Electrolytic manganese residue-based cementitious material and preparation method thereof

Abstract

The application provides a cementing material based on electrolytic manganese residue and a preparation method, wherein the preparation method comprises the following steps: heating and treating original electrolytic manganese residue in a first preset temperature range to obtain a first electrolytic manganese residue material; heating and treating the first electrolytic manganese residue material in a second preset temperature range to perform desulfurization and ammonia fixation on the first electrolytic manganese residue material, and obtain a second electrolytic manganese residue material; heating and treating the second electrolytic manganese residue material in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material, and obtain a target mineral phase with stable structure; the first preset temperature range < the second preset temperature range < the third preset temperature range; and cooling the target mineral phase to room temperature and grinding to obtain the cementing material. According to the scheme, the electrolytic manganese residue is harmlessly treated through multi-stage heating; and the cementing material is prepared according to the product after the heating treatment, so that the electrolytic manganese residue is maximally utilized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolytic manganese residue treatment, in particular to a cementing material based on electrolytic manganese residue and a preparation method thereof. BACKGROUND

[0002] Electrolytic manganese residue is an acidic waste residue produced in the production process of electrolytic manganese metal by electrolysis, and mainly contains SiO2, Al2O3 and CaSO4·2H2O, and has the characteristics of high water content, large viscosity and low activity. The electrolytic manganese residue belongs to the general industrial solid waste of the second type. 10-12 tons of electrolytic manganese residue will be produced for every 1 ton of electrolytic manganese metal.

[0003] The existing treatment and disposal technologies of electrolytic manganese residue mainly include water washing method, leaching method, electrochemical method, solidification method and valuable metal recycling, etc. However, these technologies generally have the disadvantages of large water consumption, high cost, small consumption capacity, etc., and it is difficult to truly realize large-scale harmless treatment or resource utilization. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a cementing material based on electrolytic manganese residue and a preparation method thereof, so as to realize the harmless treatment of electrolytic manganese residue, and at the same time, the cementing material is prepared according to the product after heating treatment, so as to realize the resource recycling of electrolytic manganese residue.

[0005] To solve the above technical problem, an embodiment of the present application provides a preparation method of a cementing material based on electrolytic manganese residue, comprising the following steps:

[0006] heating treatment is performed on the original electrolytic manganese residue in a first preset temperature range to obtain a first electrolytic manganese residue material;

[0007] heating treatment is performed on the first electrolytic manganese residue material in a second preset temperature range to perform desulfurization and ammonia fixation treatment on the first electrolytic manganese residue material, and a second electrolytic manganese residue material is obtained;

[0008] heating treatment is performed on the second electrolytic manganese residue material in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material, and a target mineral phase with stable structure is obtained; the first preset temperature range < the second preset temperature range < the third preset temperature range;

[0009] The target mineral phase is cooled to room temperature and ground to obtain a cementing material.

[0010] In one embodiment, heating treatment is performed on the original electrolytic manganese residue in a first preset temperature range to obtain a first electrolytic manganese residue material, comprising:

[0011] The original electrolytic manganese residue in normal temperature state is heated to a first preset temperature by an electric converter, and is kept at the first preset temperature for a first preset time period to remove free water in the original electrolytic manganese residue, to obtain the first electrolytic manganese residue material.

[0012] In one embodiment, the first electrolytic manganese residue material is heated in a second preset temperature range to perform desulfurization and fixation of ammonia on the first electrolytic manganese residue material, and to obtain a second electrolytic manganese residue material, including:

[0013] The first electrolytic manganese residue material is heated in a first target temperature range and for a second preset time period to perform removal of ammonia and removal of crystal water on the first electrolytic manganese residue material, and to obtain a first sub-electrolytic manganese residue material;

[0014] The first sub-electrolytic manganese residue material is heated in a second target temperature range and for a third preset time period to perform desulfurization on the first sub-electrolytic manganese residue material, and to obtain a second sub-electrolytic manganese residue material; the first preset temperature range < the first target temperature range < the second target temperature range ≤ the second preset temperature range.

[0015] In one embodiment, after the first electrolytic manganese residue material is heated in the first target temperature range and for the second preset time period, further including:

[0016] The first ammonia gas generated in the heating process in the first target temperature range and for the second preset time period is collected, and the first ammonia gas is dissolved in water to obtain ammonia water.

[0017] In one embodiment, after the first sub-electrolytic manganese residue material is heated in the second target temperature range and for the third preset time period, further including:

[0018] The second ammonia gas generated in the heating process in the second target temperature range and for the third preset time period is collected.

[0019] The second ammonia gas is treated in a third target temperature range to obtain a nitric acid solution.

[0020] The nitric acid and the ammonia water are mixed, and the mixed solution is crystallized to obtain ammonium nitrate crystals.

[0021] In one embodiment, the nitric acid and the ammonia water are mixed, and the mixed solution is crystallized to obtain ammonium nitrate crystals, including:

[0022] The ammonium nitrate solution obtained by mixing the nitric acid and the ammonia water is evaporated and concentrated to a preset concentration, and a first ammonium nitrate solution is obtained.

[0023] The first ammonium nitrate solution is subjected to a segmented cooling treatment and drying to obtain the ammonium nitrate crystals.

[0024] In one embodiment, the second electrolytic manganese residue material is subjected to a heating treatment in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material and obtain a target mineral phase with stable structure, including:

[0025] The second sub-electrolytic manganese residue material is subjected to a heating treatment in a fourth target temperature range and for a fourth preset time period to convert heavy metal ions in the second sub-electrolytic manganese residue material into a ceramic phase with stable structure and obtain a third sub-electrolytic manganese residue material.

[0026] The third sub-electrolytic manganese residue material is subjected to a heating treatment in a fifth target temperature range and for a fifth preset time period to convert calcium oxide, aluminum oxide and silicon oxide in the third sub-electrolytic manganese residue material into a glass phase.

[0027] The glass phase is subjected to a heating treatment in a sixth target temperature range and for a sixth preset time period to convert the glass phase into a hydraulic mineral phase; the second preset temperature range < the fourth target temperature range < the fifth target temperature range < the sixth target temperature range ≤ the third preset temperature range.

[0028] In one embodiment, during the heating treatment of the third sub-electrolytic manganese residue material in the fourth target temperature range and for the fourth preset time period, quicklime with a mass fraction of 6%-8% or clay with a mass fraction of 6%-8% is added as a reaction stabilizer.

[0029] In one embodiment, the target mineral phase is cooled to room temperature and ground to obtain a cementitious material, including:

[0030] The hydraulic mineral phase is ground to a particle size of less than 5-100 um to obtain the cementitious material.

[0031] Embodiments of the present application also provide a cementitious material based on electrolytic manganese residue, which is prepared by the preparation method of any one of the above embodiments.

[0032] The above scheme of the present application at least includes the following beneficial effects:

[0033] The cementing material based on electrolytic manganese residue and the preparation method thereof provided by the scheme have the advantages that the harmless treatment of the electrolytic manganese residue is realized through multi-stage heating roasting, and meanwhile, the cementing material is prepared according to the product after the multi-stage heating roasting, so that the electrolytic manganese residue can be maximally utilized. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a preparation method flowchart of the cementing material based on electrolytic manganese residue provided by the embodiment of the present application;

[0035] Figure 2 is an EMR mass spectrum diagram of the original electrolytic manganese residue provided by an optional embodiment of the present application;

[0036] Figure 3 is an ERM mass spectrum diagram of the first electrolytic manganese residue material provided by an optional embodiment of the present application. DETAILED DESCRIPTION

[0037] Exemplary embodiments of the present disclosure will be described more fully hereinafter with reference to the accompanying drawings. While example embodiments of the present disclosure are shown in the drawings, it is understood that the present disclosure can be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present disclosure to those skilled in the art.

[0038] In the following description, certain specific details are set forth in order to provide a thorough understanding of various disclosed embodiments. However, persons of ordinary skill in the relevant art will recognize that embodiments can be practiced without one or more of these specific details. In other instances, well-known structures, materials, and techniques have not been shown or described in order to avoid unnecessarily obscuring descriptions of embodiments.

[0039] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics can be combined in any suitable manner in one or more embodiments.

[0040] As shown in Figure 1 , the embodiment of the present application provides a method for preparing a cementitious material based on electrolytic manganese residue, specifically comprising the following steps:

[0041] Step 11, heating the original electrolytic manganese residue in a first preset temperature range to obtain a first electrolytic manganese residue material;

[0042] Step 12, heating the first electrolytic manganese residue material in a second preset temperature range to perform desulfurization and ammonia fixation on the first electrolytic manganese residue material, and obtain a second electrolytic manganese residue material;

[0043] Step 13, heating the second electrolytic manganese residue material in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material, and obtain a target mineral phase with stable structure; the first preset temperature range < the second preset temperature range < the third preset temperature range;

[0044] Step 14, cooling the target mineral phase to room temperature and grinding to obtain the cementitious material.

[0045] In this embodiment, since the electrolytic manganese residue contains a large amount of moisture and harmful substances (mainly including heavy metal ions and nitrogen and sulfur elements, such as sulfide, sulfate mineral, ammonia-containing compound, Mn 2+ , Cu 2+ , Zn 2+ , Cr 6+ , Cd 2+ , Se 4+ , Pb 2+ , Ni 2 +The different components in the electrolytic manganese residue are removed or converted in different heating roasting stages by setting different roasting temperatures (a first preset temperature range, a second preset temperature range and a third preset temperature range) in different heating roasting stages, so that the harmless treatment of the electrolytic manganese residue is realized, and meanwhile, the rational utilization of the electrolytic manganese residue can be realized according to the product prepared from the multi-stage heating roasting. In addition, the process of the multi-stage heating roasting of the electrolytic manganese residue can be carried out in an electric converter, the temperature is continuously stable during the whole heating roasting process, and by accurately controlling the heating temperature and time, the related components in the electrolytic manganese residue can be fully chemically reacted, the pollutants in the electrolytic manganese residue can be removed more completely, the effect is stable, the cost is low, and the process has great operability and popularization, so that the electrolytic manganese residue treatment problem of the manganese mine enterprises and the electrolytic manganese industry is solved.

[0046] It should be known that the first preset temperature range, the second preset temperature range and the third preset temperature range in the embodiment are empirical data obtained through a large number of tests; here, the multi-stage heating roasting can be carried out through the electric converter.

[0047] In an optional embodiment of the present application, the above step 11 can include:

[0048] Step 111, heating the original electrolytic manganese residue in a normal temperature state to a first preset temperature through the electric converter, and keeping at the first preset temperature for a first preset time period, so as to remove the free water in the original electrolytic manganese residue, and obtain a first electrolytic manganese residue material.

[0049] Since the water content in the electrolytic manganese residue raw material is high (the water content is 23% to 35%), if the water content is not removed, the water will be evaporated in the subsequent heating roasting process, and the water vapor will be condensed on the surface of the electric converter, which will affect the normal operation of the electric converter. Figure 2 As shown in the figure, the ERM spectrum of the original electrolytic manganese residue is shown; at this time, the original electrolytic manganese residue can be treated by the first-stage heating roasting, and the free water in the original electrolytic manganese residue is removed from the solid in the form of evaporation, so as to avoid the influence on the subsequent steps; here, the first preset temperature can be 100℃, and the first preset time period can be 1.5h to 2h, so as to ensure that the free water in the original electrolytic manganese residue can be completely removed; as shown in the figure, the ERM spectrum of the first electrolytic manganese residue material after removing the free water is shown. Figure 3

[0050] In an optional embodiment of the present application, the above step 12 can include:

[0051] Step 121, heating the first electrolytic manganese residue material in a first target temperature range and for a second preset time period, so as to remove the crystallization water and ammonia in the first electrolytic manganese residue material, and obtain a first sub-electrolytic manganese residue material.

[0052] ​Step 122, heating the first sub-electrolytic manganese residue material in the second target temperature range and for a third preset time period to desulfurize the first sub-electrolytic manganese residue material, and obtain a second sub-electrolytic manganese residue material; the first preset temperature range < the first target temperature range < the second target temperature range ≤ the second preset temperature range.

[0053] In this embodiment, the first electrolytic manganese residue after the first-stage heating roasting treatment contains hydrophilic dihydrate gypsum, and the crystal water is often present in the capillary pores of the manganese residue. The ordinary evaporation and air drying can only reduce the free water, but cannot reduce the crystal water. Therefore, in order to prepare the cementitious material, the first electrolytic manganese residue needs to be dried again.

[0054] At this time, the temperature is continuously increased to the first target temperature range to remove the crystal water in manganese hydroxide, hydrous manganese sulfate and hydrous manganese-iron sulfate. Preferably, the first target temperature range can be 100-200°C, and the second preset time period can be 1h.

[0055] The specific reactions occurring in the first target temperature range are as follows:

[0056] Mn(OH)2→MnO+H2O(gas);

[0057] MnSO4.H2O→MnSO4+H2O(gas);

[0058] FeSO4.H2O→FeSO4+H2O(gas);

[0059] At the same time, the deamination reaction also occurs in the first target temperature range, which is as follows:

[0060] NH3-N(ammonia-containing compound)→NH3(gas);

[0061] After the above deamination reaction, the product of the deamination reaction, the first sub-electrolytic manganese residue material, is continuously subjected to heating roasting treatment, and continuously heated to the second target temperature range. Preferably, the second target temperature range can be 200-700°C, and the third preset time period can be 1h. In the second target temperature range, the third preset time period is maintained. In the third target temperature range, the following reactions occur:

[0062] Decomposition of sulfate minerals: MnSO4→MnO+SO2+1 / 2O2, FeSO4→Fe2O3+2SO2;

[0063] Decomposition of iron-sulfur minerals: FeS2+3.5O2→Fe2O3+2SO2;

[0064] The decomposition process of the above-mentioned sulfate minerals and pyrite is to realize the desulfurization process. Preferably, the high-efficiency desulfurization temperature range is 500-700°C, so as to remove the pollutants in the electrolytic manganese residue, and the generated SO2 gas is collected to avoid environmental pollution.

[0065] In an optional embodiment of the present application, after the above-mentioned step 121, the following can also be included:

[0066] Step 121-1, collecting the first ammonia gas generated in the heating process in the first target temperature range and the second preset time period, and dissolving the first ammonia gas in water to obtain ammonia water.

[0067] In this embodiment, the generated first ammonia gas NH3 is collected and dissolved in water to avoid environmental pollution, and the captured first ammonia gas NH3 is dissolved in water to form ammonia water (physical change), and the specific process is as follows:

[0068] NH3(g)+H2O(l)→NH4 + (aq)+OH - (aq).

[0069] In an optional embodiment of the present application, after the above-mentioned step 122, the following can also be included:

[0070] Step 122-1, collecting the second ammonia gas generated in the heating process in the second target temperature range and the third preset time period;

[0071] Step 122-2, treating the second ammonia gas in the third target temperature range to obtain a nitric acid solution;

[0072] Step 122-3, mixing the nitric acid and the ammonia water, and crystallizing the mixed solution to obtain ammonium nitrate crystals.

[0073] In this embodiment, in the continuous heating roasting process, the ammonia nitrogen in the first electrolytic manganese residue is further volatilized and decomposed, and the generated second ammonia gas NH3 is captured and converted into nitric acid by using the flue gas denitration technology (SCR). The temperature of this process needs to be controlled at 250°C to 450°C to improve the reaction rate, and the reaction steps are as follows:

[0074] NH3+O2→NO2+H2O;

[0075] 2NO+O2→NO2;

[0076] NO2+H2O→HNO3+HNO2;

[0077] Nitric acid (HNO3) is the main product of the reaction, and nitrous acid (HNO2) is also a byproduct. Nitrous acid can further react with oxygen to convert into nitric acid:

[0078] HNO2 + O2 → HNO3;

[0079] Here, the generated nitric acid will react with the ammonia water generated in the above step 121-1 to generate ammonium nitrate, and the specific reaction is as follows:

[0080] NH4OH (aq) + HNO3 → NH4NO3 (aq) + H2O (l);

[0081] Through the above reaction, ammonium nitrate solution is generated, and the ammonium nitrate solution is crystallized to obtain ammonium nitrate crystals (nitrogen fertilizer), so as to convert the ammonia nitrogen component in the electrolytic manganese residue into valuable products, thereby improving the utilization rate of the electrolytic manganese residue; It should be noted that the reaction of nitric acid HNO3 and ammonia water NH4OH to generate ammonium nitrate solution needs to be controlled at a temperature of 30-70°C to avoid side reactions or ammonia gas volatilization caused by high temperature.

[0082] In an optional embodiment of the present application, the above step 122-3 can include:

[0083] Step 122-31, evaporate and concentrate the ammonium nitrate solution mixed with nitric acid and ammonia water to a preset concentration, and obtain a first ammonium nitrate solution;

[0084] Step 122-32, the first ammonium nitrate solution is subjected to segmented cooling treatment and drying to obtain ammonium nitrate crystals.

[0085] In this embodiment, in order to crystallize the ammonium nitrate solution, water needs to be evaporated to make the ammonium nitrate solution reach a supersaturated state, and attention should be paid to the process of evaporation that the temperature should not be too high (not more than 170°C) to avoid decomposition or explosion of ammonium nitrate at high temperature;

[0086] Here, the ammonium nitrate solution is first heated to about 100°C, a part of water is evaporated, and the stirring is continued (to prevent local overheating or decomposition) until the ammonium nitrate concentration reaches about 80%-90%, and the first ammonium nitrate solution is obtained;

[0087] Further, the ammonium nitrate is precipitated from the first ammonium nitrate solution by reducing the temperature of the first ammonium nitrate solution: here, the concentrated first ammonium nitrate solution is taken out of the heater, and the first ammonium nitrate solution is gradually cooled (here, a cold water bath or air cooling can be used), when the temperature is reduced to about 25°C, ammonium nitrate crystals begin to precipitate in the solution; Continue to reduce the temperature to 15°C, further precipitate ammonium nitrate crystals, and stand for more than 8 hours to promote the growth of ammonium nitrate crystals;

[0088] Further, the precipitated ammonium nitrate crystals are separated from the mother liquor by vacuum filtration or centrifugal separation, and then the ammonium nitrate crystals are placed in a low-temperature drying device (50-70°C) for drying to obtain a dried ammonium nitrate product.

[0089] In an optional embodiment of the present application, the above step 13 can include:

[0090] Step 131, heating the second sub-electrolytic manganese residue material in a fourth target temperature range and for a fourth preset time period, to convert heavy metal ions in the second sub-electrolytic manganese residue material into a structure-stable ceramsite phase, and obtain a third sub-electrolytic manganese residue material;

[0091] Step 132, heating the third sub-electrolytic manganese residue material in a fifth target temperature range and for a fifth preset time period, to convert calcium oxide, aluminum oxide and silicon oxide in the third sub-electrolytic manganese residue material into a glass phase;

[0092] Step 133, heating the glass phase in a sixth target temperature range and for a sixth preset time period, to convert the glass phase into a hydraulic mineral phase; the second preset temperature range < the fourth target temperature range < the fifth target temperature range < the sixth target temperature range ≤ the third preset temperature range.

[0093] In this embodiment, the second sub-electrolytic manganese residue material is electrolytic manganese residue from which nitrogen and sulfur components have been removed, at this time the temperature is continuously increased and the temperature is increased to the fourth target temperature range to achieve solidification of heavy metal ions in the second sub-electrolytic manganese residue material: preferably, during the heating process of the third sub-electrolytic manganese residue material in the fourth target temperature range and for the fourth preset time period, 6-8% by mass of quicklime or 6-8% by mass of clay is added as a reaction stabilizer; here, both quicklime and clay belong to ordinary industrial materials or building materials, which are easy to obtain, inexpensive, and highly operable, and by developing a compounding ratio control, new pollution to groundwater and surface water can be avoided.

[0094] Preferably, the fourth target temperature range is 800-1200°C, and the fourth preset time period can be 1h, in this temperature range, heavy metal ions are removed or converted into harmless oxides from the second sub-electrolytic manganese residue material, so that the content of heavy metals in the second sub-electrolytic manganese residue material is greatly reduced, and the product after conversion of heavy metal ions has good chemical stability to serve as a raw material for the final cementitious material;

[0095] The specific chemical reactions involving heavy metal ions in the above process are as follows:

[0096] Fe 2+ + O2→ Fe 3+ ;

[0097] Fe 2+ + O2→ Fe2O3;

[0098] Through the above reaction, iron ions are retained in the stable form of ferric oxide, which can effectively remove iron ions;

[0099] Cu 2+ + O2→ CuO;

[0100] CuO + Al2O3→ CuAl2O4 (copper aluminum spinel, stable compound);

[0101] CuO + Fe2O3→ CuFe2O4 (copper iron spinel, stable compound)

[0102] Copper ions Cu 2+ react with oxygen to form stable copper oxide CuO, and as the temperature rises, form more stable compounds copper aluminum spinel, copper aluminum spinel;

[0103] Zn 2+ + O2→ ZnO

[0104] Zinc ions Zn 2+ react with oxygen to form stable zinc oxide ZnO;

[0105] Al3 + + O2→ Al2O3

[0106] Aluminum ions Al 3+ react with oxygen to form stable aluminum oxide Al2O3;

[0107] Aluminum oxide Al2O3 further chemically reacts and cooperates with Pb 2+ solidification and stabilization:

[0108] PbO + Al2O3→ PbAl2O4 (lead aluminate, stable and material);

[0109] PbO + SiO2→ PbSiO3 (lead silicate, stable and material)

[0110] High temperature solidification reaction of arsenic As:

[0111] Arsenic As reacts with stabilizer: As2O3 + CaO + 1 / 2O2→ Ca(AsO4)2 (calcium arsenate, stable compound);

[0112] Al2O3 + Fe2O3→ FeAsO4 (arsenopyrite, stable compound);

[0113] High temperature solidification reaction of cadmium ions Cd 2+ ​

[0114] CdO + SiO2→ CdSiO2 (cadmium silicate, stable compound);

[0115] CdO + Al2O3→ CdAl2O4 (cadmium aluminum spinel, stable compound);

[0116] Chromium Cr 6+ is a highly toxic heavy metal ion, which can be converted into low-toxicity trivalent chromium Cr 3+ by reduction at high temperature, and reacts with iron oxide to form a spinel structure:

[0117] Reduction reaction: Cr2O7 2- → Cr2O3 + 1 / 2O2 (high-temperature reduction to trivalent chromium oxide);

[0118] Solidification reaction: Cr2O3 + Fe2O3→ FeCr2O4→ (chromium iron spinel, stable compound);

[0119] Add stabilizer lime 6%-8%, form more stable chromate:

[0120] Cr2O3 + CaO→ CaCrO4 (chromate, stable compound);

[0121] The spinel and related stable compounds generated in the above process are stable structures, that is, ceramic particles, which are used as raw materials for subsequent cementitious materials;

[0122] After the heating calcination treatment in the fourth target temperature range and the fourth preset time period, the heavy metal ions in the third sub-electrolytic manganese slag material are detected, and the detection results are shown in Table 1; it can be seen from the data in Table 1 that the heavy metal ions are completely removed;

[0123] Table 1, heavy metal ion content (unit g / kg) detection results table

[0124]

[0125] After the majority of heavy metal ions in the second sub-electrolytic manganese residue material are removed (converted into stable compounds), the remaining third sub-electrolytic manganese residue material contains components such as SiO2, CaO, and Al2O3; further, the temperature is continuously increased to a fifth target temperature range while maintaining a fifth preset time period, preferably, the fifth target temperature range can be 1200-1300°C, and the fifth preset time period can be 1 h; at this time, the main components (SiO2, CaO, and Al2O3) in the third sub-electrolytic manganese residue material form a low-melting-point silicate melt at high temperature, SiO2 is the framework component of the glass phase, and CaO and Al2O3 are network modifiers. This melt forms an amorphous glass phase structure when cooled, and the key chemical reactions are:

[0126] CaO + SiO2→ CaSiO3 (calcium silicate melt, glass phase basis);

[0127] Al2O3 + CaO + 2SiO2→ CaAl2Si2O8 (aluminosilicate, enhances glass phase effect);

[0128] The metal ions in the above compounds are wrapped in the glass network of the glass phase, thereby reducing toxic leaching, and on the other hand forming insoluble salts to reduce environmental risk;

[0129] Further, the temperature is continuously increased, and the glass phase is heated and treated in a sixth target temperature range and a sixth preset time period to convert the glass phase into a hydraulic mineral phase; preferably, the sixth target temperature range can be 1300-1500°C, and the sixth preset time period can be 1 h;

[0130] It should be noted that the glass phase is an intermediate product that can remove the remaining heavy metal ions (metal ions are wrapped in the glass network of the glass phase, which can reduce toxic leaching) in the third sub-electrolytic manganese residue material, and when it is necessary to prepare a cementitious material, the third sub-electrolytic manganese residue material can be directly heated to the sixth target temperature range to convert the main components (SiO2, CaO, and Al2O3) in the third sub-electrolytic manganese residue material into a hydraulic mineral phase; these hydraulic mineral phases form hydration products in the hydration reaction, which impart strength to the material, and the specific reactions are as follows:

[0131] Silicate formation:

[0132] 2CaO + SiO2→ 2CaO·SiO2 (dicalcium silicate);

[0133] 3CaO + SiO2→ 3CaO·SiO2 (tricalcium silicate);

[0134] Aluminate formation:

[0135] 3CaO + Al2O3→ 3CaO-Al2O3 (tricalcium aluminate, early strength enhancer) ;

[0136] Ferrialuminate formation:

[0137] 4CaO + Al2O3 + Fe2O3→ 4CaO-Al2O3-Fe2O3 (tetracalcium ferrialuminate, hydraulic mineral phase).

[0138] In an optional embodiment of the present application, the above step 14 can comprise:

[0139] Step 141, grinding the ceramsite phase and the hydraulic mineral phase to a particle size of less than 5-100um, and obtaining the cementitious material.

[0140] In this embodiment, after obtaining the above hydraulic mineral phase, the hydraulic mineral phase is taken as the target mineral phase, and after slow cooling and forming clinker, the grinding is carried out to obtain the granular cementitious material with a particle size of less than 5-100um, so that the final cementitious material has good hydration activity.

[0141] The method provided by the above embodiment of the present application is processed by electric heating, and in the case of heating 1 million tons of manganese slag to 1500℃, the specific process of calculating the energy consumption is as follows:

[0142] (1) The mass of the electrolytic manganese slag raw material: m = 1 million tons = 100 × 10 7 kg;

[0143] (2) The specific heat capacity of the electrolytic manganese slag raw material: the water content of the electrolytic manganese slag raw material is 25-35%, the specific heat capacity of water is 4.18 J / g·℃, and the specific heat capacity of manganese slag itself is about (0.6-1.0 J / g·℃), so the specific heat capacity of 25% manganese slag:

[0144] C 1 avg(25%) = (0.8 × 0.75) + (4.18 × 0.25) = 0.6 + 1.045 = 1.645 J / g·℃;

[0145] And the specific heat capacity of 35% of the electrolytic manganese slag raw material:

[0146] C 2 avg(35%) = (0.8 × 0.65) + (4.18 × 0.35) = 0.52 + 1.463 = 1.983 J / g·℃;

[0147] (3) Ambient temperature: T 初始温度 = 20℃;

[0148] (4) Target temperature: T 目标温度 = 1500℃;

[0149] (5) Temperature change amount: T1 = T 目标温度 -T 初始温度 = 1480℃;

[0150] (6) Total heat required for calculation: Q = mcT1;

[0151] Substituting numerical calculation can be obtained:

[0152] 20℃ ~ 200℃ interval:

[0153] Q1 = 100 × 10 7 kg × (C 1 avg + C 2 avg) × 10 3 J / kg\cdot℃×180=(296.1~356.94)×10 12 J (joule);

[0154] 200℃ ~ 1500℃ interval: Q2 = 100 × 10 7 kg × 8 × 10 2 J / kg\cdot℃×1300=1040×10 12 J (joule)

[0155] (7) Conversion to electrical energy (1kWh = 3.6 × 10 6 J)

[0156] 20℃ ~ 200℃ interval, the required electrical energy: W1 = Q1 / (3.6 × 10 6 J) = (82.25 ~ 99.15) × 10 6 kWh;

[0157] 200℃ ~ 1500℃ interval, the required electrical energy: W2 = Q2 / (3.6 × 10 6 J) = 288.88 × 10 6 kWh;

[0158] (8) Budget cost of electricity F1:

[0159] F1 = (W1 + W2) × 0.6264 (38kV) = (232.47 ~ 243.06) × 10 6 Yuan;

[0160] If using coal, the unit heat value of coal is 25MJ / kg, the amount of coal required, heat utilization rate of 80% (general furnace parameters):

[0161] Coal = (3034.25 × 10 12 ~ 3688.55 × 10 12) kgJ / (25x10 6 J / kg) x (1 / 0.55) = (220.67~268.26) x 10 6 kg

[0162] The budget cost F2 of using coal is:

[0163] F2 = (220.67~268.26 x 10 6 kg) + (220.67~268.26) x 10 3 kg x 0.3 x 700 = (267.01~324.

[0164] 48) x 10 6 yuan.

[0165] By comparison, the cost of using electricity is 10.12%~28.49% lower than that of using coal combustion price;

[0166] The above embodiment of the present application prepares the cementitious material through multi-stage heating roasting (low-temperature drying - medium-temperature desulfurization and ammonia fixation - high-temperature calcination), further solves the problems of Pb 2+ , Cu 2+ and Cr 2+ ion pollution and Mn 2+ ion, water-soluble salt and PH value exceeding the standard in roasting electrolytic manganese slag; simultaneously extracts ammonium nitrate to obtain valuable ammonium nitrate crystals; improves the utilization rate of electrolytic manganese slag; simultaneously uses green electricity, is low in cost, the results are reliable through indoor test and small test verification, and solves the problem of electrolytic manganese slag treatment for manganese mine enterprises and electrolytic manganese industry.

[0167] The embodiment of the present application also provides a cementitious material based on electrolytic manganese slag, which is prepared by the preparation method in any one of the preparation method embodiments.

[0168] In the embodiment, the prepared cementitious material can be used for first, second, third and fourth grade road construction, and can also be used for roasting electrolytic manganese slag resource recycling; since the related sulfur and nitrogen compounds are removed in the treatment process, the initial pH has no effect on the laying of the cementitious material, and the cementitious material is suitable for various pH ranges.

[0169] The above is the preferred embodiment of the present application, and it should be noted that for ordinary skilled persons in the technical field, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for the preparation of a cementitious material based on electrolytic manganese residue, characterized in that, The preparation method comprises the following steps: The original electrolytic manganese residue is heated in a first preset temperature range to obtain a first electrolytic manganese residue material; The first electrolytic manganese residue material is heated in a second preset temperature range to remove sulfur and fix ammonia in the first electrolytic manganese residue material, and a second electrolytic manganese residue material is obtained, specifically including: heating the first electrolytic manganese residue material to remove ammonia and remove crystal water to obtain a first sub-electrolytic manganese residue material, heating the first sub-electrolytic manganese residue material to obtain a second sub-electrolytic manganese residue material, collecting first ammonia gas generated in the heating process of the first electrolytic manganese residue material, and obtaining ammonia water after treatment; collecting second ammonia gas generated in the heating process of the first sub-electrolytic manganese residue material, obtaining nitric acid solution after treatment of the second ammonia gas, and obtaining ammonium nitrate crystals after treatment of the nitric acid and the ammonia water; The second electrolytic manganese residue material is heated in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material, and a target mineral phase with stable structure is obtained; the first preset temperature range < the second preset temperature range < the third preset temperature range; The target mineral phase is cooled to room temperature and ground to obtain a cementing material.

2. The method for producing a cementitious material based on electrolytic manganese residue according to claim 1, characterized in that, The original electrolytic manganese residue is heated in a first preset temperature range to obtain a first electrolytic manganese residue material, including: The original electrolytic manganese residue in normal temperature state is heated to a first preset temperature by an electric converter, and is kept at the first preset temperature for a first preset time period to remove free water in the original electrolytic manganese residue, and the first electrolytic manganese residue material is obtained.

3. The method for producing a cementitious material based on electrolytic manganese residue according to claim 1, characterized in that, The first electrolytic manganese residue material is heated in a second preset temperature range to remove sulfur and fix ammonia in the first electrolytic manganese residue material, and a second electrolytic manganese residue material is obtained, including: The first electrolytic manganese residue material is heated in a first target temperature range and a second preset time period to remove ammonia and remove crystal water in the first electrolytic manganese residue material, and a first sub-electrolytic manganese residue material is obtained; The first sub-electrolytic manganese residue material is heated in a second target temperature range and a third preset time period to remove sulfur in the first sub-electrolytic manganese residue material, and a second sub-electrolytic manganese residue material is obtained; the first preset temperature range < the first target temperature range < the second target temperature range ≤ the second preset temperature range.

4. The method for producing a cementitious material based on electrolytic manganese residue according to claim 3, characterized in that, After the first electrolytic manganese residue material is heated in the first target temperature range and the second preset time period, the following steps are further included: The first ammonia gas generated in the heating process in the first target temperature range and the second preset time period is collected, and the first ammonia gas is dissolved in water to obtain ammonia water.

5. The method for producing a cementitious material based on electrolytic manganese residue according to claim 4, characterized in that, After the first sub-electrolytic manganese residue material is heated in the second target temperature range and the third preset time period, the following steps are further included: The second ammonia gas generated in the heating process in the second target temperature range and the third preset time period is collected; The second ammonia gas is treated in a third target temperature range to obtain nitric acid solution; Mixing the nitric acid and the ammonia water and crystallizing the mixed solution to obtain ammonium nitrate crystals.

6. The method for producing a cementitious material based on electrolytic manganese residue according to claim 5, characterized in that, Mixing the nitric acid and the ammonia water and crystallizing the mixed solution to obtain ammonium nitrate crystals, comprising: Evaporating and concentrating the ammonium nitrate solution obtained after mixing the nitric acid and the ammonia water to a preset concentration to obtain a first ammonium nitrate solution; Segmentally cooling and drying the first ammonium nitrate solution to obtain the ammonium nitrate crystals.

7. The method for producing a cementitious material based on electrolytic manganese residue according to claim 3, characterized in that, Heating the second electrolytic manganese residue material in a third preset temperature range to solidify heavy metal ions in the second electrolytic manganese residue material and obtain a target mineral phase with stable structure, comprising: Heating the second sub-electrolytic manganese residue material in a fourth target temperature range and for a fourth preset time period to convert heavy metal ions in the second sub-electrolytic manganese residue material into a ceramic phase with stable structure and obtain a third sub-electrolytic manganese residue material; Heating the third sub-electrolytic manganese residue material in a fifth target temperature range and for a fifth preset time period to convert calcium oxide, aluminum oxide and silicon oxide in the third sub-electrolytic manganese residue material into a glass phase; Heating the glass phase in a sixth target temperature range and for a sixth preset time period to convert the glass phase into a hydraulic mineral phase; the second preset temperature range < the fourth target temperature range < the fifth target temperature range < the sixth target temperature range ≤ the third preset temperature range.

8. The method for producing a cementitious material based on electrolytic manganese residue according to claim 7, characterized in that, During the heating of the third sub-electrolytic manganese residue material in the fourth target temperature range and for the fourth preset time period, adding quicklime with a mass fraction of 6%-8% or clay with a mass fraction of 6%-8% as a reaction stabilizer.

9. The method for producing a cementitious material based on electrolytic manganese residue according to claim 7, characterized in that, Cooling the target mineral phase to room temperature and grinding to obtain a cementitious material, comprising: Grinding the hydraulic mineral phase to a particle size of less than 5-100 um to obtain the cementitious material.

10. A cementitious material based on electrolytic manganese residue, characterized in that, The cementitious material is prepared by the preparation method of any one of claims 1-9. The cementitious material is prepared by the preparation method of any one of claims 1-9.

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