CN113174490B - Recycling treatment method for impurity-removing slag generated in nickel sulfate production process - Google Patents
Recycling treatment method for impurity-removing slag generated in nickel sulfate production process Download PDFInfo
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- CN113174490B CN113174490B CN202110369792.XA CN202110369792A CN113174490B CN 113174490 B CN113174490 B CN 113174490B CN 202110369792 A CN202110369792 A CN 202110369792A CN 113174490 B CN113174490 B CN 113174490B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/468—Purification of calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of hazardous waste treatment, and particularly relates to a recycling treatment method of impurity-removing slag generated in a nickel sulfate production process, which comprises the following treatment steps: (1) pulping: removing impurity slag, adding water and pulping to obtain slurry; (2) acid dissolution reduction leaching: heating, sequentially adding a calcium sulfate inhibitor, sodium sulfite and sulfuric acid, controlling the pH value, and reacting for a period of time; (3) washing calcium sulfate: and carrying out solid-liquid separation after reduction leaching to obtain acid-dissolved liquid and unwashed calcium sulfate, carrying out countercurrent washing on the unwashed calcium sulfate to obtain washed calcium sulfate and calcium sulfate washing liquid, drying the washed calcium sulfate, carrying out two-stage precipitation, aeration and the like on the acid-dissolved liquid and the calcium sulfate washing liquid, and returning other waste water to the system for use or producing sodium sulfate after the other waste water is treated by a waste water treatment system. Compared with the method for treating hazardous wastes by a pyrogenic process, the method for treating impurity-removed slag generated in the production process of nickel sulfate has the advantages of large treatment capacity, low energy consumption, no dust, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of hazardous waste treatment, and particularly relates to a resource treatment method for impurity removal slag generated in a nickel sulfate production process.
Background
The production of nickel sulfate belongs to the basic chemical raw material manufacturing industry, and some dangerous wastes are inevitably generated in the production process. The hazardous waste has certain chemical, physical and biological characteristics, and can be circulated into the natural environment only by harmless treatment through a special technology. In recent years, global solid waste disposal and public health impact and border-crossing migration of hazardous wastes have become hot topics, and the problem of hazardous wastes is more severe as the most developing country in china.
With the development of traditional industry and emerging industrial technology, the disposal capacity of solid hazardous waste at home and abroad is gradually improved, but the disposal quantity of the solid hazardous waste is still far lower than the production quantity of the solid hazardous waste in terms of the current disposal technology and the disposal quantity, and the main disposal technologies comprise 3 types of storage and transportation technology, conversion utilization and incineration disposal. At present, the domestic hazardous waste treatment mostly adopts a pyrogenic process (high-temperature calcination) process, the process not only has high energy consumption, but also is accompanied by the generation of a large amount of dust and toxic gases, and meanwhile, if the raw materials contain alkali metal elements in the pyrogenic process treatment process, refractory bricks are corroded, so that the service life of equipment is shortened. Because hydrometallurgical enterprises are not equipped with a fire treatment system usually, solid wastes are generally entrusted to a third party for treatment, the treatment cost is higher, and the hydrometallurgical enterprises generating a large amount of solid hazardous wastes are not favorable for reducing the production cost.
In the prior art, the main production process of nickel sulfate is as follows: nickel enrichment → acid dissolution → impurity removal → extraction → oil removal → evaporative crystallization, wherein the impurity removal process is to avoid introducing Na + 、Mg 2+ Etc., caO, caCO and the like are usually used 3 、Ca(OH) 2 Neutralizing, settling and removing impurities such as ferrum, silicon, aluminum and the like, so that the main component of impurity-removing slag is CaSO 4 Meanwhile, a small amount of heavy metals such as nickel, cobalt, manganese, iron, zinc, chromium and the like are wrapped. Waste residues generated in the impurity removal process belong to HW46 nickel-containing waste according to relevant national regulations, and are generally entrusted to qualified companies for fire harmless disposal. However, the pyrogenic process has high cost, and the treatment capacity of part of the regions is limited, so that the requirement of nickel sulfate on capacity cannot be met.
Therefore, how to dispose the impurity removal slag generated in the nickel sulfate production process with low energy consumption and low cost provides an idea for solving hazardous wastes for nickel sulfate wet production enterprises, and becomes the key point of the current research.
Disclosure of Invention
The invention aims to solve the technical problems, provides a recycling treatment method of impurity-removing slag generated in the nickel sulfate production process, which has large treatment capacity, low energy consumption, no dust and low cost, solves the problems of high treatment cost and no fire treatment facility of the nickel sulfate impurity-removing slag of nickel sulfate wet production enterprises through a simple process, and simultaneously solves the problems of high energy consumption, large dust and toxic gas generation in the fire treatment danger in the prior art.
The technical scheme of the invention is as follows:
a resource disposal method of impurity-removing slag generated in the production process of nickel sulfate comprises the following preparation steps:
(1) Pulping: adding water into impurity-removed slag for pulping to obtain slurry with the mass concentration (namely the mass percentage of the dry basis of the impurity-removed slag in the total mass of the slurry) of 20-50%;
(2) Acid dissolution reduction leaching: heating the slurry to 55-95 ℃, sequentially adding a calcium sulfate inhibitor, sodium sulfite and sulfuric acid, controlling the pH value to be 0.5-1.5, and reacting for 1-4h;
(3) Washing with calcium sulfate: carrying out solid-liquid separation after reduction leaching to obtain acid-dissolved liquid and unwashed calcium sulfate, carrying out countercurrent washing on the unwashed calcium sulfate to obtain washed calcium sulfate and calcium sulfate washing liquid, drying the washed calcium sulfate at a constant temperature of 80-100 ℃ to obtain industrial byproduct gypsum, wherein the detection of the content of harmful substances meets the relevant regulation of hazardous waste identification standard toxic substance content identification (GB 5085.3-2007), the leaching toxicity meets the relevant regulation of Integrated wastewater discharge Standard (GB 8978-1996), and the influence on the cement performance meets the relevant regulation of Industrial byproduct Gypsum for Cement (GB/T21371-2008).
In order to further purify the waste liquid, preferably, in step (3) of the present invention, the post-acid-soluble liquid or the calcium sulfate washing liquid is treated as follows:
s1, first-stage precipitation: adding liquid alkali into the acid-dissolved liquid or calcium sulfate washing liquid obtained in the step (3), firstly adjusting the pH value to 2.5-3.5, keeping the reaction temperature at 65-85 ℃, maintaining the temperature for 0.5-1.5h, then adjusting the pH value to 7.0-8.0, continuing to react for 1-2h, carrying out solid-liquid separation after the reaction is finished to obtain a section of precipitated liquid and an unwashed mixture, adding water into the unwashed mixture to wash the unwashed mixture to obtain a washed mixture and a mixture washing liquid, wherein the main components of the unwashed mixture are zinc hydroxide and goethite, the pH value is adjusted for carrying out goethite method iron removal for the first time, the main component is zinc precipitation and impurity removal in the acid-dissolved liquid for the second time, and the obtained precipitation-washed mixture contains higher nickel and iron components, and can be handed to steel production enterprises to produce ferronickel by a pyrometallurgy to produce steel;
s2, secondary precipitation: adding liquid caustic soda into the first-stage precipitated liquid or the mixture washing liquid, controlling the end point pH value to be 8.5-9.5, controlling the reaction temperature to be 20-85 ℃, introducing air for aeration and oxidation, wherein the aeration and oxidation time is 1-4h, performing solid-liquid separation to obtain unwashed manganese slag and second-stage precipitated liquid, adding water into the unwashed manganese slag for washing to obtain washed manganese slag and manganese slag washing liquid, selling the washed manganese slag serving as a manganese raw material to a manganese series product manufacturer at a fixed point, wherein the main component of the washed manganese slag is manganese dioxide, dissolving the manganese dioxide by acid, adding a reducing agent, and producing manganese salt by the processes of solution impurity removal and the like.
In the step (2), manganese (IV) in the impurity-removed slag is reduced by sodium sulfite, so that high-valence manganese in the impurity-removed slag is reduced to + 2-valence manganese, the high-valence manganese enters into an acid-soluble solution to be separated from calcium sulfate in the impurity-removed slag, the added sulfuric acid and an oxide or hydroxide in the impurity-removed slag are subjected to acid-base neutralization reaction, and the calcium sulfate inhibitor is added to inhibit the dissolution of calcium in the calcium sulfate, so that the separation of calcium sulfate from other impurities in the impurity-removed slag is realized.
In order to purify the waste liquid deeply, in step S2 of the present invention, the two-stage post-precipitation liquid and the manganese slag washing liquid are preferably treated as follows: aerating the second-stage precipitated liquid and the manganese slag washing liquid for 1-16h, adding a flocculating agent, aging and settling, sequentially performing fine filtration and solid-liquid separation by an ultrafiltration device to obtain an aerated liquid, performing electrodialysis on the aerated liquid to obtain brine and fresh water, allowing the brine to enter a sodium sulfate production system to produce sodium sulfate, and returning the fresh water to the production system for use.
Calcium sulfate precipitation is easily generated due to calcium impurities contained in the impurity-removed slag, and when high-valence metal components are subjected to reduction leaching by using sodium sulfite, in order to prevent the calcium sulfate which is generated and precipitated from being re-dissolved into a solution, a calcium sulfate inhibitor is added in the step of acid-soluble reduction leaching. Preferably, the calcium sulfate inhibitor is one of citric acid, polyacrylic acid and polyethylene diacid, the amount of the calcium sulfate inhibitor is 0.5-1.5% of the dry basis weight of the impurity-removed slag, excessive addition of the calcium sulfate inhibitor causes waste, the treatment cost is increased, a part of calcium enters an acid solution and then enters a resource product, so that a part of calcium is contained in a precipitation product (resource product), the production cost of the precipitation product is increased in the process of secondary utilization, the dry basis of the impurity-removed slag is obtained by drying the wet basis of the impurity-removed slag at a constant temperature of 80-100 ℃, the calcium content in a first-stage precipitation and the subsequent resource product is ensured to be low by adding the calcium sulfate inhibitor, the secondary utilization of the resource product is not influenced, for example, if the calcium content in manganese slag delivered to a manganese production enterprise is high, the calcium enters a leachate along with a wet leaching process, and the enterprise needs to additionally increase a calcium removal process in the process of producing the manganese product, the cost is increased, and the production efficiency is reduced.
In order to reduce and leach high-valence metal components, sodium sulfite is added in the acid-soluble reduction leaching step, preferably, the dosage of the sodium sulfite is determined according to the content of manganese elements in the impurity-removed slag, the molar mass ratio of manganese to the sodium sulfite in the impurity-removed slag is 1. Under the same other conditions, if the sodium sulfite excess coefficient is lower than 0.8, calcium sulfate cannot be thoroughly separated from high-valence manganese in the calcium sulfate due to insufficient sodium sulfite dosage, so that the grade of the calcium sulfate is influenced, if the sodium sulfite excess coefficient is larger than 1.5, the sodium sulfite is excessively added, so that the waste of the sodium sulfite is caused, the cost is increased, and in addition, if the excess coefficient is excessively large, sulfur dioxide gas with pungent odor can be generated under the action of strong acid or concentrated acid in the reduction leaching process of the sodium sulfite, so that the environmental quality and the physical health of operators are influenced.
In order to leach out high-valence metal components as much as possible, the mass ratio of the sulfuric acid to the impurity-removed slag dry basis is 0.2-0.6, and the impurity-removed slag dry basis is obtained by drying the wet basis of the impurity-removed slag at a constant temperature of 80-100 ℃. According to the method, the impurity elements can be separated from the calcium sulfate in the impurity-removed slag according to the acid content, particularly the iron and the calcium sulfate can be separated, the iron can be dissolved out completely under the condition that the pH is less than or equal to 1.5, in order to ensure the dissolution of the iron, different amounts of acid are required to be added according to the difference of raw materials to control the pH, the acid dosage is determined according to the difference of the raw materials, but the final pH is less than or equal to 1.5, finally, the iron in the impurity-removed slag is separated from the calcium sulfate as completely as possible, and when the iron is dissolved out completely, other impurities are dissolved out basically before the iron is dissolved out.
In order to precipitate nickel, iron, manganese and other components, liquid alkali is added into the first-stage precipitation and the second-stage precipitation. Preferably, in the steps S1 and S2 of the present invention, the liquid caustic soda has a mass concentration of 10% to 50%. The liquid caustic is usually 50% undiluted liquid caustic concentration, and 10% is obtained by diluting 32% or 50% liquid caustic on the market, namely: the liquid alkali can be dilute liquid alkali or can be directly used for precipitating components such as nickel, iron, manganese and the like without dilution.
In order to effectively settle the solid matters in the liquid after the second-stage precipitation and the manganese slag washing liquid, a flocculating agent is added during aeration. Preferably, the addition amount of the flocculant is 0.5-1.5% of the total weight of the liquid after precipitation and the manganese slag washing liquid, if the flocculant is added too much, raw materials are wasted, the addition amount is not enough, the precipitation rate of the slurry after precipitation is slow, and the high-efficiency treatment of waste liquid is not facilitated.
In the prior art, in order to perform resource utilization in a segmented manner, two treatments are generally performed when one-segment precipitation is performed: (1) The pH value is directly adjusted to 7.0-8.0 at one time without removing iron from goethite, and colloidal precipitate is precipitated and is difficult to filter press; (2) carrying out iron and zinc precipitation by stages: adding an oxidant to oxidize the + 2-valent iron in advance to convert the + 2-valent iron into + 3-valent iron, converting the + 3-valent iron into goethite or other + 3-valent iron compounds by using a precipitator (otherwise, the generated + 2-valent ferrous hydroxide and ferric hydroxide are both colloidal precipitates and are difficult to carry out solid-liquid separation), carrying out primary separation, regulating the pH of the filtrate obtained after the primary separation to precipitate zinc, and having the disadvantages of multiple process steps, waste of manpower and material resources, cost saving and treatment efficiency improvement. However, the invention does not need to add an oxidant, the finally obtained precipitate contains + 2-valent and + 3-valent iron, and the problem of difficult filtration does not exist, specifically, sodium sulfite which is slightly excessive is added in the acid-soluble reduction leaching stage, so that high-valent manganese can be reduced, the + 3-valent iron dissolved in the solution after acid dissolution is partially reduced into + 2-valent iron, the part of the + 2-valent iron can not be completely precipitated during the first pH adjustment, so when the pH is increased by adding alkali for the second time, the rest + 2-valent iron is precipitated together with components such as zinc, and the iron in the final precipitate is + 3-valent goethite, the + 2-valent ferrous hydroxide and the + 3-valent ferric hydroxide.
The flocculating agent is preferably anionic or nonionic polyacrylamide, and the flocculating agent is added to accelerate the sedimentation rate of the liquid after sedimentation and improve the treatment efficiency.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention adopts the combination of processes such as acid dissolution reduction leaching, first-stage precipitation, second-stage precipitation, aeration and the like, can realize the recycling of impurity-removing slag, solves the problem of capability of treating hazardous wastes without fire in wet enterprises, reduces the cost for treating the hazardous wastes without adopting a fire process, does not generate dust and toxic gas, is green and environment-friendly, reduces the requirement on equipment, and is easy to realize.
2. The method adopts a wet method to treat the impurity-removing slag generated in the nickel sulfate production process, so that a resource product can be obtained, the obtained resource product can be recycled, specifically, the content and leaching toxicity of the harmful substances of the obtained calcium sulfate meet the standard, the obtained calcium sulfate can be used as industrial byproduct gypsum to change waste into valuable, the obtained washed mixture is used for smelting ferronickel by a steel production enterprise through a pyrogenic process to produce steel, and the obtained manganese slag is sold to manganese series product manufacturers as a manganese raw material to improve the additional output value of waste.
Drawings
FIG. 1 is a flow chart of steps of a recycling method of impurity-removed slag generated in a nickel sulfate production process in the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
100g of 1# impurity-removed slag (57.2 g of dry basis) is taken, water is added for pulping, the mixture is uniformly stirred, the mass concentration of slurry is 20%, the mixture is heated to 55 ℃, 3.4g of sodium sulfite and 0.8g of polyethylene diacid are sequentially added, 34.3g of concentrated sulfuric acid with the mass fraction of 98% is slowly added, the end point pH =0.5, solid-liquid separation is carried out after 1h of reaction, 1# acid-dissolved liquid and 1# unwashed calcium sulfate are obtained, water with the mass being 4 times that of the wet basis is added into the 1# unwashed calcium sulfate, countercurrent washing is carried out for 3 times, 1# washed calcium sulfate and 1# calcium sulfate washing liquid are obtained, and the 1# washed calcium sulfate is dried at the constant temperature of 80 ℃ to constant weight, so that 1# calcium sulfate is obtained.
Example 2
100g of 1# impurity-removed slag (57.2 g of dry basis) is taken, water is added for pulping, the mixture is uniformly stirred, the mass concentration of slurry is 35%, the mixture is heated to 80 ℃, 5.1g of sodium sulfite and 0.3g of polyacrylic acid are sequentially added, 22.9g of 98% sulfuric acid is slowly added, the end point pH =0.8, solid-liquid separation is carried out after 2h reaction, 2# acid-dissolved liquid and 2# unwashed calcium sulfate are obtained, 3 times of water of the mass of the 2# unwashed calcium sulfate is added into the 2# unwashed calcium sulfate, countercurrent washing is carried out for 4 times, 2# washed calcium sulfate and 2# calcium sulfate washing liquid are obtained, and the 2# washed calcium sulfate is dried at the constant temperature of 90 ℃ to constant weight to obtain 2# calcium sulfate.
Example 3
100g of 1# impurity-removed slag (57.2 g of dry basis) is taken, water is added for pulping, the mixture is uniformly stirred, the mass concentration of the pulp is 50%, the mixture is heated to 95 ℃, 2.7g of sodium sulfite and 0.8g of citric acid are sequentially added, 11.4g of 98% sulfuric acid is slowly added, the end point pH =1.5, solid-liquid separation is carried out after 4 hours of reaction, 3# acid-dissolved liquid and 3# unwashed calcium sulfate are obtained, 5 times of water of the mass of 3# wet basis calcium sulfate is added into 3# unwashed calcium sulfate, 3# washed calcium sulfate and 3# washing liquid are obtained after countercurrent washing, and the calcium sulfate after 3# washing is dried to constant weight at 100 ℃ to obtain 3# calcium sulfate.
The dry basis of the trash residue and the calcium sulfate content in examples 1 to 3 are shown in Table 1.
TABLE 1 content of the dry basis of the impure slag and the calcium sulfate content of the product
| Ni | Co | Mn | Fe | Zn | Al | Ca | Cr | |
| 1# impurity removal residue dry basis (%) | 0.29 | 0.086 | 2.60 | 1.44 | 2.20 | 0.56 | 18.59 | 0.048 |
| 1# calcium sulfate (%) | 0.0032 | 0.0016 | 0.032 | 0.070 | 0.0023 | 0.031 | 22.08 | 0.0052 |
| 2# calcium sulfate (%) | 0.0057 | 0.0019 | 0.019 | 0.045 | 0.0030 | 0.028 | 21.74 | 0.0064 |
| 3# calcium sulfate (%) | 0.0076 | 0.0022 | 0.039 | 0.066 | 0.0035 | 0.033 | 22.12 | 0.0059 |
Note: the No. 1 impurity-removed slag dry basis is obtained by drying the wet basis of the impurity-removed slag at a constant temperature of 90 ℃ to constant weight.
As can be seen from table 1, the acid dissolution reduction leaching of the impurity-removed slag is performed by adding a calcium sulfate inhibitor, sodium sulfite, and concentrated sulfuric acid, and the detection by the method of GB5085.3-2007 shows that the content of harmful substances in calcium sulfate can be significantly reduced, the obtained calcium sulfate meets the standard in "identification of hazardous waste standard toxic substance content identification" (GB 5085.3-2007), and can be used for producing cement, specifically, the detection of leaching toxicity of # 1 calcium sulfate, # 2 calcium sulfate, and # 3 calcium sulfate is shown in table 4.
Example 4
(1) 1kg of 2# impurity-removed slag (555 g of dry basis) is taken, water is added for pulping, the mixture is uniformly stirred, the mass concentration of slurry is 30%, the mixture is heated to 80 ℃, 37.1g of sodium sulfite and 8.3g of citric acid are sequentially added, 222.0g of 98% sulfuric acid is slowly added, the end point pH =0.8, solid-liquid separation is carried out after 4h reaction, 4# acid-dissolved liquid and 4# unwashed calcium sulfate are obtained, 4# unwashed calcium sulfate is added with 4 times of water with wet basis mass, 4# washed calcium sulfate and 4# calcium sulfate washing liquid are obtained after countercurrent washing, the 4# washed calcium sulfate is dried at constant temperature of 100 ℃ to obtain 4# calcium sulfate dry basis, and the 4# calcium sulfate washing liquid is returned to be mixed with new impurity-removed slag for pulping;
(2) Adding liquid alkali with the mass concentration of 10% into the 4# acid-dissolved solution, firstly adjusting the pH value to 2.5, keeping the temperature of the system at 65 ℃, reacting for 0.5h, continuously adding the liquid alkali with the same concentration, adjusting the pH value to 7.0, continuously reacting for 1h, carrying out solid-liquid separation after the reaction is finished to obtain a 4# unwashed mixture and a 4# primary precipitation solution, adding water into the 4# unwashed mixture, pulping and washing to obtain a 4# mixture washing solution and a 4# washed mixture;
(3) Adding liquid alkali with the mass concentration of 10% into the 4# primary precipitated liquid at the temperature of 20 ℃, introducing air for aeration oxidation and manganese precipitation, controlling the pH value to be 8.5 in the precipitation process, carrying out aeration oxidation for 16h, carrying out solid-liquid separation to obtain 4# secondary precipitated liquid and 4# unwashed manganese slag, and washing the 4# unwashed manganese slag with water to obtain 4# manganese slag washing liquid and 4# washed manganese slag;
(4) Aerating the 4# second-stage precipitated liquid and the 4# manganese slag washing liquid for 1h, adding 1.5% of nonionic polyacrylamide accounting for the total weight of the 4# manganese slag washing liquid and the 4# second-stage precipitated liquid, aging and precipitating for 4h, sequentially performing solid-liquid separation by a fine filtration and ultrafiltration device to obtain the 4# aerated liquid, performing electrodialysis on the 4# aerated liquid to obtain brine and fresh water, allowing the brine to enter a sodium sulfate production system to produce sodium sulfate, and returning the fresh water to the production system for use.
The components of the 2# impurity-removing slag, the 4# acid-dissolved liquid, the 4# calcium sulfate dry base, the 4# washed mixture dry base, the 4# primary precipitation liquid, the 4# washed manganese slag dry base, the 4# secondary precipitation liquid and the 4# aeration liquid are shown in the table 2, and the 4# calcium sulfate leaching toxicity test is shown in the table 4.
Table 2 example 4 product composition content at different stages
| Ni | Co | Mn | Fe | Zn | Al | Ca | Cr | |
| 2# impurity removal slag dry basis (%) | 0.34 | 0.12 | 1.95 | 2.16 | 1.31 | 0.60 | 19.06 | 0.033 |
| Post-acid-soluble solution (g/L) | 1.15 | 0.40 | 6.52 | 7.30 | 4.41 | 2.01 | 0.017 | 0.37 |
| 4# calcium sulfate Dry basis (%) | 0.0035 | 0.0009 | 0.027 | 0.041 | 0.0026 | 0.042 | 22.13 | 0.0061 |
| No. 4 first-stage precipitation solution (g/L) | 0.57 | 0.16 | 6.01 | 0.0015 | 0.40 | 0.0001 | 0.015 | 0.0001 |
| 4# mixture after washing dry basis (%) | 2.95 | 0.93 | 0.32 | 12.22 | 6.67 | 3.39 | 0.010 | 0.62 |
| 4# two-stage post-precipitation solution (mg/L) | 0.2 | 0.2 | 0.7 | 0.1 | 0.2 | 0.1 | 1.1 | 0.05 |
| 4# post-wash manganese slag dry basis (%) | 0.31 | 0.23 | 35.01 | 0.021 | 2.33 | - | - | - |
| Aeration back liquid No. 4 (mg/L) | 0.04 | 0.05 | 0.5 | 0.1 | 0.1 | 0.1 | 1.0 | 0.01 |
Note: the dry bases mentioned in the above table are all obtained by drying the corresponding wet bases to constant weight at a constant temperature of 100 ℃.
Example 5
(1) Taking 500kg of No. 2 impurity-removed slag (275 kg of dry basis), adding water for pulping, uniformly stirring, heating the slurry to the concentration of 20%, sequentially adding 9.83kg of sodium sulfite and 1.37kg of citric acid, then slowly adding 165kg of 98% sulfuric acid, wherein the final pH is =0.5, reacting for 4 hours, then carrying out solid-liquid separation to obtain 5# acid-soluble solution and 5# unwashed calcium sulfate, adding 4 times of water with wet basis mass into 5# unwashed calcium sulfate, carrying out countercurrent washing for 4 times to obtain 5# washed calcium sulfate and 5# calcium sulfate washing solution, drying the 5# washed calcium sulfate at the constant temperature of 100 ℃ to obtain 5# calcium sulfate dry basis, and returning the 5# calcium sulfate washing solution to be mixed with new impurity-removed slag for pulping;
(2) Adding liquid caustic soda with the mass concentration of 50% into the 5# acid-dissolved solution and the calcium sulfate washing solution, firstly adjusting the pH value to be 3.5, keeping the system temperature at 85 ℃, reacting for 1.5h, continuously adding the liquid caustic with the same concentration, adjusting the pH value to be 8.0, reacting for 1.5h, then carrying out solid-liquid separation to obtain a 5# unwashed mixture and a 5# primary precipitation solution, adding water into the 5# unwashed mixture for slurrying and washing to obtain a 5# mixture washing solution and a 5# washed mixture;
(3) Adding liquid caustic soda with the mass concentration of 50% into the first-stage precipitated 5# solution at 85 ℃, introducing air for aeration oxidation to precipitate manganese, controlling the pH to be 9.5 in the precipitation process, carrying out aeration oxidation for 4 hours, carrying out solid-liquid separation to obtain second-stage precipitated 5# solution and 5# unwashed manganese slag, and washing the 5# unwashed manganese slag with water to obtain 5# manganese slag washing solution and 5# washed manganese slag;
(4) Aerating the 5# two-stage precipitated liquid and the 5# manganese slag washing liquid for 16h, adding anionic polyacrylamide accounting for 0.5% of the total weight of the 5# manganese slag washing liquid and the 5# two-stage precipitated liquid, aging and precipitating for 2h, sequentially performing solid-liquid separation by a fine filtration and ultrafiltration device to obtain the 5# aerated liquid, performing electrodialysis on the 5# aerated liquid to obtain saline water and fresh water, allowing the saline water to enter a sodium sulfate production system to produce sodium sulfate, and returning the fresh water to the production system for use.
The components of the 2# impurity-removing slag, the 5# acid-soluble liquid plus the 5# calcium sulfate washing liquid, the 5# calcium sulfate dry basis, the 5# washed mixture dry basis, the 5# primary precipitation liquid, the 5# washed manganese slag dry basis, the 5# secondary precipitation liquid and the 5# aeration liquid are shown in table 3, and the 5# calcium sulfate leaching toxicity detection is shown in table 4.
Table 3 example 5 content of ingredients of the product at different stages
Note: the dry bases mentioned in the table above are all obtained by drying the corresponding wet bases at a constant temperature of 80 ℃ to a constant weight.
It can be seen from tables 2 and 3 that the purpose of the first-stage precipitation is mainly to remove iron, precipitate zinc and precipitate part of nickel and cobalt, and from the component contents of the first-stage precipitation solution and the acid-dissolved solution, the contents of iron and zinc in the first-stage precipitation solution are significantly reduced, and the contents of nickel, cobalt and the like are correspondingly reduced, and in addition, because the pH values of the complete precipitation of aluminum and chromium are about 4.7 and 5.6 respectively, when the pH value is adjusted to 7.0-8.0 and the temperature is adjusted to 20-85 ℃, the aluminum and chromium are already basically and completely precipitated. The purpose of the second-stage precipitation is to precipitate the nickel, cobalt and manganese which are not completely precipitated in the first-stage precipitation, and the generated precipitated manganese hydroxide is oxidized into manganese dioxide mainly by aeration oxidation, so that the content of all impurity components in the liquid after the second-stage precipitation is obviously reduced, and the wastewater discharge standard is reached. The calcium sulfate and manganese slag obtained by the method has low impurity content, wherein the purity of the calcium sulfate reaches over 75 percent, and the purity of the manganese dioxide reaches over 60 percent, so that the calcium sulfate and manganese slag can be used for secondary use, and the resource treatment is realized.
Table 4 identification of leaching toxicity of calcium sulfate in examples 1 to 5: sulfuric acid nitric acid method (leachate component mg/L)
From table 4, it can be seen that the leaching toxicity of the calcium sulfate obtained in examples 1 to 5 is compared with "identification standard for hazardous waste toxic substance content identification" (GB 5085.3-2007) and the toxic substance content meets the standard, so it can be seen that the solid substance calcium sulfate obtained in the present invention does not belong to hazardous waste, and the impurity-removed slag is effectively recycled.
The parts not mentioned in the above examples were carried out according to the conventional art.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (9)
1. A resource treatment method for impurity removal slag generated in a nickel sulfate production process is characterized by comprising the following treatment steps:
(1) Pulping: adding water into the impurity-removed slag for pulping to obtain slurry with the mass concentration of 20-50%;
(2) Acid dissolution reduction leaching: heating the slurry to 55-95 ℃, sequentially adding a calcium sulfate inhibitor, sodium sulfite and sulfuric acid, controlling the pH value to be 0.5-1.5, and reacting for 1-4h, wherein the calcium sulfate inhibitor is one of citric acid, polyacrylic acid and polyethylene diacid, and the dosage of the calcium sulfate inhibitor is 0.5-1.5% of the dry basis weight of the impurity-removed slag;
(3) Washing with calcium sulfate: and carrying out solid-liquid separation after reduction leaching to obtain an acid-dissolved solution and unwashed calcium sulfate, carrying out countercurrent washing on the unwashed calcium sulfate to obtain washed calcium sulfate and a calcium sulfate washing solution, and drying the washed calcium sulfate.
2. The method for recycling the impurity-removed slag generated in the production process of nickel sulfate according to claim 1, which is characterized in that: in the step (3), the acid-dissolved solution or the calcium sulfate washing solution is treated as follows:
s1, first-stage precipitation: adding liquid alkali into the acid-dissolved liquid or calcium sulfate washing liquid obtained in the step (3), firstly adjusting the pH value to 2.5-3.5, keeping the reaction temperature at 65-85 ℃, maintaining the temperature for 0.5-1.5h, continuously adding the liquid alkali to adjust the pH value to 7.0-8.0, reacting for 1-2h, carrying out solid-liquid separation after the reaction is finished to obtain a section of precipitated liquid and an unwashed mixture, and adding water into the unwashed mixture to wash the unwashed mixture to obtain a washed mixture and a washing liquid mixture;
s2, secondary precipitation: adding liquid caustic soda into the first-stage precipitated liquid or the mixture washing liquid, controlling the end point pH value to be 8.5-9.5, controlling the reaction temperature to be 20-85 ℃, introducing air for aeration and oxidation, carrying out solid-liquid separation to obtain unwashed manganese slag and second-stage precipitated liquid, and washing the unwashed manganese slag by adding water to obtain washed manganese slag and manganese slag washing liquid.
3. The method for recycling the impurity-removed slag generated in the nickel sulfate production process according to claim 2, characterized in that: in the step S2, the two-stage post-precipitation solution and the manganese slag washing solution are subjected to the following wastewater treatment: aerating the second-stage precipitated liquid and the manganese slag washing liquid for 1-16h, adding a flocculating agent, aging and settling, sequentially performing fine filtration and solid-liquid separation by an ultrafiltration device to obtain an aerated liquid, performing electrodialysis on the aerated liquid to obtain brine and fresh water, allowing the brine to enter a sodium sulfate production system to produce sodium sulfate, and returning the fresh water to the production system for use.
4. The method for recycling the impurity-removed slag generated in the production process of nickel sulfate according to claim 1, which is characterized in that: the sodium sulfite dosage is standard dosage according to the molar mass ratio of 1.
5. The method for recycling the impurity-removed slag generated in the production process of nickel sulfate according to claim 1, which is characterized in that: the mass ratio of the sulfuric acid to the impurity-removed slag dry basis in the step (2) is 0.2-0.6.
6. The method for recycling the impurity-removed slag generated in the production process of nickel sulfate according to claim 2, which is characterized in that: in the steps S1 and S2, the mass concentration of the liquid caustic soda is 10-50%.
7. A resource treatment method of impurity-removed slag generated in the nickel sulfate production process according to claim 3, which is characterized in that: the addition amount of the flocculating agent is 0.5-1.5% of the total weight of the liquid after precipitation and the manganese slag washing liquid.
8. The method for recycling the impurity-removed slag generated in the production process of nickel sulfate according to claim 7, which comprises the following steps: the flocculant is anionic or nonionic polyacrylamide.
9. The method for recycling the impurity-removed slag generated in the nickel sulfate production process according to claim 1 or 5, which is characterized in that: the dry base of the impurity-removing slag is obtained by drying the wet base of the impurity-removing slag at a constant temperature of 80-100 ℃.
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