CN111621644A - Treatment method of electroplating sludge - Google Patents
Treatment method of electroplating sludge Download PDFInfo
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- CN111621644A CN111621644A CN202010477657.2A CN202010477657A CN111621644A CN 111621644 A CN111621644 A CN 111621644A CN 202010477657 A CN202010477657 A CN 202010477657A CN 111621644 A CN111621644 A CN 111621644A
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention relates to a treatment method of electroplating sludge, which comprises the following steps: (1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; (2) carrying out membrane separation on the pickle liquor obtained in the step (1) to obtain sulfuric acid and concentrated liquor; (3) carrying out alkaline leaching on the acid leaching residue obtained in the step (1), and carrying out solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; (4) electrolyzing the alkali leaching solution obtained in the step (3) to obtain sulfuric acid and alkali liquor. The treatment method combines the acid leaching method with the membrane separation method, so that the concentration of valuable metals in the acid leaching solution is improved, and the subsequent treatment of the valuable metals is facilitated; in addition, the treatment method provided by the invention does not additionally generate waste liquid, the acid liquid and the alkali liquid generated in the treatment process can be reused in the treatment process, and the generated calcium hydroxide can be used in other processes; the treatment method is generally environmentally friendly.
Description
Technical Field
The invention belongs to the technical field of waste solid treatment, relates to a waste solid treatment method, and particularly relates to a treatment method of electroplating sludge.
Background
The electroplating industry is an important industrial industry in China and plays an important role in national economy. The electroplating sludge contains a large amount of heavy metals, and if the heavy metals enter the environment, the electroplating sludge causes great harm to the environment. At present, the following methods are roughly used for treating and disposing the electroplating sludge: (1) used for making bricks or used as a raw material of cement; (2) carrying out pyrometallurgical treatment; (3) acid leaching method; (4) ammonia leaching method.
When the electroplating sludge is used for making bricks or used as a raw material of cement, valuable metals such as Cu, Ni and Zn in the electroplating sludge cannot be recovered; the copper-nickel product obtained by pyrogenic recovery has low added value and the process is not environment-friendly; the ammonia leaching method requires the use of ammonia water, which is a volatile gas with a strong pungent odor, and seriously affects the working environment.
The acid leaching method is the hottest and most mature process for comprehensively recycling valuable metals from electroplating sludge, and CN102417987A discloses a method for recycling the valuable metals from the electroplating sludge, wherein the method takes the electroplating sludge as a raw material, comprehensively uses the leaching principle, the oxidation reduction principle, the extraction principle, the scrap iron replacement principle, the evaporative crystallization principle and other theories and means in hydrometallurgy, adopts the processes of acid decomposition of the electroplating sludge, purification of leaching solution for removing ferrochromium, purification of P204 for removing impurities, enrichment of P507 and concentrated crystallization, and simultaneously adopts the method for extracting and removing calcium and magnesium to remove calcium and magnesium to replace the traditional sodium fluoride for removing calcium and magnesium. Although the method can recover valuable metals in the electroplating sludge, the process flow is complex, the content of the valuable metals in the electroplating sludge is low, and the recovery rate of the valuable metals is low.
CN 105907972A discloses a method for comprehensively recovering various valuable metals from electroplating sludge, which comprises an oxidation slurrying process, a P204 saponification leaching process, a nickel anolyte total stripping process, an iron stripping and hydrochloric acid regeneration process, a copper extraction electrodeposition process, a chromium deposition process, a P204 nickel soap process, a P204 zinc extraction electrodeposition process, a nickel electrodeposition process, a calcium-nickel separation process, a calcium-magnesium separation process and an industrial circulating water treatment process. The method for enriching and separating multiple valuable metals in the electroplating sludge step by step requires the use of a large amount of extracting agent and the use of oxidant, the extracting agent wastewater generated in the extraction process is difficult to treat, the energy consumption is high, and the burden of treating the electroplating sludge is increased.
CN 108754150A discloses a method for comprehensively recovering valuable metals in electroplating sludge, which comprises the following steps: leaching valuable metals in the electroplating sludge, and separating acid leaching slag and acid leaching solution; adding iron powder into the pickle liquor, stirring the iron powder, and separating to obtain copper powder and mother liquor; adding hydrogen peroxide and a sodium carbonate solution into the mother liquor, adding a composite flocculant to enable iron ions in the solution to form ferric hydroxide precipitates and chromium ions to form chromium hydroxide precipitates and quickly settle down, and separating out chromium-iron slag and the mother liquor containing zinc and nickel; extracting zinc in the mother liquor containing zinc and nickel by using a P507 extracting agent, carrying out sulfuric acid back extraction on an organic phase to obtain a zinc sulfate solution, and crystallizing the zinc sulfate solution to obtain zinc sulfate heptahydrate; adding sodium hydroxide solution into the nickel-containing raffinate, filtering to obtain nickel hydroxide precipitate, and crystallizing the filtrate to obtain sodium sulfate.
The method needs more agents, improves the cost of comprehensively recovering valuable metals, and has adverse effect on the recovery of the valuable metals due to the existence of a large amount of calcium ions in the electroplating sludge.
Therefore, the method which is simple in process and capable of reducing the difficulty in recovering valuable metals in the electroplating sludge is provided, the treatment cost of the electroplating sludge is favorably reduced, and the treatment process of the electroplating sludge is environment-friendly.
Disclosure of Invention
The invention aims to provide a treatment method of electroplating sludge, which combines an acid leaching method with a membrane separation method, improves the concentration of valuable metals in acid leaching solution, and is beneficial to the subsequent treatment of the valuable metals; in addition, the treatment method provided by the invention does not additionally generate waste liquid, the acid liquid and the alkali liquid generated in the treatment process can be reused in the treatment process, and the generated calcium hydroxide can be used in other processes; the treatment method is generally environmentally friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a treatment method of electroplating sludge, which comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue;
(2) carrying out membrane separation on the pickle liquor obtained in the step (1) to obtain sulfuric acid and concentrated liquor;
(3) carrying out alkaline leaching on the acid leaching residue obtained in the step (1), and carrying out solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue;
(4) electrolyzing the alkali leaching solution obtained in the step (3) to obtain sulfuric acid and alkali liquor.
The invention firstly uses sulfuric acid to dissolve soluble components in the electroplating sludge, and deposits calcium in the electroplating sludge in the form of calcium sulfate in acid leaching residue. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Preferably, the sulfuric acid obtained in the step (2) is recycled for the acid leaching treatment in the step (1).
Preferably, the sulfuric acid obtained in the step (4) is recycled for the acid leaching treatment in the step (1).
Preferably, the sulfuric acid obtained in the step (2) is mixed with the sulfuric acid obtained in the step (4) and then is recycled for the acid leaching treatment in the step (1).
The invention recycles the sulfuric acid obtained by electrolysis and/or the sulfuric acid obtained by nanofiltration for acid leaching of electroplating sludge, so that no additional waste liquid is generated in the treatment method.
Preferably, the lye obtained in step (4) is reused for the alkaline leaching in step (3).
Preferably, the temperature of the acid leaching treatment in step (1) is 10-30 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the concentration of the sulfuric acid in step (1) is 1 to 10 wt.%, for example 1 wt.%, 3 wt.%, 5 wt.%, 7 wt.%, 8 wt.% or 10 wt.%, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the liquid-solid ratio of the sulfuric acid to the electroplating sludge in the step (1) is (2-3):1, for example, 2:1, 2.2:1, 2.5:1, 2.7:1, 2.8:1 or 3:1, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable, and the unit of the liquid-solid ratio is mL/g.
In the present invention, the acid leaching treatment in step (1) is performed for dissolving soluble components in the plating sludge, and the acid leaching treatment is performed for a time period until the plating sludge is not dissolved. Preferably, the acid leaching treatment in step (1) of the present invention is performed under the ultrasonic wave-assisted condition.
Preferably, the solid-liquid separation method in step (1) comprises filtration and/or centrifugation.
Preferably, the membrane separation method in step (2) is nanofiltration.
Preferably, the membrane used in the membrane separation in the step (2) is an acid-resistant nanofiltration membrane.
The method uses an acid-resistant nanofiltration membrane to carry out nanofiltration on the pickle liquor obtained in the step (1), sulfate ions and hydrogen ions pass through the membrane, and valuable metal ions are intercepted, so that the separation of sulfuric acid and valuable metals is realized.
Preferably, the alkali solution used in the alkaline leaching in the step (3) comprises a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the alkaline solution used in the alkaline leaching in step (3) has a concentration of 5 to 10 wt%, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the ratio of the alkaline leach solution to the acid leaching residue in the alkaline leaching in the step (3) to the liquid-solid ratio is (2-3):1, and may be, for example, 2:1, 2.2:1, 2.5:1, 2.7:1, 2.8:1 or 3:1, but is not limited to the values listed, and other values not listed in the range of values are also applicable, and the unit of the liquid-solid ratio is mL/g.
Preferably, the solid-liquid separation method in step (3) comprises filtration and/or centrifugation.
Preferably, the electrolysis in the step (4) is bipolar membrane electrolysis.
The method utilizes a bipolar membrane electrolysis method to treat the alkaline leaching solution obtained in the step (3) and recycles the obtained sulfuric acid and alkaline solution, so that no waste liquid is generated in the treatment method. The device and method for the bipolar membrane electrolysis are conventional in the field, and the invention is not limited to a great extent.
Preferably, the concentration of the sulfuric acid obtained in step (4) is 3 to 8% by weight, and may be, for example, 3%, 4%, 5%, 6%, 7% or 8% by weight, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
Preferably, the concentration of the lye of step (4) is in the range of 3 to 8% by weight, and may for example be 3%, 4%, 5%, 6%, 7% or 8% by weight, but is not limited to the values recited and other values not recited in the numerical ranges are equally applicable.
As a preferable technical solution of the treatment method of the present invention, the treatment method comprises the steps of:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 1-10 wt% at the temperature of 10-30 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is (2-3) to 1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline liquor with the concentration of 5-10 wt% is used for alkaline leaching of the acid leaching residue obtained in the step (1), and an alkaline leaching solution and the alkaline leaching residue are obtained after solid-liquid separation; the ratio of alkali leaching solution to acid leaching residue to liquid to solid for alkali leaching is (2-3) to 1, and the unit of the liquid to solid ratio is mL/g;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain 3-8 wt% sulfuric acid and 3-8 wt% alkali liquid;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the alkali liquor obtained in the step (4) for the alkali leaching in the step (3).
Compared with the prior art, the invention has the following beneficial effects:
(1) the method comprises the steps of firstly dissolving soluble components in the electroplating sludge by using sulfuric acid, precipitating calcium in the electroplating sludge in the form of calcium sulfate in acid leaching residues, then recovering the sulfuric acid by membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis.
(2) The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Drawings
FIG. 1 is a process flow diagram of a method for treating electroplating sludge according to the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a treatment method of electroplating sludge, and the process flow chart of the treatment method is shown in figure 1, and the treatment method comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 5 wt% at the temperature of 20 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 2.5:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline leaching the acid leaching residue obtained in the step (1) by using a sodium hydroxide solution with the concentration of 8 wt%, and performing solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali leaching solution to acid leaching residue to liquid-solid for alkali leaching is 2.5:1, and the unit of the liquid-solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain sulfuric acid with the concentration of 5 wt% and sodium hydroxide solution with the concentration of 5 wt%;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the sodium hydroxide solution obtained in the step (4) in the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, and calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Example 2
The embodiment provides a treatment method of electroplating sludge, which comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using 3 wt% sulfuric acid at the temperature of 25 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 2.7:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) carrying out alkaline leaching on the acid leaching residue obtained in the step (1) by using a sodium hydroxide solution with the concentration of 9 wt%, and carrying out solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali leaching solution to acid leaching residue to liquid-solid for alkali leaching is 2.3:1, and the unit of the liquid-solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain sulfuric acid with the concentration of 4 wt% and sodium hydroxide solution with the concentration of 4 wt%;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the sodium hydroxide solution obtained in the step (4) in the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, and calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Example 3
The embodiment provides a treatment method of electroplating sludge, which comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 7 wt% at 15 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 2.2:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline leaching the acid leaching residue obtained in the step (1) by using a sodium hydroxide solution with the concentration of 6 wt%, and performing solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali leaching solution to acid leaching residue to liquid-solid for alkali leaching is 2.7:1, and the unit of the liquid-solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain sulfuric acid with the concentration of 6 wt% and sodium hydroxide solution with the concentration of 6 wt%;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the sodium hydroxide solution obtained in the step (4) in the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, and calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Example 4
The embodiment provides a treatment method of electroplating sludge, which comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 10 wt% at the temperature of 10 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 2:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline leaching the acid leaching residue obtained in the step (1) by using a potassium hydroxide solution with the concentration of 5 wt%, and performing solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali immersion liquid to acid leaching residue to liquid to solid is 3:1, and the unit of the liquid to solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain sulfuric acid with the concentration of 8 wt% and potassium hydroxide solution with the concentration of 8 wt%;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) recycling the potassium hydroxide solution obtained in the step (4) for the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, and calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Example 5
The embodiment provides a treatment method of electroplating sludge, which comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 1 wt% at the temperature of 30 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 3:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline leaching the acid leaching residue obtained in the step (1) by using a potassium hydroxide solution with the concentration of 10 wt%, and performing solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali leaching solution to acid leaching residue to liquid-solid ratio for alkali leaching is 2:1, and the unit of the liquid-solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain 3 wt% sulfuric acid and 3 wt% potassium hydroxide solution;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) recycling the potassium hydroxide solution obtained in the step (4) for the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, and calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
Example 6
The embodiment provides a treatment method of electroplating sludge, which comprises the following steps:
(1) under the condition of ultrasonic wave assistance, carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 5 wt% at 20 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is 2.5:1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline leaching the acid leaching residue obtained in the step (1) by using a sodium hydroxide solution with the concentration of 8 wt%, and performing solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue; the ratio of alkali leaching solution to acid leaching residue to liquid-solid for alkali leaching is 2.5:1, and the unit of the liquid-solid ratio is mL/g; the alkaline leaching residue is calcium hydroxide;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain sulfuric acid with the concentration of 5 wt% and sodium hydroxide solution with the concentration of 5 wt%;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the sodium hydroxide solution obtained in the step (4) in the alkaline leaching in the step (3).
In the embodiment, firstly, sulfuric acid is used for dissolving soluble components in the electroplating sludge, calcium in the electroplating sludge is precipitated in acid leaching residue in the form of calcium sulfate, and the ultrasonic-assisted use promotes the dissolution of ions in the electroplating sludge. Then, recovering sulfuric acid through membrane separation and recovery, and enriching valuable metal elements; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
In conclusion, the soluble components in the electroplating sludge are dissolved by using sulfuric acid, calcium in the electroplating sludge is precipitated in acid leaching residues in the form of calcium sulfate, and then the sulfuric acid is recovered through membrane separation recovery, so that valuable metal elements are enriched; the acid leaching residue realizes the recovery of calcium element and the recycling of acid and alkali through the operation of alkaline leaching and electrolysis. The treatment method provided by the invention can realize the recovery of valuable metals in the electroplating sludge, and the whole process flow of the treatment method is free from waste liquid through the cooperation of electrolysis, so that the treatment method is environment-friendly.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The treatment method of the electroplating sludge is characterized by comprising the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue;
(2) carrying out membrane separation on the pickle liquor obtained in the step (1) to obtain sulfuric acid and concentrated liquor;
(3) carrying out alkaline leaching on the acid leaching residue obtained in the step (1), and carrying out solid-liquid separation to obtain an alkaline leaching solution and an alkaline leaching residue;
(4) electrolyzing the alkali leaching solution obtained in the step (3) to obtain sulfuric acid and alkali liquor.
2. The process according to claim 1, wherein the sulfuric acid obtained in step (2) is reused for the acid leaching treatment in step (1);
preferably, the sulfuric acid obtained in the step (4) is recycled for the acid leaching treatment in the step (1);
preferably, the sulfuric acid obtained in the step (2) is mixed with the sulfuric acid obtained in the step (4) and then is recycled for the acid leaching treatment in the step (1).
3. The process according to claim 1 or 2, characterized in that the lye obtained in step (4) is reused for the alkaline leaching in step (3).
4. The process according to any one of claims 1 to 3, wherein the temperature of the acid leaching treatment in step (1) is 10 to 30 ℃;
preferably, the concentration of the sulfuric acid in the step (1) is 1 to 10 wt%.
5. The treatment method according to claim 4, wherein the liquid-solid ratio of the sulfuric acid to the electroplating sludge in the step (1) is (2-3) to 1, and the unit of the liquid-solid ratio is mL/g;
preferably, the solid-liquid separation method in step (1) comprises filtration and/or centrifugation.
6. The process according to any one of claims 1 to 5, wherein the membrane separation method of step (2) is nanofiltration;
preferably, the membrane used in the membrane separation in the step (2) is an acid-resistant nanofiltration membrane.
7. The process according to any one of claims 1 to 6, wherein the alkaline solution used in the alkaline leaching in step (3) comprises a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the concentration of the alkali liquor used in the alkaline leaching in the step (3) is 5-10 wt%;
preferably, the ratio of alkali leaching solution to acid leaching residue to liquid-solid in the alkali leaching in the step (3) is (2-3) to 1, and the unit of the liquid-solid ratio is mL/g;
preferably, the solid-liquid separation method in step (3) comprises filtration and/or centrifugation.
8. The process according to any one of claims 1 to 6, wherein the electrolysis of step (4) is bipolar membrane electrolysis.
9. The process according to any one of claims 1 to 8, wherein the concentration of the sulfuric acid obtained in step (4) is from 3 to 8 wt%;
preferably, the concentration of the alkali liquor in the step (4) is 3-8 wt%.
10. The process according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) carrying out acid leaching treatment on the electroplating sludge by using sulfuric acid with the concentration of 1-10 wt% at the temperature of 10-30 ℃, and carrying out solid-liquid separation to obtain acid leaching solution and acid leaching residue; the liquid-solid ratio of the sulfuric acid to the electroplating sludge is (2-3) to 1, and the unit of the liquid-solid ratio is mL/g;
(2) carrying out nanofiltration on the pickle liquor obtained in the step (1) by using an acid-resistant nanofiltration membrane to obtain sulfuric acid and concentrated liquor;
(3) alkaline liquor with the concentration of 5-10 wt% is used for alkaline leaching of the acid leaching residue obtained in the step (1), and an alkaline leaching solution and the alkaline leaching residue are obtained after solid-liquid separation; the ratio of alkali leaching solution to acid leaching residue to liquid to solid for alkali leaching is (2-3) to 1, and the unit of the liquid to solid ratio is mL/g;
(4) electrolyzing the alkali immersion liquid obtained in the step (3) by using a bipolar membrane to obtain 3-8 wt% sulfuric acid and 3-8 wt% alkali liquid;
mixing the sulfuric acid obtained in the step (2) with the sulfuric acid obtained in the step (4) and then reusing the mixed sulfuric acid for acid leaching treatment in the step (1); and (5) reusing the alkali liquor obtained in the step (4) for the alkali leaching in the step (3).
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| JPH11269699A (en) * | 1998-03-24 | 1999-10-05 | Kawasaki Steel Corp | Treatment of sludge |
| US6110349A (en) * | 1998-03-25 | 2000-08-29 | Kawasaki Steel Corporation | Method for recovering metallic tin from electroplating sludge |
| CN105217582A (en) * | 2014-06-20 | 2016-01-06 | 王鹏 | The method of a kind of titanium white waste acid film process |
| CN107287428A (en) * | 2017-07-05 | 2017-10-24 | 盛隆资源再生（无锡）有限公司 | A kind of method that Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN111172390A (en) * | 2020-02-06 | 2020-05-19 | 中国恩菲工程技术有限公司 | Method for treating valuable metal sulfide concentrate by oxygen pressure |
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2020
- 2020-05-29 CN CN202010477657.2A patent/CN111621644A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269699A (en) * | 1998-03-24 | 1999-10-05 | Kawasaki Steel Corp | Treatment of sludge |
| US6110349A (en) * | 1998-03-25 | 2000-08-29 | Kawasaki Steel Corporation | Method for recovering metallic tin from electroplating sludge |
| CN105217582A (en) * | 2014-06-20 | 2016-01-06 | 王鹏 | The method of a kind of titanium white waste acid film process |
| CN107287428A (en) * | 2017-07-05 | 2017-10-24 | 盛隆资源再生（无锡）有限公司 | A kind of method that Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN111172390A (en) * | 2020-02-06 | 2020-05-19 | 中国恩菲工程技术有限公司 | Method for treating valuable metal sulfide concentrate by oxygen pressure |
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