Cascaded generation and classified resource utilization of manganese slag

Abstract

The present invention discloses a method for the stepwise generation and classified resource utilization of manganese slag. It belongs to the technical field of industrial waste slag utilization. The present invention uses manganese ore as raw material, and utilizes leaching, neutralization precipitation and step-by-step sulfidation precipitation and filtration operations alternately to stepwise generate and separate acid leaching slag, neutralization slag, zinc sulfide, cobalt-nickel-manganese sulfide, and obtain purified manganese sulfate liquid at the same time. The acid leaching slag and neutralization slag are used to prepare calcium sulfate, molecular sieve and cement clinker respectively. The present invention generates manganese slag in steps and purifies the leaching liquid in steps, which solves the problem that different components are difficult to utilize as resources after mixing. The method is easy to operate, has mild reaction conditions, and has high added value of products, and has good industrial application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial waste slag utilization, and in particular to a method for stepwise generation and classified resource utilization of manganese slag. Background Art

[0002] my country is the world's largest producer, consumer and exporter of manganese products, with electrolytic manganese production accounting for more than 97% of global production. Manganese and its compounds, as important basic raw materials, are widely used in metallurgy, chemical industry, electronic information and other fields. In the past 20 years, my country's manganese industry has made rapid progress. While developing rapidly, it has also caused serious environmental pollution problems, among which manganese slag pollution is particularly prominent. The national ecological environment standard "Technical Specifications for Manganese Slag Pollution Control" (HJ1241-2022) came into effect on October 1, 2022. This standard puts forward specific requirements for strengthening the prevention and control of pollution throughout the manganese slag process. Therefore, manganese slag pollution control has become an urgent problem to be solved in the manganese industry.

[0003] Manganese slag primarily originates from the acid leaching of manganese ore during the production of electrolytic manganese, electrolytic manganese dioxide, and manganese sulfate. This includes the acid leaching residue from manganese ore, the neutralization precipitate residue from the neutralization and precipitation of the leachate, and the organic sulfides from the sulfide precipitation purification process. Existing production processes typically perform acid leaching, neutralization precipitation, and sulfide precipitation sequentially within the same combining tank, resulting in a mixture of acid leaching residue, neutralization precipitate residue, and organic sulfides. The acid leaching residue primarily consists of unleached quartz and other gangue from the manganese ore, the neutralization precipitate residue primarily consists of calcium sulfate and ferric hydroxide, and the organic sulfides primarily consist of dimethyldithiocarbamates of heavy metals such as cobalt and nickel. Furthermore, the residual water after filter pressing also contains soluble manganese, magnesium, and ammonium salts. Consequently, manganese slag primarily consists of gypsum, quartz, and soluble manganese, magnesium, and ammonium salts, along with small amounts of heavy metals such as cobalt and nickel. Its complex composition makes it difficult to process and recycle.

[0004] In recent years, many scholars have conducted beneficial explorations on the harmless treatment and resource utilization of manganese slag, and designed and developed some effective utilization methods. At present, the treatment of manganese slag is mainly divided into two ways: harmless treatment and resource utilization.

[0005] The harmless treatment of manganese slag mainly utilizes water washing / leaching or solidification / stabilization to remove or solidify harmful elements such as manganese, ammonia nitrogen, cobalt, and nickel in the manganese slag. Chinese patent CN116274306A discloses a harmless treatment and ammonia recovery process for electrolytic manganese slag, which adopts a multi-stage pulping operation to remove soluble manganese and ammonia nitrogen from the manganese slag, and the process water is recycled in reverse flow. The pH, manganese, and ammonia nitrogen of the leachate of the treated manganese slag can meet the requirements of Class I general industrial solid waste, and the treatment cost is low. Chinese patent CN116173703A discloses a method and mineralization product for the mineralization of electrolytic manganese slag with CO2 to synergistically solidify metal ions, which uses electrolytic manganese slag to solidify CO2 in situ and solidify Mn in the electrolytic manganese slag at the same time. 2+ Mg 2+ , achieving high-value utilization of electrolytic manganese slag. Chinese patent CN103320621A discloses a method for solidifying heavy metals in electrolytic manganese slag and co-producing sulfur. A raw material containing calcium sulfite and / or calcium sulfate is mixed with a carbon-based reducing agent and roasted to obtain calcine containing calcium sulfide. The calcine containing calcium sulfide is mixed with manganese slag, stirred in water, and filtered to obtain a filtrate and a filter residue. The filtrate is allowed to stand to precipitate sulfur, and the filter residue is the solidified manganese slag.

[0006] The resource utilization of manganese slag usually involves further processing the manganese slag to produce cement / cement clinker, bricks, plates, ceramics and other products. Chinese patent CN115716720A discloses a cement material made from manganese slag and its preparation method. The cement material is composed of: 70% cement clinker, 10% limestone, 10% desulfurized gypsum, 3% to 5% coal-fired furnace slag, and 5% to 7% manganese slag. The above raw materials are fed into a grinder for grinding to obtain the cement material. Chinese patent CN116462429A discloses a method for co-processing waste incineration fly ash and manganese slag to prepare a cementitious material. The manganese slag and waste incineration fly ash are calcined, dissolved in water, and calcined in oxygen-enriched conditions to prepare a fly ash manganese slag detoxification active material. The fly ash manganese slag detoxification active material is mixed with a silicon-based material to obtain a cementitious material. Chinese patent CN111644269A discloses a method for the comprehensive utilization of manganese slag resources. The method adopts closed-circuit flotation with the addition of cationic collectors in roughing stages, three stages of fine separation, and the sequential return of the fine middlings to the previous stage to obtain concentrate foam and tailings slurry, thereby achieving efficient separation of gypsum from gangue such as quartz. The obtained concentrate foam is processed into white gypsum, and the obtained tailings slurry is further processed to make unburned bricks or cement clinker.

[0007] The above-mentioned manganese slag harmless treatment and resource utilization technologies provide diversified treatment and utilization methods for manganese slag, which is of great significance and value in promoting the technological progress of manganese slag treatment technology and the manganese industry. However, the above-mentioned technical solutions are all based on the situation where mixed slag is obtained in the existing production process. There are no reports on pre-separating manganese slag into acid leaching slag, neutralization slag, and sulfide during the manganese ore leaching and leachate purification process. Summary of the Invention

[0008] In response to the aforementioned shortcomings, the present invention provides a method for the tiered generation and classified resource utilization of manganese slag. Using manganese ore as the raw material, the method utilizes leaching, neutralization precipitation, and step-by-step sulfidation precipitation, alternating with filtration, to sequentially generate and separate acid leaching residue, neutralization residue (or a mixture of the acid leaching and neutralization residues), zinc sulfide, and cobalt, nickel, and manganese sulfides. A purified manganese sulfate solution is also obtained, and the acid leaching residue and neutralization residue are used to prepare calcium sulfate, molecular sieves, and cement clinker, respectively. The present method utilizes tiered generation of manganese slag and purification of the leachate, resolving the difficulty in resource utilization after mixing different components. This method is easy to operate, offers mild reaction conditions, and produces high-value-added products, promising promising industrial applications.

[0009] In order to achieve the above object, the present invention provides a method for the stepwise generation and classified resource utilization of manganese slag, wherein the manganese slag includes acid leaching residue, neutralization residue, zinc sulfide and cobalt-nickel-manganese sulfide;

[0010] When the acid leaching residue and the neutralization residue in the manganese slag are not mixed, the method comprises the following steps:

[0011] A1: Crushing and grinding manganese ore, leaching with sulfuric acid, and filtering to obtain acid leaching residue and leachate;

[0012] A2: The leachate from A1 is oxidized with hydrogen peroxide, neutralized with lime, and filtered using activated carbon as a filter aid to obtain neutralized residue and filtrate I;

[0013] A3: The neutralized residue in A2 is leached with sulfuric acid, and the activated carbon is recycled for flotation. After filtration, calcium sulfate and filtrate II are obtained respectively;

[0014] When the acid leaching residue and the neutralization residue in the manganese slag are used as mixed slag, the method comprises the following steps:

[0015] B1: crushing and grinding the manganese ore, leaching it with sulfuric acid, oxidizing it with hydrogen peroxide, and neutralizing it with lime. Filtering the mixture of acid leaching residue and neutralization residue and filtrate I;

[0016] B2: washing the mixed residue of the acid leaching residue and the neutralized residue in B1, filtering to obtain a mixed residue water washing liquid and a water-washed manganese residue, and recycling the mixed residue water washing liquid after purification;

[0017] B3: Dispersing the washed manganese slag in B2 in water to form a slurry, and converting part of the calcium sulfate in the mixed slag into a calcium carbonate phase with sodium carbonate. At the same time, adjusting the pH of the slurry to 7.5, stirring for 1 to 3 minutes, adding an anionic flocculant to the slurry and stirring for 1 to 5 minutes, then adding sodium oleate and stirring for 3 to 5 minutes to carry out flotation, flotation to obtain a concentrate and tailings, and treating the flotation wastewater for recycling; the anionic flocculant includes one or both of polyacrylamide and sodium polyacrylate;

[0018] B4: The refined residue in B3 is acid-leached with sulfuric acid and filtered to obtain filter residue and filtrate II, respectively. The main component of the filter residue is calcium sulfate;

[0019] The treatment of the filtrate I, filtrate II, acid leaching residue and tailings comprises the following steps:

[0020] C1: Add sodium sulfide or sodium hydrosulfide to the filtrate I in A2 or B1 to perform sulfide precipitation I, and obtain filtrate III and zinc sulfide after filtration;

[0021] C2: Sodium sulfide or sodium hydrosulfide is added to the filtrate III in C1 to perform sulfide precipitation II, and after filtration, cobalt nickel manganese sulfide and manganese sulfate purified liquid are obtained respectively;

[0022] C3: Add an appropriate amount of aluminum salt to the filtrate II in A3 or B4, and prepare polyaluminum ferric sulfate through polymerization reaction, evaporation and crystallization;

[0023] C4: The acid leaching residue in A1 or the tailings in B3 are leached with sodium hydroxide to obtain alkaline leaching residue and alkaline leaching solution. The alkaline leaching residue and limestone are ground and roasted to obtain cement clinker. After adding aluminum salt to the alkaline leaching solution, the molecular sieve is prepared through hydrothermal reaction.

[0024] According to one aspect of the present invention, the leaching conditions of A1 and B1 are: the liquid-to-solid volume mass ratio is 5-10:1; the sulfuric acid concentration is 1.0-3.0 mol / L, and the leaching is carried out under stirring at a reaction temperature of 30-80°C for 2-4 hours.

[0025] According to one aspect of the present invention, the conditions for oxidizing A2 or B1 with hydrogen peroxide and then neutralizing with lime are: the reaction temperature is 30-60°C, the molar ratio of hydrogen peroxide to ferrous ions is 1.1-1.2:1, and after oxidation for 2 hours, neutralization and precipitation are carried out with quicklime at room temperature to a pH of 3.5-5.0.

[0026] According to one aspect of the present invention, the neutralized residue in A3 is acid-leached with 1.0-2.0 mol / L sulfuric acid solution at room temperature for 2 h and then filtered to obtain calcium sulfate and filtrate II, respectively.

[0027] According to one aspect of the present invention, the flotation conditions in B3 are as follows: the pulp concentration is 15% to 30%; the amount of sodium oleate is 1 to 6 kg / t; the amount of sodium carbonate is 2 to 80 kg / t; the concentrate obtained by flotation is acid-leached with 1.0 to 2.0 mol / L sulfuric acid solution at room temperature for 2 hours, and then filtered to obtain calcium sulfate and filtrate II, respectively.

[0028] According to one aspect of the present invention, the conditions for the sulfide precipitation I in C1 and the sulfide precipitation II in C2 are: pH 5.0-7.0, the molar ratio of sodium sulfide or sodium hydrosulfide to zinc ions is 1.0-1.5:1, and the sulfide precipitation is carried out at room temperature for 1-2 hours.

[0029] According to one aspect of the present invention, in C3, the aluminum salt is any one of sodium metaaluminate, aluminum hydroxide, and aluminum sulfate.

[0030] According to one aspect of the present invention, the C3 uses filtrate II as raw material, with an Al / Fe substance ratio of 0.25 to 0.50:1, a pH of 0.5 to 3.0, a polymerization reaction at a reaction temperature of 30 to 80°C for 8 hours, and aging at room temperature for 24 hours, and then evaporation crystallization at an evaporation temperature of 90 to 100°C to obtain polyaluminum ferric sulfate.

[0031] According to one aspect of the present invention, the conditions for leaching sodium hydroxide in the C4 are: sodium hydroxide concentration 5.0-12.0 mol / L, liquid-solid volume mass ratio 5-10:1, and stirring and leaching for 3-6 hours at a reaction temperature of 90-130°C; the conditions for preparing the molecular sieve are: sodium hydroxide concentration 2.0-4.0 mol / L, liquid-solid volume mass ratio 5-10:1, initial silicon-aluminum ratio 1-3.5:1, stirring and reacting at a reaction temperature of 80-100°C for 1-3 hours, and aging at 80-100°C for 6-10 hours.

[0032] According to one aspect of the present invention, the mass ratio of limestone to the alkali leached residue is 5:1-4, and the roasting temperature is 1250-1400°C; the cement clinker is mixed with the calcium sulfate, and the amount of calcium sulfate added is 1%-3% of the mass of the cement clinker to prepare silicate cement.

[0033] Beneficial effects of the present invention:

[0034] (1) The present invention creatively proposes that in the process of manganese ore leaching and leachate purification, zinc and other metal sulfides K sp The significant difference, K sp (ZnS) = 8.9 × 10 -25 , and K sp (MnS) = 2.5 × 10 -13 , K sp (NiS) = 2.8 × 10-20 , K sp (CoS) = 1.8 × 10 -22 , the sulfides are divided into two types of products: zinc sulfide and nickel-cobalt-manganese sulfide. Through multi-stage filtration and step-by-step precipitation, the manganese slag is divided into three types of products: acid leaching residue, neutralization residue, and sulfides (zinc sulfide and nickel-cobalt-manganese sulfide) or a mixed residue of acid leaching residue and neutralization residue, and sulfides (zinc sulfide and nickel-cobalt-manganese sulfide). This achieves source separation of manganese slag, which is beneficial to subsequent treatment and resource utilization;

[0035] (2) The present invention uses acid leaching residue and neutralization residue or refined residue and tailings as raw materials to prepare calcium sulfate, polyaluminum ferric sulfate, cement clinker and molecular sieve respectively, thereby realizing efficient recovery and resource utilization of gypsum, quartz and a large amount of metals in manganese slag; the prepared cement clinker and calcium sulfate are bulk chemical products, both of which can be used to prepare silicate cement; polyaluminum ferric sulfate and molecular sieve are fine chemical products, which are conducive to the large-scale multi-pathway disposal of manganese slag.

[0036] (3) The molecular sieve preparation process of the present invention is carried out in an alkaline environment, and a single-phase zeolite P molecular sieve is prepared for the first time using manganese slag. The cation adsorption capacity can be as high as 3.04 mmol / g. The preparation of polyaluminum ferric sulfate can be carried out at normal pressure and a reaction temperature of 30 to 80°C. The preparation conditions are mild, and it has the advantages of energy saving and safety, which is conducive to industrialization.

[0037] (4) The zinc sulfide product obtained by the present invention has high purity and can be used as a chemical product or as a raw material for zinc smelting; nickel-cobalt-manganese sulfide contains only three metal elements, nickel, cobalt, and manganese, and can be used as a raw material for preparing ternary battery materials or lithium iron manganese phosphate battery materials, thus realizing the organic connection between the manganese industry and the new energy battery material industry chain.

[0038] (5) The present invention adds excess Na2CO3 to the ore pulp, so that a part of Na2CO3 reacts with CaSO4 in the water-washed manganese slag to produce CaCO3, and CaCO3 wraps CaSO4; the other part of Na2CO3 is combined with an anionic flocculant and sodium oleate to float the CaSO4 wrapped in CaCO3. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the process flow of the method for cascade generation and classification resource utilization of part of manganese slag described in Example 1 of the present invention Figure 1 ;

[0040] Figure 2 This is the XRD analysis pattern of calcium sulfate prepared in Example 1 of the present invention;

[0041] Figure 3This is the process flow of the method for cascade generation and classification resource utilization of part of manganese slag described in Example 2 of the present invention Figure 2 ;

[0042] Figure 4 This is a process flow chart for resource utilization of filtrate I described in Example 3 of the present invention;

[0043] Figure 5 This is the XRD analysis pattern of zinc sulfide prepared in Example 3 of the present invention;

[0044] Figure 6 This is the XRD analysis pattern of the cobalt-nickel-manganese sulfide prepared in Example 3 of the present invention;

[0045] Figure 7 This is a process flow chart for resource utilization of filtrate I described in Example 4 of the present invention;

[0046] Figure 8 This is the XRD analysis pattern of the polyaluminium ferric sulfate prepared in Example 4 of the present invention;

[0047] Figure 9 This is a process flow chart for resource utilization of the acid leaching residue described in Example 5 or the tailings described in Example 6 of the present invention;

[0048] Figure 10 This is the XRD analysis pattern of the molecular sieve prepared in Example 5 of the present invention. DETAILED DESCRIPTION

[0049] To make the present invention easier to understand, the present invention is further described below with reference to specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Unless otherwise defined, the professional terms used below are consistent with the meanings understood by professional and technical personnel in this field; unless otherwise specified, the raw materials and reagents involved in this article can be purchased from the market or prepared by known methods.

[0050] It should be noted that, unless otherwise specified, all percentages in the examples of the present application refer to mass percentages.

[0051] Example 1

[0052] Manganese ore comes from Guizhou, and its main elements and contents are: manganese 15.12%, silicon 19.44%, calcium 4.988%, magnesium 1.42%, iron 3.157%, aluminum 6.738%, nickel 0.004%, cobalt 0.002%, zinc 0.005%. Figure 1The method shown is used to process manganese ore, and the specific steps are as follows:

[0053] S1: crush and grind the manganese ore, pass it through a 100-mesh sieve, and then stir and leach it at a liquid-to-solid volume ratio of 5:1 and a sulfuric acid concentration of 1.0 mol / L at a reaction temperature of 40°C for 2 hours. After filtering, obtain the acid leaching residue and leachate;

[0054] S2: The leachate from S1 was oxidized at a reaction temperature of 40°C with a molar ratio of hydrogen peroxide to ferrous ions of 1.2:1 for 1 h, and activated carbon was added as a filter aid at a solid-liquid mass volume ratio of 1:10. The mixture was neutralized and precipitated with lime at room temperature to a pH of 4.5, and filtered to obtain a neutralized residue and filtrate I;

[0055] S3: The neutralized residue in S2 was acid-leached at room temperature for 2 hours with 1.0 mol / L sulfuric acid solution at a liquid-to-solid volume ratio of 5:1, and then flotated and filtered to obtain calcium sulfate and filtrate II, respectively. The XRD analysis results of calcium sulfate are shown in Figure 2. Figure 2 As shown in the figure, the main phase of calcium sulfate is calcium sulfate dihydrate. The purity of calcium sulfate is 91.23%. The molar ratio of Al to Fe in filtrate II is 0.20. After flotation treatment, the activated carbon is reused as a filter aid.

[0056] Example 2

[0057] Manganese ore is the same as in Example 1, using Figure 3 The method shown is used to process manganese ore, and the specific steps are as follows:

[0058] S1: crush and grind the manganese ore, pass it through a 100-mesh sieve, and then leach it at a liquid-to-solid volume ratio of 5:1 and a sulfuric acid concentration of 1.0 mol / L at a reaction temperature of 40°C for 2 h;

[0059] S2: The leachate from S1 was oxidized at a reaction temperature of 40°C with a molar ratio of hydrogen peroxide to ferrous ions of 1.2:1 for 1 hour, and then neutralized and precipitated with lime at room temperature to a pH of 4.5. The mixture of acid leaching residue and neutralized residue was filtered to obtain a filtrate I;

[0060] S3: washing the mixture of the acid leaching residue and the neutralization residue in S2 with water at a liquid-to-solid volume mass ratio of 4:1 and a temperature of 25°C, filtering to obtain a washing liquid and a washed manganese residue, and recycling the washing liquid;

[0061] S4: dispersing the washed manganese slag in S3 in water to a pulp concentration of 20%, adjusting the pulp pH to 7.5 with 8.0 kg / t sodium carbonate, stirring for 1 to 3 minutes, adding 15 g / t anionic polyacrylamide to the pulp and stirring for 1 to 5 minutes, then adding 2.4 kg / t sodium oleate and stirring for 3 to 5 minutes for flotation, obtaining concentrate and tailings by flotation, and recycling the flotation wastewater after treatment;

[0062] S5: The refined residue in S4 was acid-leached with 1.0 mol / L sulfuric acid solution at room temperature for 2 h, and then filtered to obtain calcium sulfate and filtrate II, respectively. The content of calcium sulfate was 75.29%, and the molar ratio of Al to Fe in filtrate II was 0.15.

[0063] Example 3

[0064] Filtrate I was prepared from Example 1 or 2 using Figure 4 The method shown is for resource utilization of filtrate I, and the specific steps are as follows:

[0065] S1: Sodium sulfide was added to the filtrate I to carry out sulfide precipitation I. The conditions for preparing zinc sulfide were as follows: pH 7.0, the molar ratio of sodium sulfide to zinc ion was 1.3:1, and the sulfide precipitation was carried out at room temperature for 2 hours to obtain zinc sulfide (phase analysis see Figure 5 ) and filtrate III;

[0066] S2: The filtrate III in S1 was subjected to sulfidation precipitation II to obtain cobalt-nickel-manganese sulfide under the following conditions: pH 7.0, the molar ratio of sodium sulfide to cobalt-nickel was 1.05:1, sulfidation precipitation was carried out at room temperature for 2 hours, and filtration was performed to obtain cobalt-nickel-manganese sulfide (phase analysis see Figure 6 ) and manganese sulfate purified liquid, wherein the Mn content in the manganese sulfate purified liquid is 32.22 g / L, which meets the production index requirements of electrolytic manganese metal.

[0067] Example 4

[0068] Filtrate II is prepared from Example 1 or 2, and the resource utilization process of filtrate II is as follows: Figure 7 The specific steps are as follows:

[0069] S1: Using filtrate II in Example 1 or Example 2 as raw material, with an Al / Fe molar ratio of 0.25:1, a pH of 3.0, a reaction temperature of 80°C, a polymerization time of 8 hours, aging at room temperature for 24 hours, and then evaporating and crystallizing at 90°C to obtain polyaluminum ferric sulfate. The phase analysis results are as follows: Figure 8 shown.

[0070] Example 5

[0071] The acid leaching residue was prepared from Example 1 using Figure 9The method shown is for resource utilization of acid leaching residue, and the specific steps are as follows:

[0072] S1: Leaching the acid leached residue in a sodium hydroxide concentration of 10.0 mol / L and a liquid-to-solid volume mass ratio of 5:1 at a reaction temperature of 130° C. for 6 h with stirring, filtering to obtain an alkaline leached residue and an alkaline leaching solution. The alkaline leached residue was dried, calcined at 1250° C. at a mass ratio of limestone to alkaline leached residue of 5:1, ball-milled, and passed through a 200-mesh sieve to prepare cement clinker. The SO3 content of the cement clinker was 1.46%, meeting the SO3 control index requirements for slag Portland cement in the national standard "Portland Cement Clinker" (GB / T 21372-2008);

[0073] S2: The alkaline leaching solution was stirred at a sodium hydroxide concentration of 2.0 mol / L and an initial silicon-aluminum ratio of 1:1 at a reaction temperature of 100°C for 2 hours, and aged at 100°C for 10 hours. After filtration and drying, a P-type molecular sieve material was obtained. The phase analysis results are as follows: Figure 10 As shown, its cation adsorption capacity can be as high as 3.04mmol / g.

[0074] Example 6

[0075] The tailings are prepared by Example 2, and the tailings resource utilization process is as follows Figure 9 The specific steps are as follows:

[0076] S1: Leach the tailings in a sodium hydroxide solution with a concentration of 10.0 mol / L and a liquid-to-solid volume mass ratio of 5:1 at a reaction temperature of 130°C for 6 h, and obtain an alkaline leaching residue and an alkaline leaching solution after filtration. The alkaline leaching residue is dried, roasted, ball-milled, and passed through a 200-mesh sieve to obtain cement clinker.

[0077] S2: The alkaline leaching solution is stirred at a sodium hydroxide concentration of 2.0 mol / L and an initial silicon-aluminum ratio of 1:1 at a reaction temperature of 100°C for 2 hours, and aged at 100°C for 10 hours. After filtration and drying, a P-type molecular sieve material is obtained, whose cation adsorption capacity can be as high as 3.24 mmol / g.

[0078] Example 7

[0079] Manganese ore is manganese oxide ore, and its main elements and contents are: manganese 25.85%, silicon 10.38%, calcium 3.34%, magnesium 3.12%, iron 0.98%, aluminum 0.35%, nickel 0.0105%, cobalt 0.018%, and zinc 0.020%. The specific steps for the cascade generation and classified resource utilization of manganese slag are as follows:

[0080] S1: crushing and grinding the manganese ore, passing it through a 100-mesh sieve, and then reducing roasting. At a liquid-to-solid volume ratio of 5:1 and a sulfuric acid concentration of 1.0 mol / L, stirring and leaching were carried out at a reaction temperature of 40°C for 2 h, and then filtering to obtain acid leaching residue and leachate;

[0081] S2: The acid leaching residue is stirred and leached at a reaction temperature of 130°C for 6 hours at a sodium hydroxide concentration of 10.0 mol / L and a liquid-to-solid volume mass ratio of 5:1. After filtering, an alkaline leaching residue and an alkaline leaching liquid are obtained. The alkaline leaching residue is dried, calcined at 1350°C at a mass ratio of limestone to alkaline leaching residue of 4:1, and then ball-milled and passed through a 200-mesh sieve to prepare cement clinker. The SO3 content of the cement clinker is 1.18%, which meets the SO3 control index requirements of slag silicate cement in the national standard "Silicate Cement Clinker" (GB / T 21372-2008). At the same time, the alkaline leaching liquid is stirred and reacted at a reaction temperature of 100°C for 2 hours at a sodium hydroxide concentration of 2.0 mol / L and an initial silicon-aluminum ratio of 1:1, and then aged at 100°C for 10 hours. After filtering and drying, a zeolite P molecular sieve material is obtained;

[0082] S3: The leachate from S1 was treated at a reaction temperature of 40°C, activated carbon was added as a filter aid at a solid-liquid mass volume ratio of 1:10, and lime was used for neutralization and precipitation at room temperature to a pH of 4.5. The neutralized residue and filtrate I were obtained by filtration;

[0083] S4: The neutralized residue in S3 was acid-leached with a 1.0 mol / L sulfuric acid solution at room temperature for 2 h, and then filtered to obtain calcium sulfate and filtrate II, respectively. Filtrate II was used as a raw material, and a polymerization reaction was carried out at a reaction temperature of 80°C for 8 h at an Al / Fe molar ratio of 0.25:1 and a pH of 3.0. After aging at room temperature for 24 h, polyaluminum ferric sulfate was obtained by evaporation and crystallization at an evaporation temperature of 100°C.

[0084] S5: Sodium sulfide was added to the filtrate I in S3 to perform sulfide precipitation I to prepare zinc sulfide under the following conditions: pH 7.0, a molar ratio of sodium sulfide to zinc ion of 1.2:1, and sulfide precipitation at room temperature for 2 h to obtain zinc sulfide (composition analysis results are shown in Table 1) and filtrate III, respectively;

[0085] S6: Filtrate III from S5 was subjected to sulfidation precipitation II to obtain cobalt-nickel-manganese sulfide under the following conditions: pH 7.0, a molar ratio of sodium sulfide to cobalt-nickel of 1.05:1, sulfidation precipitation at room temperature for 2 hours, and filtration to obtain cobalt-nickel-manganese sulfide (composition analysis results are shown in Table 1) and purified manganese sulfate solution. The concentration of the purified manganese sulfate solution was 35.34 g / L, meeting the production index requirements for electrolytic manganese metal.

[0086] Table 1 Composition analysis results of sulfide prepared in Example 7

[0087]

[0088] Example 8

[0089] The manganese ore is the same as that in Example 7. The specific steps of the cascade generation and classification resource utilization of manganese slag are as follows:

[0090] S1: crushing and grinding the manganese ore, passing it through a 100-mesh sieve, and then reducing roasting. At a liquid-to-solid volume ratio of 5:1 and a sulfuric acid concentration of 2.0 mol / L, stirring and leaching were carried out at a reaction temperature of 40°C for 2 h, and then filtering to obtain acid leaching residue and leachate;

[0091] S2: The acid leaching residue is stirred and leached at a reaction temperature of 130°C for 6 hours at a sodium hydroxide concentration of 10.0 mol / L and a liquid-to-solid volume mass ratio of 5:1. After filtration, the alkaline leaching residue and alkaline leaching liquid are obtained. The alkaline leaching residue is dried, roasted, ball-milled, and passed through a 200-mesh sieve to prepare cement clinker. At the same time, the alkaline leaching liquid is stirred and reacted at a reaction temperature of 90°C for 2 hours at a sodium hydroxide concentration of 2.0 mol / L and an initial silicon-aluminum ratio of 1.5:1, and then aged at 100°C for 10 hours. After filtration and drying, the molecular sieve material is obtained;

[0092] S3: The leachate from S1 was treated at a reaction temperature of 50°C, activated carbon was added as a filter aid at a solid-liquid mass volume ratio of 1:10, and the solution was neutralized and precipitated with lime at room temperature to a pH of 5.0. The neutralized residue and filtrate I were obtained by filtration.

[0093] S4: The neutralized residue in S3 was acid-leached with a 1.0 mol / L sulfuric acid solution at room temperature for 2 h, and then filtered to obtain calcium sulfate and filtrate II, respectively. Filtrate II was used as a raw material, and a polymerization reaction was carried out at a reaction temperature of 90°C for 8 h at an Al / Fe molar ratio of 0.35:1 and a pH of 2.0. After aging at room temperature for 24 h, polyaluminum ferric sulfate was obtained by evaporation and crystallization at an evaporation temperature of 90°C.

[0094] S5: Sodium sulfide was added to the filtrate I in S3 to perform sulfide precipitation I to prepare zinc sulfide under the following conditions: pH 6.0, a molar ratio of sodium sulfide to zinc ion of 1.1:1, and sulfide precipitation at room temperature for 1.5 h to obtain zinc sulfide (composition analysis results are shown in Table 2) and filtrate III, respectively;

[0095] S6: The filtrate III in S5 was subjected to sulfidation precipitation II to obtain cobalt-nickel-manganese sulfide under the following conditions: pH 7.0, a molar ratio of sodium sulfide to cobalt-nickel of 1.1:1, sulfidation precipitation at room temperature for 2 hours, and filtration to obtain cobalt-nickel-manganese sulfide (composition analysis see Table 2) and manganese sulfate purified liquid, wherein the concentration of the manganese sulfate purified liquid is 35.06 g / L, which meets the production index requirements of electrolytic manganese metal.

[0096] Table 2 Composition analysis results of sulfides prepared in Example 8

[0097]

[0098] Example 9

[0099] The manganese ore is the same as that in Example 7. The specific steps of the cascade generation and classification resource utilization of manganese slag are as follows:

[0100] S1: The manganese ore is crushed and ground, passed through a 100-mesh sieve, and then subjected to reduction roasting. The ore is stirred and leached at a liquid-to-solid volume mass ratio of 5:1 and a sulfuric acid concentration of 1.0 mol / L at a reaction temperature of 40°C for 2 hours. The ore is then oxidized with 1.2 times the theoretical amount of hydrogen peroxide for 2 hours, and then neutralized and precipitated with lime at room temperature to a pH of 5.0. The mixture of acid leaching residue and neutralized residue and filtrate I are filtered.

[0101] S2: washing the manganese slag in S1 with water at a liquid-to-solid volume mass ratio of 4:1 and a temperature of 25°C, obtaining a manganese slag washing liquid and a washed manganese slag after filtration, and recycling the manganese slag washing liquid after treatment;

[0102] S3: Dispersing the washed manganese slag in S2 in water to a pulp concentration of 20%, adjusting the pulp pH to 7.5 with 8.0 kg / t sodium carbonate, stirring for 1 to 3 minutes, adding 15 g / t anionic polyacrylamide to the pulp and stirring for 1 to 5 minutes, then adding 2.4 kg / t sodium oleate and stirring for 3 to 5 minutes for flotation, obtaining concentrate and tailings by flotation, and recycling the flotation wastewater after treatment;

[0103] S4: The refined residue in S3 was acid-leached with a 1.0 mol / L sulfuric acid solution at room temperature for 2 h, and then filtered to obtain calcium sulfate and filtrate II, respectively. Filtrate II was used as a raw material, and a polymerization reaction was carried out at a reaction temperature of 90°C for 8 h at an Al / Fe molar ratio of 0.35:1 and a pH of 2.0. After aging at room temperature for 24 h, polyaluminum ferric sulfate was obtained by evaporation and crystallization at an evaporation temperature of 85°C.

[0104] S5: Sodium sulfide was added to the filtrate I in S1 to perform sulfide precipitation I to prepare zinc sulfide under the following conditions: pH 6.0, a molar ratio of sodium sulfide to zinc ion of 1.2:1, and sulfide precipitation at room temperature for 1.5 h to obtain zinc sulfide (composition analysis see Table 3) and filtrate III, respectively;

[0105] S6: The filtrate III in S5 was subjected to sulfidation precipitation II to obtain cobalt-nickel-manganese sulfide under the following conditions: pH 7.5, a molar ratio of sodium sulfide to cobalt-nickel of 1.05:1, sulfidation precipitation at room temperature for 2 hours, and filtration to obtain cobalt-nickel-manganese sulfide (component analysis results are shown in Table 3) and manganese sulfate purified liquid, wherein the concentration of the manganese sulfate purified liquid is 33.12 g / L, which meets the production index requirements of electrolytic manganese metal.

[0106] Table 3 Composition analysis results of sulfides prepared in Example 9

[0107]

[0108] Example 10

[0109] The calcium sulfate obtained in Example 1 was added to the cement clinker obtained in Example 5 as a retarder, the amount of calcium sulfate added was 1.5% of the mass of the cement clinker, the mixture was mixed evenly, and the mixture was ground to -0.074 mm. The SO3 content was 2.23%, and the obtained cement product met the SO3 ≤ 4.0% index requirement of slag silicate cement in the national standard "General Portland Cement" (GB 175-2020).

[0110] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for the cascade generation and classification of manganese slag for resource utilization, characterized in that: The manganese slag includes acid leaching residue, neutralization residue, zinc sulfide and cobalt-nickel-manganese sulfide; When the acid leaching residue and the neutralization residue in the manganese slag are not mixed, the method comprises the following steps: A1: Crushing and grinding manganese ore, leaching with sulfuric acid, and filtering to obtain acid leaching residue and leachate; A2: The leachate from A1 is oxidized with hydrogen peroxide, neutralized with lime, and filtered using activated carbon as a filter aid to obtain neutralized residue and filtrate I; A3: The neutralized residue in A2 is leached with sulfuric acid, and the activated carbon is recycled by flotation. After filtration, calcium sulfate and filtrate II are obtained respectively; When the acid leaching residue and the neutralization residue in the manganese slag are used as mixed slag, the method comprises the following steps: B1: crushing and grinding the manganese ore, leaching it with sulfuric acid, oxidizing it with hydrogen peroxide, and neutralizing it with lime. Filtering the mixture of acid leaching residue and neutralization residue and filtrate I; B2: washing the mixed residue of the acid leaching residue and the neutralized residue in B1, filtering to obtain a mixed residue water washing liquid and a water-washed manganese residue, and recycling the mixed residue water washing liquid after purification; B3: Dispersing the washed manganese slag in B2 in water to form a slurry, and converting part of the calcium sulfate in the mixed slag into a calcium carbonate phase with sodium carbonate. At the same time, adjusting the pH of the slurry to 7.5, stirring for 1 to 3 minutes, adding an anionic flocculant to the slurry and stirring for 1 to 5 minutes, then adding sodium oleate and stirring for 3 to 5 minutes to carry out flotation, flotation to obtain a concentrate and tailings, and treating the flotation wastewater for recycling; the anionic flocculant includes one or both of polyacrylamide and sodium polyacrylate; B4: The refined residue in B3 is acid-leached with sulfuric acid and filtered to obtain filter residue and filtrate II, respectively. The main component of the filter residue is calcium sulfate; The treatment of the filtrate I, filtrate II, acid leaching residue and tailings comprises the following steps: C1: Add sodium sulfide or sodium hydrosulfide to the filtrate I in A2 or B1 to perform sulfide precipitation I, and obtain filtrate III and zinc sulfide after filtration; C2: adding sodium sulfide or sodium hydrosulfide to the filtrate III in C1 to perform sulfide precipitation II, and filtering to obtain cobalt nickel manganese sulfide and manganese sulfate purified solution respectively; C3: Add an appropriate amount of aluminum salt to the filtrate II in A3 or B4, and prepare polyaluminum ferric sulfate through polymerization reaction, evaporation and crystallization; C4: The acid leaching residue in A1 or the tailings in B3 are leached with sodium hydroxide to obtain alkaline leaching residue and alkaline leaching solution. The alkaline leaching residue and limestone are ground and roasted to obtain cement clinker. After adding aluminum salt to the alkaline leaching solution, the molecular sieve is prepared through hydrothermal reaction.

2. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The leaching conditions of A1 and B1 are as follows: the liquid-to-solid volume mass ratio is 5-10:1; the sulfuric acid concentration is 1.0-3.0 mol / L; and the leaching is carried out under stirring at a reaction temperature of 30-80° C. for 2-4 hours.

3. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The conditions for A2 or B1 to be oxidized with hydrogen peroxide and then neutralized with lime are: the reaction temperature is 30-60°C, the molar ratio of hydrogen peroxide to ferrous ions is 1.1-1.2:1, after oxidation for 2 hours, neutralization and precipitation are carried out with quicklime at room temperature to neutralize to a pH of 3.5-5.

0.

4. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The neutralized residue in A3 is acid-leached with a 1.0-2.0 mol / L sulfuric acid solution at room temperature for 2 hours, and then filtered to obtain calcium sulfate and filtrate II, respectively.

5. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The flotation conditions in B3 are as follows: the pulp concentration is 15% to 30%; the amount of sodium oleate is 1 to 6 kg / t; the amount of sodium carbonate is 2 to 80 kg / t; the concentrate obtained by flotation is acid-leached with 1.0 to 2.0 mol / L sulfuric acid solution at room temperature for 2 hours, and then filtered to obtain calcium sulfate and filtrate II, respectively.

6. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The conditions for the sulfide precipitation I in C1 and the sulfide precipitation II in C2 are: pH 5.0-7.0, the molar ratio of sodium sulfide or sodium hydrosulfide to zinc ion is 1.0-1.5:1, and the sulfide precipitation is carried out at room temperature for 1-2 hours.

7. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: In C3, the aluminum salt is any one of sodium metaaluminate, aluminum hydroxide, and aluminum sulfate.

8. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The C3 uses filtrate II as raw material, and is subjected to polymerization reaction at a reaction temperature of 30-80°C for 8 hours at an Al / Fe substance ratio of 0.25-0.50:1 and a pH of 0.5-3.0, and is matured at room temperature for 24 hours, and then evaporated and crystallized at an evaporation temperature of 90-100°C to obtain polyaluminum ferric sulfate.

9. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The conditions for leaching sodium hydroxide in the C4 are: sodium hydroxide concentration of 5.0-12.0 mol / L, liquid-solid volume mass ratio of 5-10:1, and stirring and leaching for 3-6 hours at a reaction temperature of 90-130°C; the conditions for preparing the molecular sieve are: sodium hydroxide concentration of 2.0-4.0 mol / L, liquid-solid volume mass ratio of 5-10:1, initial silicon-aluminum ratio of 1-3.5:1, stirring and reacting at a reaction temperature of 80-100°C for 1-3 hours, and aging at 80-100°C for 6-10 hours.

10. The method for cascade generation and classification resource utilization of manganese slag according to claim 1, characterized in that: The mass ratio of limestone to the alkali leached residue is 5:1-4, and the roasting temperature is 1250-1400°C; the cement clinker is mixed with the calcium sulfate, and the addition amount of calcium sulfate is 1%-3% of the mass of the cement clinker to prepare silicate cement.

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