CN216514040U - System for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture - Google Patents
System for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture Download PDFInfo
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- CN216514040U CN216514040U CN202122427754.3U CN202122427754U CN216514040U CN 216514040 U CN216514040 U CN 216514040U CN 202122427754 U CN202122427754 U CN 202122427754U CN 216514040 U CN216514040 U CN 216514040U
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Abstract
The utility model provides a system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures, which comprises a first reaction device, a first filtering device, a second reaction device, a second filtering device, a third reaction device, a third filtering device, a fourth reaction device, a first drying calciner, a first reduction smelting furnace, a fifth reaction device, a fourth filtering device, a steam stripping deamination device, a fifth filtering device, a second drying calciner and a second reduction smelting furnace; the method ensures that valuable elements of the multi-metal mixture such as the electroplating sludge or the laterite-nickel ore and the like are all recovered, achieves the effect of recovering all elements, and has important economic benefit and social benefit.
Description
Technical Field
The utility model relates to a method for recovering metals in electroplating sludge or a multi-metal mixture, in particular to a system and a process for recovering copper, nickel, zinc, chromium and iron from electroplating sludge and the multi-metal mixture.
Background
Electroplating is one of three major global pollution industries. According to incomplete statistics, more than 1 million electroplating enterprises in China discharge electroplating wastewater of about 40 billions and cubic meters every year in the electroplating industry. The electroplating sludge with a large amount of heavy metals is generated after the electroplating wastewater is chemically treated, and the electroplating sludge has high content of heavy metals, so the electroplating sludge is named as dangerous waste by the national name; but the electroplating sludge is rich in a large amount of metal resources and has recovery value.
The laterite-nickel ore is a multi-metal mixture, the main components of the laterite-nickel ore are elements such as iron, silicon, nickel, chromium, magnesium and the like, high-value elements such as nickel, cobalt and the like can be obtained by a high-pressure acid leaching process which is mainly adopted at present, but iron and silicon are left in leached slag, so that natural slag is generated, and adverse effects are generated on the environment, so that how to effectively recover the elements such as iron, chromium and the like in the laterite-nickel ore has important social value and economic value.
Accordingly, there is a need for improvements in the art.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a system and a process for efficiently recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures.
The utility model provides a system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures, which comprises a first reaction device, a first filtering device, a second reaction device, a second filtering device, a third reaction device, a third filtering device, a fourth reaction device, a first drying and calcining furnace, a first reduction smelting furnace, a fifth reaction device, a fourth filtering device, a stripping and deamination device, a fifth filtering device, a second drying and calcining furnace and a second reduction smelting furnace;
the outlet of the first reaction device is connected with the inlet of the first filtering device;
the filtrate outlet of the first filtering device is connected with the inlet of the second reaction device;
the outlet of the second reaction device is connected with the inlet of the second filtering device;
the filtrate outlet of the second filtering device is connected with the inlet of the third reaction device;
the solid outlet of the second filtering device is connected with the inlet of the first drying and calcining furnace;
the outlet of the first drying calciner is connected with the inlet of the first reduction smelting furnace;
the outlet of the third reaction device is connected with the inlet of a third filtering device;
a filtrate outlet of the third filtering device is connected with an inlet of the fourth reaction device;
the solid outlet of the third filtering device is connected with the inlet of the fifth reaction device;
the outlet of the fifth reaction device is connected with the inlet of the fourth filtering device;
the solid outlet of the fourth filtering device is connected with the inlet of the second drying and calcining furnace;
the outlet of the second drying calciner is connected with the inlet of the second reduction smelting furnace;
a filtrate outlet of the fourth filtering device is connected with an inlet of the stripping deamination device;
an ammonia water outlet of the stripping deamination device is connected with an inlet of the fifth reaction device;
and a tower bottom liquid outlet of the stripping deamination device is connected with an inlet of the fifth filtering device.
As an improvement of the system for recovering copper, nickel, zinc, chromium and iron from the electroplating sludge or other multi-metal mixture of the utility model:
the first reaction device, the second reaction device, the third reaction device, the fourth reaction device and the fifth reaction device are all used for material reaction;
the first filtering device, the second filtering device, the third filtering device, the fourth filtering device and the fifth filtering device are used for filtering;
the stripping deamination device is used for stripping deamination;
the first drying and calcining furnace and the second drying and calcining furnace are used for drying and calcining;
and the first reduction smelting furnace and the second reduction smelting furnace are both used for reduction smelting.
As an improvement of the system for recovering copper, nickel, zinc, chromium and iron from the electroplating sludge or other multi-metal mixture of the utility model:
the first reaction device, the second reaction device, the third reaction device, the fourth reaction device and the fifth reaction device are one or more of a stirring kettle and a tubular reactor.
As an improvement of the system for recovering copper, nickel, zinc, chromium and iron from the electroplating sludge or other multi-metal mixture of the utility model:
the first filtering device, the second filtering device, the third filtering device, the fourth filtering device and the fifth filtering device are one or more of a centrifugal machine, a plate-and-frame filter press, a belt filter and a disc dehydrator.
As an improvement of the system for recovering copper, nickel, zinc, chromium and iron from the electroplating sludge or other multi-metal mixture of the utility model:
the stripping deamination device is formed by combining a preheater, a stripping deamination tower, a condenser and a reboiler.
The system and the process for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures have the technical advantages that:
1. the method comprises the steps of leaching valuable metals such as iron, aluminum, copper, nickel, chromium, zinc and the like in the electroplating sludge by using acid, wherein leaching residues mainly comprise calcium sulfate, silicon dioxide and the like and are almost free of chromium, and the leaching residues can be used as cement raw materials for treatment, so that the leaching residues have a place;
2. adding liquid alkali or ammonia water step by step to respectively obtain iron hydroxide and other metal mixtures, firstly adjusting the pH value to 2-3, precipitating the iron hydroxide, firstly separating most iron elements, drying, calcining and then preparing reduced iron in a reduction smelting mode, thus recycling the iron elements and avoiding the condition that the proportion of chromium elements cannot meet the standard requirement of GB5683-1987 ferrochrome in the subsequent preparation of ferrochrome alloy; secondly, adjusting the pH value to 9-12, and precipitating other heavy metals such as chromium, aluminum, nickel, copper, zinc and the like by hydroxide;
3. the method is characterized in that the principle that ammonia and copper, nickel and zinc can form a complex is adopted, the mixture of ammonia water and ammonium bicarbonate is used for ammonia leaching, the nickel, copper and zinc are separated from chromium, iron, aluminum and a small amount of magnesium, and the nickel, copper and zinc are subjected to leaching extraction treatment to respectively obtain products of nickel sulfate, copper sulfate and zinc sulfate. Chromium, aluminum and a small amount of iron and magnesium are dried and calcined firstly, and then the chromium-iron alloy is prepared by reduction, and aluminum and magnesium are furnace slag, so that valuable elements of the multi-metal mixture such as electroplating sludge or laterite-nickel ore and the like can be recovered, the effect of recovering all elements is achieved, and the method has important economic benefit and social benefit.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic flow diagram of a system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures according to the present invention.
Detailed Description
The utility model will be further described with reference to specific examples, but the scope of the utility model is not limited thereto.
Example 1, a system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture, as shown in fig. 1, comprises a first reaction device 1, a first filtering device 2, a second reaction device 3, a second filtering device 4, a third reaction device 5, a third filtering device 6, a fourth reaction device 7, a first drying calciner 8, a first reduction smelting furnace 9, a fifth reaction device 10, a fourth filtering device 11, a stripping deamination device 12, a fifth filtering device 13, a second drying calciner 14 and a second reduction smelting furnace 15.
The outlet of the first reaction device 1 is connected with the inlet of the first filtering device 2;
the filtrate outlet of the first filtering device 2 is connected with the inlet of the second reaction device 3;
the outlet of the second reaction device 3 is connected with the inlet of the second filtering device 4;
the filtrate outlet of the second filtering device 4 is connected with the inlet of the third reaction device 5;
the solid outlet of the second filtering device 4 is connected with the inlet of the first drying and calcining furnace 8;
the outlet of the first drying calciner 8 is connected with the inlet of the first reduction smelting furnace 9;
the outlet of the third reaction device 5 is connected with the inlet of the third filtering device 6;
the filtrate outlet of the third filtering device 6 is connected with the inlet of the fourth reaction device 7;
the solid outlet of the third filtering device 6 is connected with the inlet of the fifth reaction device 10;
the outlet of the fifth reaction device 10 is connected with the inlet of the fourth filtering device 11;
the solid outlet of the fourth filtering device 11 is connected with the inlet of the second drying and calcining furnace 14;
the outlet of the second drying calciner 14 is connected with the inlet of the second reduction smelting furnace 15;
a filtrate outlet of the fourth filtering device 11 is connected with an inlet of a stripping deamination device 12;
an ammonia water outlet of the stripping deamination device 12 is connected with an inlet of the fifth reaction device 10;
the tower bottom liquid outlet of the stripping deamination device 12 is connected with the inlet of the fifth filtering device 13.
The first reaction device 1, the second reaction device 3, the third reaction device 5, the fourth reaction device 7 and the fifth reaction device 10 are all used for material reaction and are one or more of a stirring kettle and a tubular reactor;
the first filtering device 2, the second filtering device 4, the third filtering device 6, the fourth filtering device 11 and the fifth filtering device 13 are used for filtering and can be one or more of a centrifugal machine, a plate-and-frame filter press, a belt filter and a disc dehydrator;
the stripping deamination device 12 is used for stripping deamination and is composed of a preheater, a stripping deamination tower, a condenser, a reboiler and the like;
the first drying calciner 8 and the second drying calciner 14 are both used for dry calcination;
the first reduction smelting furnace 9 and the second reduction smelting furnace 15 are used for reduction smelting.
The process for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures comprises the following steps:
1) the electroplating sludge comes from a certain electroplating factory and is in a block shape and in a gray green color. And (3) pretreating the electroplating sludge by adopting a crushing or ball milling mode. The water content of the electroplating sludge is about 60%, and the main metal components (dry basis) are as follows: 6.3 percent of Cr, 4.2 percent of Cu, 10.2 percent of Fe, 9.1 percent of Ni, 1.1 percent of Zn, 33.0 percent of Ca, 3.6 percent of Mg and 4.2 percent of Al.
Adding the pretreated electroplating sludge or other multi-metal mixture into a first reaction device 1 for acid leaching reaction, adding dilute sulfuric acid with the mass concentration of 10-20%, and keeping the liquid-solid ratio of the dilute sulfuric acid to the pretreated electroplating sludge to be about 5: 1 (range 2: 1 to 10: 1); the hydroxides or oxides of nickel, copper, zinc, chromium, iron, calcium, magnesium and aluminum in the sludge are converted into sulfates. The whole leaching reaction is carried out in a first reaction device 1, the pH is controlled to be about 0.5-2, after the reaction is carried out for 0.5-5 hours, the first filtering device 2 is added for filtering, a filter cake and a filtrate which are filtered by the first filtering device 2 are obtained, the main component of the filter cake which is filtered by the first filtering device 2 is calcium sulfate dihydrate, and the filter cake is used for landfill or cement kiln cooperative treatment. The leaching reaction may be carried out by using hydrochloric acid or nitric acid instead of dilute sulfuric acid.
2) The pH of the filtrate filtered by the first filtering device 2 is firstly adjusted to about 2-3 by using liquid caustic soda with the mass concentration of 15-32% or ammonia water with the mass concentration of 10-20%, the reaction is carried out in the second reaction device 3, ferric sulfate is converted into ferric hydroxide, the ferric hydroxide is precipitated and separated out, then the filtrate is filtered by the second filtering device 4 to obtain a filter cake and filtrate filtered by the second filtering device 4, the filter cake ferric hydroxide filtered by the second filtering device 4 is dried and decomposed in the first drying and calcining furnace 8 to obtain ferric oxide, and then reducing agents such as coal gas or natural gas are added into the first reducing and smelting furnace 9 to be reduced and smelted to obtain iron or magnetic materials.
3) Continuously adjusting the pH value of the filtrate filtered by the second filtering device 4 to 9-12, carrying out reaction in a third reaction device 5, converting aluminum sulfate, chromium sulfate, nickel sulfate, copper sulfate, zinc sulfate and magnesium sulfate into hydroxide, and filtering by a third filtering device 6 to obtain a filter cake and filtrate filtered by the third filtering device 6; ensuring that the heavy metals in the wastewater reach the standard, adding sulfuric acid or hydrochloric acid into the filtrate obtained after filtration by the third filtration device 6 to adjust the pH value to be neutral in the fourth reaction device 7, discharging or evaporating and crystallizing sodium sulfate wastewater after adjusting the pH value to obtain sodium sulfate, and drying the sodium sulfate wastewater to obtain anhydrous sodium sulfate for sale; the ammonium sulfate wastewater is treated by adopting one of the following schemes: the first scheme is as follows: and after the pH value is adjusted, evaporating and crystallizing to obtain ammonium sulfate crystals for external sale, adding liquid alkali or calcium hydroxide to adjust the pH value to 12, then stripping and deaminating to recover ammonia, and discharging the wastewater after reaching the standard.
The filter cake filtered by the third filtering device 6 mainly comprises nickel hydroxide, copper hydroxide, zinc hydroxide, chromium hydroxide and a small amount of aluminum hydroxide, iron hydroxide and magnesium hydroxide;
4) and the filter cake filtered by the third filtering device 6 is subjected to ammonia leaching reaction in a fifth reaction device 10 by using a mixture of ammonia water (the mass ratio is 12-20%) and ammonium bicarbonate (the mass ratio is 8-15%), the reaction time of the ammonia leaching reaction is 0.5-10 hours, the reaction temperature is 50-90 ℃, the pressure is 0-1.0Mpa, and a copper ammonia, nickel ammonia and zinc ammonia complex is formed due to the existence of the ammonia water, and the specific reaction is as follows:
Cu(OH)2+nNH3——>Cu(NH3)n 2++2OH-
Ni(OH)2+nNH3——>Ni(NH3)n 2++2OH-
Zn(OH)2+nNH3——>Zn(NH3)n 2++2OH-
the dissolution reaction takes place while the remaining hydroxides of chromium, iron, aluminum, magnesium, etc. do not react with ammonia and remain in solid form. And filtering in a fourth filtering device 11 after leaching to obtain a filter cake and filtrate filtered by the fourth filtering device 11, wherein the filter cake filtered by the fourth filtering device 11 mainly comprises chromium hydroxide, aluminum hydroxide, iron hydroxide and magnesium hydroxide.
The filter cake filtered by the fourth filtering device 11 is added into a second drying and calcining furnace 14 for calcining and dewatering, wherein the chromium hydroxide, the aluminum hydroxide, the magnesium hydroxide and a small amount of ferric hydroxide are converted into chromium oxide, aluminum oxide, magnesium oxide and ferric oxide, and then the chromium oxide, the aluminum hydroxide, the magnesium hydroxide and the small amount of ferric hydroxide are added into a second reduction smelting furnace 15 for reduction smelting by using reducing agents such as coal gas or natural gas and the like to obtain ferrochrome alloy, the aluminum oxide and the magnesium oxide are used as slag for treatment, and the slag is buried or used as cement raw materials.
5) And the filtrate filtered by the fourth filtering device 11 is subjected to stripping deamination in a stripping deamination device 12, a mixture of ammonia water and ammonium bicarbonate is recovered, a copper ammonia, nickel ammonia and zinc ammonia complex is decomplexed to form basic copper carbonate, nickel carbonate and zinc carbonate precipitate, the basic copper carbonate, nickel carbonate and zinc carbonate precipitate is separated out, the basic copper carbonate, nickel carbonate and zinc carbonate precipitate are filtered by a fifth filtering device 13 to obtain a filter cake and filtrate filtered by the fifth filtering device 13, the filter cake filtered by the fifth filtering device 13 is collected for sale, the filtrate filtered by the two-stage filtering contains ammonia nitrogen less than 15mg/L, nickel less than 0.5PPM, copper less than 0.5PPM and zinc less than 0.5PPM, and the wastewater is discharged after pH is adjusted by sulfuric acid or hydrochloric acid and reaches the standard.
The mixture of the condensed product ammonia water at the top of the stripping rectification tower and the ammonium bicarbonate is supplemented with a small amount of 20% ammonia water and carbon dioxide, so that the mass concentration of the ammonia water of the mixture is between 12 and 20%, and the mass concentration of the ammonium bicarbonate is between 8 and 15% (the reaction can be carried out in an absorption tower or a storage tank), and then the mixture is added into a fifth reaction device 10.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the utility model. It is obvious that the utility model is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the utility model.
Claims (5)
1. Electroplating sludge or other multi-metal mixture retrieves system of copper, nickel, zinc, chromium, iron, its characterized in that: comprises a first reaction device (1), a first filtering device (2), a second reaction device (3), a second filtering device (4), a third reaction device (5), a third filtering device (6), a fourth reaction device (7), a first drying calciner (8), a first reduction smelting furnace (9), a fifth reaction device (10), a fourth filtering device (11), a stripping deamination device (12), a fifth filtering device (13), a second drying calciner (14) and a second reduction smelting furnace (15);
the outlet of the first reaction device (1) is connected with the inlet of the first filtering device (2);
the filtrate outlet of the first filtering device (2) is connected with the inlet of the second reaction device (3);
the outlet of the second reaction device (3) is connected with the inlet of the second filtering device (4);
the filtrate outlet of the second filtering device (4) is connected with the inlet of a third reaction device (5);
the solid outlet of the second filtering device (4) is connected with the inlet of the first drying and calcining furnace (8);
the outlet of the first drying and calcining furnace (8) is connected with the inlet of the first reduction smelting furnace (9);
the outlet of the third reaction device (5) is connected with the inlet of a third filtering device (6);
the filtrate outlet of the third filtering device (6) is connected with the inlet of a fourth reaction device (7);
the solid outlet of the third filtering device (6) is connected with the inlet of a fifth reaction device (10);
the outlet of the fifth reaction device (10) is connected with the inlet of a fourth filtering device (11);
the solid outlet of the fourth filtering device (11) is connected with the inlet of the second drying and calcining furnace (14);
the outlet of the second drying and calcining furnace (14) is connected with the inlet of the second reduction smelting furnace (15);
a filtrate outlet of the fourth filtering device (11) is connected with an inlet of a stripping deamination device (12);
an ammonia water outlet of the stripping deamination device (12) is connected with an inlet of a fifth reaction device (10);
and a tower bottom liquid outlet of the stripping deamination device (12) is connected with an inlet of the fifth filtering device (13).
2. The system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures according to claim 1, wherein:
the first reaction device (1), the second reaction device (3), the third reaction device (5), the fourth reaction device (7) and the fifth reaction device (10) are all used for material reaction;
the first filtering device (2), the second filtering device (4), the third filtering device (6), the fourth filtering device (11) and the fifth filtering device (13) are used for filtering;
the stripping deamination device (12) is used for stripping deamination;
the first drying and calcining furnace (8) and the second drying and calcining furnace (14) are used for drying and calcining;
the first reduction smelting furnace (9) and the second reduction smelting furnace (15) are used for reduction smelting.
3. The system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixtures according to claim 2, wherein:
the first reaction device (1), the second reaction device (3), the third reaction device (5), the fourth reaction device (7) and the fifth reaction device (10) are one or more of a stirring kettle and a tubular reactor.
4. The system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture according to claim 3, wherein:
the first filtering device (2), the second filtering device (4), the third filtering device (6), the fourth filtering device (11) and the fifth filtering device (13) are one or more of a centrifugal machine, a plate-and-frame filter press, a belt filter and a disc dehydrator.
5. The system for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture according to claim 4, wherein:
the stripping deamination device (12) is formed by combining a preheater, a stripping deamination tower, a condenser and a reboiler.
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| CN114058848A (en) * | 2021-10-09 | 2022-02-18 | 杭州逐真科技有限公司 | System and process for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114058848A (en) * | 2021-10-09 | 2022-02-18 | 杭州逐真科技有限公司 | System and process for recovering copper, nickel, zinc, chromium and iron from electroplating sludge or other multi-metal mixture |
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