CN102642953A - Chemical treatment method for high-salinity heavy-metal-containing production sewage - Google Patents
Chemical treatment method for high-salinity heavy-metal-containing production sewage Download PDFInfo
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- CN102642953A CN102642953A CN2012101439553A CN201210143955A CN102642953A CN 102642953 A CN102642953 A CN 102642953A CN 2012101439553 A CN2012101439553 A CN 2012101439553A CN 201210143955 A CN201210143955 A CN 201210143955A CN 102642953 A CN102642953 A CN 102642953A
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Abstract
The invention discloses a chemical treatment method for high-salinity heavy-metal-containing production sewage. According to the chemical treatment method, manganese ions in the sewage are utilized and adjusted to reach a certain concentration; the sewage is subjected to aeration and pre-oxidation, alkaline and oxidant are added to the sewage, the pH value and Eh value of the sewage are controlled, hydrated manganese oxide is prepared in water, and heavy metal elements in the sewage are removed through adsorption and coprecipitation; the precipitation product is manganese, and nickel concentrate is recycled; proper amount alkaline is added to a small part of the supernatant liquor, magnesium ions in the sewage are utilized to prepare certain amount of magnesium hydrate adsorbent for adsorbing all residual heavy metal ions in the sewage; after dense precipitation, underflow magnesium hydrate paste is recovered to serve as the alkaline neutralizer in the wet metallurgy impurity removal process, and nickel and cobalt and other metals are recovered; the supernatant liquor is purified magnesium salt solution which reaches the emission standard, and the purified magnesium salt solution can be directly used for producing magnesium hydrate products of different grades or discharged according to regulations.
Description
Technical field
The present invention relates to a kind of treatment technology to non-ferrous metal hydrometallurgy production waste, particularly red soil nickel ore sulfuric acid leaches the treatment process that the high salinity that produces behind the hydrometallurgy contains the heavy metal production waste.
Background technology
Follow development of modern industry, the demand of metallic nickel is increased rapidly.Over past ten years, the consumption of China's nickel increases with average annual 25% speedup, becomes the first in the world nickel consumption big country.70% of whole world nickel resources amount is a red soil nickel ore.Sulfuric acid leaches (pressurization, normal pressure) wet method smelting process becomes the hot topic of exploitation red soil nickel ore.
No matter leach wet method at the sulfuric acid of red soil nickel ore and carry in the metallurgy of nickel flow process, be in leaching or going with the noumeite slurry and removal of impurities.Magnesium strippings a large amount of in the ore get into solution.In process, can produce the production waste (heavy nickel mother liquor) of a large amount of high magnesium sulfate concentrations with alkali neutralization, precipitate and separate output nickel hydroxide.These sewage solution compositions are complicated, contain manganese, nickel, and cobalt, lead, chromium, the multinomial heavy metal contamination of cadmium (content 0.5-50mg/l, the highest 50-500mg/l of manganese content) will be handled and reaches emission standard, and current technology is complicated, and construction investment is big, and working cost is high.The lime method sludge quantity that industry is used always is big, needs huge tailings storehouse and admits, and condition restriction is big, causes secondary pollution and security context hidden danger easily.And metals such as the manganese that contains in the aqueous solution, nickel enter the waste that resource is also caused in the tailings storehouse with mud, more and more can not satisfy the requirement of modern industry cleaner production.Therefore effectively handle these high magnesium salts degree, contain the production waste that multinomial heavy metal content such as manganese, nickel, cobalt, chromium, cadmium exceed standard, cost-effective recovery useful metal does not wherein produce mud discharging again, can produce huge economy and environmental benefit.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high magnesium salts degree; And the inorganic sewage water treatment method that multinomial heavy metal content such as manganese, nickel, cobalt, chromium, cadmium exceed standard; The manganese of this method in can cost-effective recovery sewage; Metals such as nickel make sewage purification and do not produce sewage sludge waste slag, stop secondary pollution.And, realize that green recycling economy creates conditions for efficient recovery production magnesium products.
A kind of high salinity of the present invention contains the change treatment process of heavy metal production waste, and it may further comprise the steps:
A) sewage is regulated in regulating the aeration tank evenly and preoxidation;
B) sewage evenly continuously gets in the reaction kettle and alkaline neutraliser and oxidant reaction; The control pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between; At room temperature reacted 40 ~ 90 minutes, and generated the manganese oxide hydrate throw out, the heavy metal ion in co-precipitation and adsorbing and removing liquid phase;
C) realize solid-liquid separation through efficient dense filtration, the solid phase slag is higher-grade Mn-Ni-concentrate, and drying and packaging supplies the special steel raw materials for metallurgy;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio >=98%; In magnesium salt solution, add alkali output particulate Marinco H, residual micro heavy in the adsorbing and removing solution;
E) flocculating settling Marinco H in Hhigh-efficient thickener, thickened underflow Marinco H slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim metals such as nickel cobalt;
F) supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for the discharging of each grade magnesium hydroxide products of direct production or standard.
In the said step a), the mass concentration ratio of manganese element and other heavy metal element summations is at 2 ~ 5:1 in the adjustment sewage.
Above-mentioned steps b) in, be sodium hydroxide through alkaline neutraliser, oxygenant is the hydrogen peroxide of 10 ~ 20% mass percents.
In said step d), in magnesium salt solution, add the sodium hydroxide solution that alkali is 30% mass percent, dosage is 10 ~ 16L/m
3
Beneficial effect of the present invention: the manganese, the magnesium elements that utilize existing q.s in the sewage; Preparation manganese oxide hydrate and Marinco H sorbent material in water; Remove the heavy metal in the sewage; Realize that sewage purification reaches emission standard, and reclaim useful element such as manganese nickel, realized that WWT do not have the target of sewage sludge waste slag discharging.The present invention carries has great economic benefit and environmental benefit, and techniqueflow is short, energy consumption is low (normal temperature and pressure); Make full use of the associated metal ion in the sewage; Material consumption is few, cost is low; High and all recyclings of heavy metal removing rate; Do not produce sewage sludge waste slag, reduced investment; It is the sewage treatment process of realizing green recycling economy.Leach the high salinity that produces behind the hydrometallurgy for red soil nickel ore sulfuric acid and contain the heavy metal production waste, the present invention's experiment shows every gram manganese oxide hydrate absorption removal nickel, cobalt, and heavy metal amounts such as cadmium can reach 0.25 gram.Eliminating rate of absorption can reach more than 98%.After adsorption precipitation was filtered, all kinds of concentration of heavy metal ion can reach the relevant emission standards of country.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention leaches the characteristics of hydrometallurgy production waste in view of sulfuric acid: manganese content is high in the heavy metal ion, the high magnesium salts degree of sewage; To existing be the deficiency of the treatment process of representative with the lime method: sludge quantity is big, secondary pollution etc.; A kind of manganese in the sewage that utilizes is proposed, mg ion, preparation manganese oxide hydrate and Marinco H in water, the method for heavy metal is removed in absorption.
Below be example with the heavy nickel mother liquor that produced behind the neutralization precipitation nickel hydroxide in the red soil nickel ore hydrometallurgy flow process, in conjunction with accompanying drawing the present invention is further described.
Like Fig. 1; Sewage is the heavy nickel mother liquor that is produced behind the neutralization precipitation nickel hydroxide in the red soil nickel ore hydrometallurgy flow process, and the PH initial value is 8 ~ 8.8, but non-constant; PH can progressively be reduced to about 7.6 after leaving standstill for some time; Wherein generally about 200mg/l, other concentration of heavy metal ion sums generally about 50mg/l, can satisfy the loading capacity requirement to the concentration of mn ion basically.Therefore, sewage is introduced in the aerating regulation pond and stays for some time, and regulates that water quality makes it PH and composition is relatively stable gets off, and through the divalent manganesetion in the aeration preoxidation water.Regulate PH between 8 ~ 8.5 through adding alkali then, oxidizer regulate EH-100 ~-120mV between, make the divalent manganesetion oxidation generate hydrated manganese dioxide.Here alkali is with 10% sodium hydroxide solution, and oxygenant uses the ydrogen peroxide 50 of 10 ~ 20% mass percents; These two kinds of materials are simple and easy to cheaply, and do not have the by product deposition, and the common hypostasis purity of the hydrated manganese dioxide of generation and nickel, cobalt etc. is very high, can be directly as the raw material of smelting manganese alloy after the press filtration oven dry.This method heavy metal removing rate height generally can reach more than 95%, and the water outlet heavy metal content can satisfy the relevant emission request of country basically.
The clear liquid behind the manganese of having sunk reaches the emission request of country basically, quantitatively in clear liquid, adds an amount of alkali this moment, and the control pH value is below 10, makes that the part mg ion generates Mg (OH) in the sewage
2, deposition is dense in the entering Hhigh-efficient thickener after Coagulation and Adsorption, thickened underflow Mg (OH)
2Slurry is back to main line removal of impurities operation and makes the alkali neutralizing agent and reclaim metal such as nickel cobalt, and supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for each grade Mg (OH) of direct production
2Product or discharging.
This treatment technology flow process is short, energy consumption is low (normal temperature and pressure); Make full use of the associated metal ion in the sewage; Material consumption is few, cost is low; High and all recyclings of heavy metal removing rate; Do not produce sewage sludge waste slag, reduced investment; It is the sewage treatment process of realizing green recycling economy.
Specify technical process of the present invention below in conjunction with specific embodiment.
Embodiment 1:
A) high salinity is contained the heavy metal production waste and in regulating the aeration tank, regulate evenly and preoxidation, the mass concentration ratio that makes manganese element and other heavy metal element summations in the sewage through adjustment is at 3:1;
B) sewage evenly continuously gets in the reaction kettle hydroperoxidation with sodium hydroxide and 15% mass percent; The control pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between; At room temperature reacted 60 minutes; Generate the manganese oxide hydrate throw out, the heavy metal ion in co-precipitation and adsorbing and removing liquid phase;
C) realize solid-liquid separation through efficient dense filtration, the solid phase slag is higher-grade Mn-Ni-concentrate, and drying and packaging supplies the special steel raw materials for metallurgy;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio>=98%; In magnesium salt solution, add the sodium hydroxide solution of 30% mass percent, dosage is 12L/m
3, output particulate Marinco H, residual micro heavy in the adsorbing and removing solution;
E) flocculating settling Marinco H in Hhigh-efficient thickener, thickened underflow Marinco H slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim metals such as nickel cobalt;
F) supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for the discharging of each grade magnesium hydroxide products of direct production or standard.
Embodiment 2:
A) high salinity is contained the heavy metal production waste and in regulating the aeration tank, regulate evenly and preoxidation, the mass concentration ratio that makes manganese element and other heavy metal element summations in the sewage through adjustment is at 2:1;
B) sewage evenly continuously gets in the reaction kettle hydroperoxidation with sodium hydroxide and 10% mass percent; The control pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between; At room temperature reacted 40 minutes; Generate the manganese oxide hydrate throw out, the heavy metal ion in co-precipitation and adsorbing and removing liquid phase;
C) realize solid-liquid separation through efficient dense filtration, the solid phase slag is higher-grade Mn-Ni-concentrate, and drying and packaging supplies the special steel raw materials for metallurgy;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio>=98%; In magnesium salt solution, add the sodium hydroxide solution of 30% mass percent, dosage is 10L/m
3, output particulate Marinco H, residual micro heavy in the adsorbing and removing solution;
E) flocculating settling Marinco H in Hhigh-efficient thickener, thickened underflow Marinco H slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim metals such as nickel cobalt;
F) supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for the discharging of each grade magnesium hydroxide products of direct production or standard.
Embodiment 3:
A) high salinity is contained the heavy metal production waste and in regulating the aeration tank, regulate evenly and preoxidation, the mass concentration ratio that makes manganese element and other heavy metal element summations in the sewage through adjustment is at 5:1;
B) sewage evenly continuously gets in the reaction kettle hydroperoxidation with sodium hydroxide and 20% mass percent; The control pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between; At room temperature reacted 90 minutes; Generate the manganese oxide hydrate throw out, the heavy metal ion in co-precipitation and adsorbing and removing liquid phase;
C) realize solid-liquid separation through efficient dense filtration, the solid phase slag is higher-grade Mn-Ni-concentrate, and drying and packaging supplies the special steel raw materials for metallurgy;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio>=98%; In magnesium salt solution, add the sodium hydroxide solution of 30% mass percent, dosage is 16L/m
3, output particulate Marinco H, residual micro heavy in the adsorbing and removing solution;
E) flocculating settling Marinco H in Hhigh-efficient thickener, thickened underflow Marinco H slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim metals such as nickel cobalt;
F) supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for the discharging of each grade magnesium hydroxide products of direct production or standard.
Table 1 is sewage composition and treatment effect table of the present invention:
The concrete application approach of the present invention is a lot, and the above only is a preferred implementation of the present invention, should be understood that; For those skilled in the art; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement, these improvement also should be regarded as protection scope of the present invention.
Claims (4)
1. a high salinity contains the change treatment process of heavy metal production waste, it is characterized in that may further comprise the steps:
A) sewage is regulated in regulating the aeration tank evenly and preoxidation;
B) sewage evenly continuously gets in the reaction kettle and alkaline neutraliser and oxidant reaction; The control pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between; At room temperature reacted 40 ~ 90 minutes, and generated the manganese oxide hydrate throw out, the heavy metal ion in co-precipitation and adsorbing and removing liquid phase;
C) realize solid-liquid separation through efficient dense filtration, the solid phase slag is higher-grade Mn-Ni-concentrate, and drying and packaging supplies the special steel raw materials for metallurgy (to contain Ni5-13%; Contain Mn15-48%);
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio >=98%; In magnesium salt solution, add alkali output particulate Marinco H, residual micro heavy in the adsorbing and removing solution;
E) flocculating settling Marinco H in Hhigh-efficient thickener, thickened underflow Marinco H slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim metals such as nickel cobalt;
F) supernatant is the clean magnesium salt solution that heavy metal free pollutes, and can be used for the discharging of each grade magnesium hydroxide products of direct production or standard.
2. high salinity according to claim 1 contains the change treatment process of heavy metal production waste, it is characterized in that, in said step a), the mass concentration ratio of manganese element and other heavy metal element summations is at 2 ~ 5:1 in the adjustment sewage.
3. high salinity according to claim 1 and 2 contains the change treatment process of heavy metal production waste, it is characterized in that, and in said step b), be sodium hydroxide through alkaline neutraliser, oxygenant is the hydrogen peroxide of 10 ~ 20% mass percents.
4. high salinity according to claim 1 and 2 contains the change treatment process of heavy metal production waste, it is characterized in that, in said step d), in magnesium salt solution, adds the sodium hydroxide solution that alkali is 30% mass percent, and dosage is 10 ~ 16L/m
3
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112963A (en) * | 2013-01-15 | 2013-05-22 | 昆明理工大学 | Acidolysis laterite nickel ore wastewater treatment and slag utilization method |
| CN103880211A (en) * | 2014-03-14 | 2014-06-25 | 浙江迪邦化工有限公司 | Process for resourceful treatment of high-salt wastewater containing magnesium |
| CN105110518A (en) * | 2015-09-30 | 2015-12-02 | 河北泽世康化工有限公司 | Treatment method for acidic organic wastewater |
| CN105152402A (en) * | 2015-09-13 | 2015-12-16 | 常州大学 | Heavy metal wastewater pretreatment device |
| CN106086474A (en) * | 2016-08-30 | 2016-11-09 | 荆门市格林美新材料有限公司 | A kind of method recycling magnesium from heavy metal sewage sludge |
| CN109607909A (en) * | 2018-11-27 | 2019-04-12 | 核工业北京化工冶金研究院 | A kind of high ammonia nitrogen uranium containing manganese wastewater treatment method |
| CN110255588A (en) * | 2019-06-21 | 2019-09-20 | 镇江市富来尔制冷工程技术有限公司 | A kind of regeneration treating method for lithium-bromide solution in Absorption Refrigerator |
| CN115093050A (en) * | 2022-06-28 | 2022-09-23 | 广东邦普循环科技有限公司 | Treatment method of manganese-containing wastewater |
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| JP2004261637A (en) * | 2003-02-06 | 2004-09-24 | Idemitsu Kosan Co Ltd | Treatment method for hardly decomposable harmful substance-containing waste water |
| CN101628764A (en) * | 2009-07-30 | 2010-01-20 | 浙江华友钴业股份有限公司 | Processing method of industrial waste water generated in hydrometallurgical process of nickel, cobalt and copper |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112963A (en) * | 2013-01-15 | 2013-05-22 | 昆明理工大学 | Acidolysis laterite nickel ore wastewater treatment and slag utilization method |
| CN103880211A (en) * | 2014-03-14 | 2014-06-25 | 浙江迪邦化工有限公司 | Process for resourceful treatment of high-salt wastewater containing magnesium |
| CN103880211B (en) * | 2014-03-14 | 2015-11-04 | 浙江迪邦化工有限公司 | A kind of recycling treatment process containing magnesium high-salt wastewater |
| CN105152402A (en) * | 2015-09-13 | 2015-12-16 | 常州大学 | Heavy metal wastewater pretreatment device |
| CN105110518A (en) * | 2015-09-30 | 2015-12-02 | 河北泽世康化工有限公司 | Treatment method for acidic organic wastewater |
| CN106086474A (en) * | 2016-08-30 | 2016-11-09 | 荆门市格林美新材料有限公司 | A kind of method recycling magnesium from heavy metal sewage sludge |
| CN106086474B (en) * | 2016-08-30 | 2018-03-27 | 荆门市格林美新材料有限公司 | A kind of method that magnesium is recycled from heavy metal sewage sludge |
| CN109607909A (en) * | 2018-11-27 | 2019-04-12 | 核工业北京化工冶金研究院 | A kind of high ammonia nitrogen uranium containing manganese wastewater treatment method |
| CN110255588A (en) * | 2019-06-21 | 2019-09-20 | 镇江市富来尔制冷工程技术有限公司 | A kind of regeneration treating method for lithium-bromide solution in Absorption Refrigerator |
| CN115093050A (en) * | 2022-06-28 | 2022-09-23 | 广东邦普循环科技有限公司 | Treatment method of manganese-containing wastewater |
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