value of 4.0-5.0.
6. The method for deeply removing thallium in the wastewater with high ammonia nitrogen and high COD in claim 1, wherein the amount of the added sodium cobalt nitrite in step S2 is one thousandth to two thousandth of the volume of the wastewater;
the adding amount of the sodium sulfide is one thousandth to four thousandth of the volume of the wastewater;
the reaction time is 15-25 minutes.
7. The method for deeply removing thallium in the wastewater with high ammonia nitrogen and high COD in claim 1, wherein the final pH of the wastewater in step S2 is adjusted to 7-9.
8. The method for deeply removing thallium from high ammonia nitrogen and high COD wastewater according to claim 1, wherein the total thallium removal rate of the wastewater treated in step S4 is above 98%, and ammonia nitrogen and COD are discharged after reaching standards.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062326A (en) * | 2020-08-05 | 2020-12-11 | 衡阳华宏化工实业有限公司 | Industrial wastewater thallium removal treatment method |
| CN115196789A (en) * | 2022-07-20 | 2022-10-18 | 铜陵有色金属集团股份有限公司 | Method for deeply removing thallium from pyrite waste acid |
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| CN112062326A (en) * | 2020-08-05 | 2020-12-11 | 衡阳华宏化工实业有限公司 | Industrial wastewater thallium removal treatment method |
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| CN115504597B (en) * | 2022-09-19 | 2023-11-21 | 安徽铜冠产业技术研究院有限责任公司 | Thallium removal process for pyrite contaminated acid |
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