CN102642953B - Treatment method for high-salinity heavy-metal-containing production sewage - Google Patents
Treatment method for high-salinity heavy-metal-containing production sewage Download PDFInfo
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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 high salinity that the present invention relates to produce after a kind for the treatment of technology for non-ferrous metal hydrometallurgy production waste, particularly laterite nickel ore by sulfuric acid leaching hydrometallurgy contains the treatment process of heavy metal production waste.
Background technology
Follow the 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 and consumes big country.70% of whole world nickel resources amount is red soil nickel ore.Sulfuric acid leaching (pressurization, normal pressure) wet method smelting process becomes the hot topic of exploitation red soil nickel ore.
In the sulfuric acid leaching wet method of red soil nickel ore is put forward the metallurgy of nickel flow process, it no matter is in leaching or going with the noumeite slurry and removal of impurities.Magnesium strippings a large amount of in ore enter solution.In the process with alkali neutralization, precipitate and separate output nickel hydroxide, can produce the production waste (heavy nickel mother liquor) of a large amount of high magnesium sulfate concentrations.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 processed and reaches emission standard, and current technology is complicated, and construction investment is large, and working cost is high.The lime method sludge quantity that industry is commonly used is large, and huge tailings storehouse admittance need to be arranged, and condition restriction is large, easily causes secondary pollution and security context hidden danger.And the metals such as the manganese that contains in the aqueous solution, nickel enter with mud the waste that resource is also caused in the tailings storehouse, more and more can not satisfy the requirement of modern industry cleaner production.Therefore effectively process these high magnesium salts degree, contain the production waste that the multinomial heavy metal content such as manganese, nickel, cobalt, chromium, cadmium exceed standard, cost-effective recovery useful metal does not wherein produce again mud discharging, can produce huge economy and environment benefit.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of high magnesium salts degree, and the inorganic sewage water treatment method that the multinomial heavy metal content such as manganese, nickel, cobalt, chromium, cadmium exceed standard, the manganese of the method in can cost-effective recovery sewage, the metals such as nickel, make sewage purification and do not produce sewage sludge waste slag, stop secondary pollution.And produce magnesium products for efficient recovery, realize that green circulation economy creates conditions.
A kind of high salinity of the present invention contains the treatment process of heavy metal production waste, and it comprises the following steps:
A) sewage is regulated in regulating the aeration tank evenly and preoxidation;
B) sewage evenly enters in reactor and alkaline neutraliser and oxidant reaction continuously, control the pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between, at room temperature reacted 40 ~ 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 is for the Melting of Special Steels raw material;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio 〉=98%; Add alkali output particulate magnesium hydroxide in magnesium salt solution, residual micro heavy in adsorbing and removing solution;
E) flocculating settling magnesium hydroxide in Hhigh-efficient thickener, thickened underflow magnesium hydroxide slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim the metals such as nickel cobalt;
F) supernatant liquor 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.
Described step a) in, adjust the mass concentration ratio of manganese element and other heavy metal element summations in sewage at 2 ~ 5:1.
Above-mentioned steps b) in, be sodium hydroxide by alkaline neutraliser, oxygenant is the hydrogen peroxide of 10 ~ 20% mass percents.
In described steps d) in, adding the sodium hydroxide solution that alkali is 30% mass percent in magnesium salt solution, dosage is 10 ~ 16L/m
3
Beneficial effect of the present invention: the manganese, the magnesium elements that utilize existing q.s in sewage, preparation manganese oxide hydrate and magnesium hydroxide adsorbent in water, remove the heavy metal in sewage, realize that sewage purification reaches emission standard, and reclaim the useful element such as manganese nickel, realized the target of sewage disposal without the 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); Take full advantage of the associated metal ion in sewage; Material consumption is few, cost is low; High and the whole recyclings of heavy metal removing rate; Do not produce sewage sludge waste slag, reduced investment; It is the sewage treatment process of realizing green circulation economy.Contain the heavy metal production waste for the high salinity that produces after the laterite nickel ore by sulfuric acid leaching hydrometallurgy, the present invention's experiment shows every gram manganese oxide hydrate Adsorption nickel, cobalt, and the 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 process flow sheet of the present invention.
Embodiment
The present invention is in view of the characteristics of sulfuric acid leaching hydrometallurgy production waste: in heavy metal ion, manganese content is high, the high magnesium salts degree of sewage; Deficiency for existing treatment process take lime method as representative: sludge quantity is large, secondary pollution etc.; A kind of manganese in sewage that utilizes is proposed, magnesium ion, preparation manganese oxide hydrate and magnesium hydroxide in water, the method for Adsorption heavy metal.
Below the heavy nickel mother liquor that produced after the neutralization precipitation nickel hydroxide in the red soil nickel ore hydrometallurgy flow process as example, the invention will be further described by reference to the accompanying drawings.
As Fig. 1, sewage is the heavy nickel mother liquor that produces after the neutralization precipitation nickel hydroxide in red soil nickel ore hydrometallurgy flow process, the PH initial value is 8 ~ 8.8, but non-constant, after standing for some time, PH can progressively be reduced to 7.6 left and right, wherein the concentration of mn ion is generally in the 200mg/l left and right, and other concentration of heavy metal ion sums generally in the 50mg/l left and right, can satisfy the loading capacity requirement substantially.Therefore, sewage is introduced in the aerating regulation pond and stays for some time, and regulating water quality makes it PH and composition is relatively stable gets off, and by the divalent manganesetion in aeration preoxidation water.Then regulate PH between 8 ~ 8.5 by adding alkali, 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 hydrogen peroxide of 10 ~ 20% mass percents; These two kinds of materials are simple and easy to cheaply, and there is no by product precipitation, and the coprecipitated thing purity of the hydrated manganese dioxide of generation and nickel, cobalt etc. is very high, can be directly after press filtration is dried as the raw material of smelting manganese alloy.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 substantially.
The clear liquid after manganese of having sunk reaches the emission request of country substantially, and quantitatively add appropriate alkali this moment in clear liquid, control pH value below 10, makes part magnesium ion generation Mg (OH) in sewage
2, enter in Hhigh-efficient thickener precipitation dense 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 the metal such as nickel cobalt, and supernatant liquor is the clean magnesium salt solution that heavy metal free pollutes, and can be used for each grade of direct production Mg (OH)
2Product or discharging.
This treatment technology flow process is short, energy consumption is low (normal temperature and pressure); Take full advantage of the associated metal ion in sewage; Material consumption is few, cost is low; High and the whole recyclings of heavy metal removing rate; Do not produce sewage sludge waste slag, reduced investment; It is the sewage treatment process of realizing green circulation economy.
Describe technical process of the present invention in detail below in conjunction with specific embodiment.
Embodiment 1:
A) high salinity is contained the heavy metal production waste and regulate in regulating the aeration tank evenly and preoxidation, make the mass concentration ratio of manganese element and other heavy metal element summations in sewage at 3:1 by adjustment;
B) sewage evenly enters in reactor the hydroperoxidation with sodium hydroxide and 15% mass percent continuously, 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 is for the Melting of Special Steels raw material;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio 〉=98%; The sodium hydroxide solution that adds 30% mass percent in magnesium salt solution, dosage are 12L/m
3, output particulate magnesium hydroxide, residual micro heavy in adsorbing and removing solution;
E) flocculating settling magnesium hydroxide in Hhigh-efficient thickener, thickened underflow magnesium hydroxide slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim the metals such as nickel cobalt;
F) supernatant liquor 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 regulate in regulating the aeration tank evenly and preoxidation, make the mass concentration ratio of manganese element and other heavy metal element summations in sewage at 2:1 by adjustment;
B) sewage evenly enters in reactor the hydroperoxidation with sodium hydroxide and 10% mass percent continuously, 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 is for the Melting of Special Steels raw material;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio 〉=98%; The sodium hydroxide solution that adds 30% mass percent in magnesium salt solution, dosage are 10L/m
3, output particulate magnesium hydroxide, residual micro heavy in adsorbing and removing solution;
E) flocculating settling magnesium hydroxide in Hhigh-efficient thickener, thickened underflow magnesium hydroxide slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim the metals such as nickel cobalt;
F) supernatant liquor 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 regulate in regulating the aeration tank evenly and preoxidation, make the mass concentration ratio of manganese element and other heavy metal element summations in sewage at 5:1 by adjustment;
B) sewage evenly enters in reactor the hydroperoxidation with sodium hydroxide and 20% mass percent continuously, 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 is for the Melting of Special Steels raw material;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio 〉=98%; The sodium hydroxide solution that adds 30% mass percent in magnesium salt solution, dosage are 16L/m
3, output particulate magnesium hydroxide, residual micro heavy in adsorbing and removing solution;
E) flocculating settling magnesium hydroxide in Hhigh-efficient thickener, thickened underflow magnesium hydroxide slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim the metals such as nickel cobalt;
F) supernatant liquor 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 is only the preferred embodiment 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 considered as protection scope of the present invention.
Claims (4)
1. a high salinity contains the treatment process of heavy metal production waste, it is characterized in that comprising the following steps:
A) sewage is regulated in regulating the aeration tank evenly and preoxidation;
B) sewage evenly enters in reactor and alkaline neutraliser and oxidant reaction continuously, control the pH value between 8.5 ~ 8.96 and the Eh value-90 ~-115mV between, at room temperature reacted 40 ~ 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 is for the Melting of Special Steels raw material, and the solid phase slag contains Ni5-13%; Contain Mn15-48%;
D) magnesium salt solution of liquid phase heavy metal element decreasing ratio 〉=98%; Add alkali output particulate magnesium hydroxide in magnesium salt solution, residual micro heavy in adsorbing and removing solution;
E) flocculating settling magnesium hydroxide in Hhigh-efficient thickener, thickened underflow magnesium hydroxide slurry are back to the removal of impurities operation and make the alkali neutralizing agent and reclaim nickel cobalt metal;
F) supernatant liquor is the clean magnesium salt solution that heavy metal free pollutes, and is used for the discharging of each grade magnesium hydroxide products of direct production or standard.
2. high salinity according to claim 1 contains the treatment process of heavy metal production waste, it is characterized in that, described step a) in, adjust the mass concentration ratio of manganese element and other heavy metal element summations in sewage at 2 ~ 5:1.
3. high salinity according to claim 1 and 2 contains the treatment process of heavy metal production waste, it is characterized in that, at described step b) in, be sodium hydroxide by alkaline neutraliser, oxygenant is the hydrogen peroxide of 10 ~ 20% mass percents.
4. high salinity according to claim 1 and 2 contains the treatment process of heavy metal production waste, it is characterized in that, in described steps d) in, adding the sodium hydroxide solution that alkali is 30% mass percent in magnesium salt solution, dosage is 10 ~ 16L/m
3
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| CN103112963B (en) * | 2013-01-15 | 2014-01-15 | 昆明理工大学 | Acidolysis laterite nickel ore wastewater treatment and slag utilization method |
| 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 |
| 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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| CN101628764B (en) * | 2009-07-30 | 2011-10-19 | 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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