CN113387390A - Manganese slag and calcium chloride waste slag recycling method - Google Patents
Manganese slag and calcium chloride waste slag recycling method Download PDFInfo
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- C01G45/00—Compounds of manganese
- C01G45/06—Halides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
The invention discloses a method for recycling manganese slag and calcium chloride waste slag, which realizes the recycling by two-stage roasting of the manganese slag and the calcium chloride waste slag, utilizes the reaction characteristics of calcium silicate and hydrogen chloride formed by calcium chloride, silicon dioxide and water vapor in the air at high temperature, mixes manganese slag containing low-valence manganese phases formed by reduction roasting with the materials for high-temperature chlorination roasting, and obtains manganese chloride by water leaching and separating roasted products, and the water leaching residue consisting of the mixture of calcium silicate, calcium sulfate and silicon dioxide is obtained, so that the synergistic resource utilization of the manganese residue and the calcium chloride waste residue is realized, the resource value of the solid waste is improved, the economic benefit is higher, the environmental pollution caused by the independent treatment of the corresponding solid waste is reduced, the whole treatment process has simple and easy steps and low energy consumption, and can be widely popularized and applied in the electrolytic manganese industry.
Description
Technical Field
The invention belongs to resource utilization of smelting waste residues, and particularly relates to a resource treatment method of manganese residue and calcium chloride waste residues.
Background
In the production process of electrolytic manganese dioxide, after manganese carbonate is leached by sulfuric acid, a large amount of electrolytic manganese dioxide slag (referred to as manganese slag herein) is generated in the lime neutralization stage, about 4 tons of manganese slag are generated in each 1 ton of manganese dioxide, and the manganese slag is equal to a small amount of manganese oxide except calcium sulfate as a main component.
At present, the main bulk disposal mode of manganese slag is landfill, and particularly in areas such as Guizhou province and the like, the geographical conditions of hilly and mountainous areas are favorable for construction of million-ton or even million-ton landfill sites. However, the landfill method has the problems that the leachate is difficult to treat, the leachate pollutes surface and underground water sources and the like, is a treatment mode for temporarily covering pollution in essence, and cannot fundamentally realize the consumption of manganese slag.
Because the electrolytic manganese slag contains a large amount of silicon and calcium components, the electrolytic manganese slag can be used for recycling and preparing cement building materials, and related industrial practices are developed in a few domestic enterprises at present, and the electrolytic manganese slag is used for preparing the cement building material. However, the manganese metal contained in the electrolytic manganese slag has the risk of environmental pollution in the preparation of cement building materials, and has great hidden danger on the strength performance and the safety performance of the cement building materials.
And the manganese resource in the manganese slag with higher manganese content is seriously lost, and no ideal treatment process for separating the manganese phase in the manganese slag exists at present. If the aim is achieved, the recycling of the metal manganese in the manganese slag can be realized, the harmless treatment of solid slag can be realized, and the foundation is laid for the subsequent preparation of building materials.
The Chinese patent application with the application number of CN201910588744.2 discloses a method for producing manganese carbonate and iron powder by chlorination-reduction roasting of high-iron manganese ores, which comprises the steps of uniformly mixing anhydrous magnesium chloride, anhydrous calcium chloride, a carbonaceous reducing agent and high-iron manganese ore powder to obtain a mixture, carrying out primary reduction roasting on all the mixture, and cooling to obtain a reduced product. In the reaction process, the ionic anhydrous chlorine salt is directly used as a reactant of chlorination reaction to carry out high-temperature strong reduction reaction with the high-iron manganese raw material, and the chlorine salt has a stable structure, so that the chlorination reaction efficiency is not high; in a high-temperature reaction system of mixing reduction and chlorination, iron in a high-iron manganese material can be quickly chlorinated into ferric trichloride in preference to manganese, the boiling point of the ferric trichloride is only 316 ℃, the low-boiling point ferric trichloride quickly volatilizes and enters flue gas to be dissipated, a large amount of chlorinating agent is consumed, the manganese chlorination recovery rate is reduced, and a large amount of manganese still remains in the finally obtained secondary waste residue.
Therefore, the manganese recovery mode aiming at the high ferro-manganese ore is not applicable to the electrolytic manganese slag.
Disclosure of Invention
The technical problem solved by the invention is as follows: aiming at the problems in the process of carrying out resource treatment on the building materials by the existing electrolytic manganese residues, the resource treatment method of the manganese residues and the calcium chloride waste residues is provided, so that the manganese phase in the manganese residues can be separated and recovered in a manganese chloride form, and meanwhile, the separated waste residues can meet the requirements of the building materials.
The invention is realized by adopting the following technical scheme:
a manganese slag and calcium chloride waste residue resource treatment method comprises the following steps of respectively roasting manganese slag and calcium chloride waste residue in a segmented manner to perform reduction chlorination reaction:
s1, mixing the manganese slag and the coal powder to form a mixed material A, adding the mixed material A into a rotary kiln, introducing air for reduction roasting, and reducing all high-valence manganese phases in the manganese slag into low-valence manganese phases by taking carbon in the coal powder as a reducing agent;
s2, mixing the calcium chloride waste residue and quartz sand to form a mixed material B, adding the mixed material B and the reduction roasting product obtained in the step S1 into a chlorination kiln, introducing gas and air to carry out chlorination roasting, converting water vapor in the calcium chloride waste residue and calcium chloride at high temperature in the kiln to form hydrogen chloride atmosphere, and chlorinating a low-valence manganese phase in the reduction roasting product in the hydrogen chloride atmosphere to obtain manganese chloride;
and S3, cooling the chloridized roasted product, then soaking in water, separating a water soaking solution and water soaking slag, wherein the water soaking solution is evaporated and crystallized to obtain manganese chloride, and the water soaking slag is dried to obtain calcium salt and silicon dioxide for the cement building material.
The method for recycling manganese slag and calcium chloride waste slag according to claim 1, wherein the calcium chloride waste slag is paste with a water content of 15-30%.
Specifically, in the method for recycling manganese slag and calcium chloride waste slag, the manganese slag and the coal powder are mixed according to the weight ratio of 5-10: 1 in the step S1.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the mixing ratio of the calcium chloride waste slag and the quartz sand in the step S2 is calculated according to the calcium content in the slag, and the mass ratio of the calcium chloride in the mixed material B to the silicon dioxide in the quartz sand is controlled to be 1.5-2: 1.
Specifically, in the method for recycling manganese slag and calcium chloride waste slag, the proportion of the mixed material B subjected to chlorination roasting in the step S2 to the reduction roasting product is calculated according to the content of manganese monoxide in the roasting reduction product, and the mass ratio of calcium chloride to manganese monoxide is controlled to be 1.5-2: 1.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the reduction roasting in the step S1 is carried out, the temperature is raised to 800-1200 ℃, and the temperature is kept for 60-150 min.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the chlorination roasting combustion in the step S2 is heated to 600-1000 ℃ and stays for 30-60 min.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the liquid-solid ratio of water leaching in the step S3 is 2-5: 1.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the water leaching process in the step S3 is performed in a water-cooling stirring tank at the tail of the kiln.
Specifically, in the method for recycling the manganese slag and the calcium chloride waste slag, the water extract is subjected to evaporative crystallization through heat exchange with high-temperature tail gas at the tail of a kiln.
Considering that a large amount of calcium sulfate except manganese in the manganese slag can be used as a cement retarder, the invention forms manganese chloride by a large amount of chlorine in the calcium chloride waste slag and manganese in the manganese slag. The specific reaction is as follows:
firstly, reducing a manganese phase in the manganese slag into a low-valence manganese phase through reduction roasting, wherein the main reaction chemical equation is as follows:
Mn2O3 + C= MnO + CO↑；
Mn2O3 + C= MnO + CO2↑；
Mn2O3+ CO = MnO + CO2↑。
in the chloridizing roasting stage, firstly, a hydrogen chloride atmosphere is formed through high-temperature conversion of calcium chloride, and the main equation is as follows:
CaCl2 + SiO2 + H2O = CaSiO3 + HCl↑。
performing chloridizing roasting on the manganese slag after the reduction roasting by using hydrogen chloride atmosphere generated by calcium chloride conversion to ensure that a low-valence manganese phase generates manganese chloride through the following reaction, wherein the main reaction chemical equation is as follows:
MnO + HCl↑= MnCl2 + H2O。
the product after chloridizing roasting comprises a mixture of manganese chloride, calcium salt and silicon dioxide, manganese resource in manganese slag is recovered by separating the manganese chloride through water leaching by utilizing the characteristic that the manganese chloride is easy to dissolve in water and other calcium salt and silicon dioxide are not easy to dissolve in water, and the leaching slag with low manganese content is used for cement production, so that solid waste synergistic recycling of the manganese slag and calcium chloride waste slag is realized, and the safety performance of the leaching slag without metal manganese for cement materials is also ensured.
In the treatment process, a cooling water system and high-temperature tail gas in the roasting process are used for water leaching and drying and crystallizing of a water leaching product, so that the energy consumption for recovering solid waste residue resources is reduced.
The invention has the following beneficial effects:
(1) the invention respectively mixes the electrolytic manganese slag and the calcium chloride waste slag as raw materials, and adopts two stages of sectional reduction roasting and chlorination roasting, the two processes have no interference with each other, each process has single reaction, the reaction process can be more effectively controlled, and the implementation of the whole process is more facilitated.
(2) The invention firstly carries out reduction roasting on the manganese slag, then utilizes the calcium chloride waste slag to carry out chlorination reaction, in the process of reducing and roasting the mixed material A of the electrolytic manganese slag in the step S1, only the reduction reaction of reducing high-valence manganese into low-valence manganese is carried out, the reduction reaction of all manganese in the manganese slag is ensured to be complete, then the mixed material B of calcium chloride waste slag is subjected to secondary chloridizing and roasting in the step S2, in the secondary chloridizing roasting reaction process, the calcium chloride waste residue adopted by the invention is a pasty material with the water content of 15-30%, compared with anhydrous calcium chloride, the calcium chloride waste residue is prepared by the steps of converting calcium chloride, silicon dioxide and water molecules at high temperature to form hydrogen chloride and calcium silicate, replacing chloride ions in the calcium chloride with hydrogen chloride, wherein the hydrogen chloride is gas at high temperature, and forming hydrogen chloride reaction atmosphere in the chlorination kiln, and performing chlorination reaction on the manganese slag product after reduction roasting in the hydrogen chloride atmosphere. The manganese slag reduction reaction and the chlorination reaction are carried out in two stages, the manganese reduction can be more thoroughly carried out in the step S1, meanwhile, the chlorination reaction carried out in the hydrogen chloride atmosphere can more efficiently extract the reduced low-valence manganese phase from the manganese slag, the water molecules generated by the chlorination reaction circularly react with calcium chloride and silicon dioxide in the kiln to continuously provide the hydrogen chloride atmosphere in the chlorination kiln, and the efficiency of chlorinating the manganese in the reduction roasting product is further improved.
(3) According to the invention, after the electrolytic manganese slag and the calcium chloride waste slag are subjected to resource treatment, in the obtained product, manganese in the electrolytic manganese slag is combined with chloride ions in the calcium chloride waste slag to form manganese chloride dissolved in water for recycling, and the rest of solid slag components are calcium silicate and silicon dioxide left after manganese removal.
In conclusion, in the method for recycling the manganese slag and the calcium chloride waste slag provided by the invention, the method for realizing the cooperative recycling by two-stage roasting of the manganese slag and the calcium chloride waste residue utilizes the reaction characteristic that calcium chloride can form calcium silicate and hydrogen chloride gas with silicon dioxide and water vapor in the air at high temperature, the manganese slag which is completely reduced in advance and contains a low-valence manganese phase is mixed with the materials for high-temperature chlorination roasting, the roasted product is separated to obtain manganese chloride, and the water leaching solid slag consisting of the mixture of calcium silicate, calcium sulfate and silicon dioxide is obtained, so that the synergistic resource utilization of the manganese slag and the calcium chloride waste slag is realized, the resource value of the solid waste is improved, the economic benefit is higher, the environmental pollution caused by the separate treatment of the two solid wastes is reduced, the whole treatment process has simple and easy steps and high recovery efficiency, and can be widely popularized and applied in the electrolytic manganese industry.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
FIG. 2 is the XRD phase diagram of manganese slag in example 1.
FIG. 3 is the water leaching slag XRD phase diagram of example 1.
Detailed Description
The invention is illustrated below with reference to examples, but the scope of protection of the invention is not limited to the examples.
Example 1
As shown in fig. 1, in step S1 of this embodiment, 1 ton of manganese slag is weighed, 200kg of standard coal powder is added to mix uniformly to form a mixed material a, the mixed material a is added into a reduction roasting kiln through a screw feeder, air is introduced into the kiln, the temperature is raised to 1200 ℃, and the mixed material stays in the temperature interval for a retention time of 150 min.
The manganese slag treated by the embodiment mainly comprises calcium sulfate, silicon dioxide, a small amount of manganese sesquioxide and the like, as shown in a manganese slag XRD phase diagram in figure 2, the element content of each component in the manganese slag is shown in table 1, and the corresponding element content of each component in the manganese slag is expressed by oxides in the table (wherein calcium is expressed in a CaO form, and sulfur is expressed by SO)3Formally expressed, manganese is expressed by MnO-form).
TABLE 1 electrolytic manganese slag main component (%)
| Physical phase | SiO2 | Al2O3 | CaO | MgO | SO3 | MnO | Others |
| Content (wt.) | 30.60 | 4.83 | 17.10 | 0.94 | 24.50 | 5.45 | 16.58 |
Step S2, weighing 700kg of calcium chloride waste residues with the water content of 15% and 56kg of quartz sand, uniformly mixing the calcium chloride waste residues with the quartz sand to form a mixed material B, wherein the mass ratio of the calcium chloride in the mixed material B to the silicon dioxide in the quartz sand is 1.5:1, directly adding a reduction roasting product into a chlorination roasting kiln, simultaneously adding the mixed material B into the chlorination roasting kiln, the mass ratio of the calcium chloride in the mixed material B to the manganese monoxide in the reduction roasting product system is 2:1, introducing air and natural gas into the chlorination roasting kiln as fuel gas for combustion heating, controlling the roasting temperature to be 1000 ℃, and keeping the time to be 60 min.
In this example, the element contents of the main components of the synergistic calcium chloride waste residue are shown in table 2, the mass content of calcium chloride in the calcium chloride waste residue is 15.52%, and the whole residue is alkaline.
Table 2 main component of calcium chloride waste (%)
| Physical phase | CaCO3 | CaSO4 | Fe2O3 | Al2O3 | SiO2 | CaCl2 | Mg(OH)2 | CaO | Loss |
| Content (wt.) | 40.23 | 3.94 | 0.7 | 1.3 | 2.1 | 15.52 | 8.06 | 5.47 | 22.68 |
Step S3, cooling the chlorinated roasting product, directly pouring the product into a water-cooled stirring tank at the tail of a kiln for water leaching, controlling the solid-to-solid ratio of slurry in the stirring tank to be 5:1, pumping the slurry into a filter press through a slurry pump for water-slag separation and filtration, pumping the water leaching solution filtered out at the medium pressure into a heat exchange evaporation system for evaporation and crystallization, wherein the obtained product is manganese chloride crystals, and the phase of the dried water leaching slag is shown in figure 3.
Through measurement and calculation, 94.2kg of manganese chloride with the purity of 95% is finally obtained in the embodiment, the manganese recovery rate is 92.56% compared with the manganese content in the electrolytic manganese slag, 1.3 tons of filter residues are obtained after the water leaching slag is dried, and the final slag contains 51.67% of calcium silicate, 2.46% of silicon dioxide and 33.15% of calcium sulfate which can be directly used as a cement building material through detection.
Example 2
In this example, manganese slag and calcium chloride having the same composition as in example 1 were selected.
In the step S1 of this embodiment, 1 ton of manganese slag is weighed, 100kg of standard coal powder is added to mix uniformly to form a mixed material a, the mixed material a is added into a reduction roasting kiln through a screw feeder, air is introduced into the kiln, the temperature is raised to 800 ℃, and the mixed material is kept for 60min in the temperature interval.
Step S2, weighing 520kg of calcium chloride waste residues with the water content of 20% and 32kg of quartz sand, uniformly mixing the calcium chloride waste residues with the quartz sand to form a mixed material B, wherein the mass ratio of the calcium chloride in the mixed material B to the silicon dioxide in the quartz sand is 2:1, directly adding a reduction roasting product into a chlorination roasting kiln, simultaneously adding the mixed material B into the chlorination roasting kiln, the mass ratio of the calcium chloride in the mixed material B to the manganese monoxide in the reduction roasting product system is 1.5:1, introducing air and natural gas into the chlorination roasting kiln as fuel gas for combustion heating, controlling the roasting temperature to be 600 ℃, and keeping the time to be 30 min.
Step S3 is to cool the chloridized roasted product, directly pour the chloridized roasted product into a water-cooled stirring tank at the kiln tail for water leaching, control the solid-to-solid ratio of slurry in the stirring tank to be 2:1, pump the slurry into a filter press through a slurry pump for water-slag separation and filtration, pump the water leaching solution filtered out at medium pressure into a heat exchange evaporation system for evaporation and crystallization, and obtain a product of manganese chloride crystals, wherein the water leaching slag phase after drying in this embodiment has a slight difference in the content of each component obtained through a chemical phase analysis method, but is limited by the low sensitivity of XRD analysis on the phase with low crystallinity, and the XRD pattern of the water leaching slag in this embodiment has no significant difference from that of embodiment 1, and can refer to the XRD pattern of the water leaching slag in embodiment 1.
Through detection, 26.37kg of manganese chloride with the purity of 95% is finally obtained in the embodiment, the recovery rate of manganese is 25.91% compared with the manganese content in the electrolytic manganese slag, 1.5 tons of filter residue is obtained after the water leaching slag is dried, and through detection, the main components of the manganese chloride comprise 39.82% of calcium silicate, 3.91% of calcium chloride, 2.98% of silicon dioxide and 28.70% of calcium sulfate. In addition, because the manganese phase is not fully chlorinated, the manganese content in the slag reaches 2.08%, and calcium chloride is difficult to leach in a water leaching process due to the wrapping of outer calcium silicate and finally enters a water leaching slag phase.
The reason for the low recovery rate of manganese in this example is that the temperature is lowered in the chlorination roasting stage, and although the decomposition of calcium chloride can proceed spontaneously at 600 ℃ from the thermodynamic point of view, the reaction activity of quartz sand is low at this temperature, which results in insufficient hydrogen chloride generation and insufficient chlorination of manganese. However, the recovery yield of the manganese in the electrolytic manganese residue under the reaction conditions in the embodiment can be basically equal to the cost, and if the reaction parameters are further reduced, the recovery cost exceeds the recovery yield, and the significance of resource recovery is lost.
Example 3
In this example, manganese slag and calcium chloride having the same composition as in example 1 were selected.
As shown in fig. 1, in step S1 of this embodiment, 1 ton of manganese slag is weighed, 150kg of standard coal powder is added to mix uniformly to form a mixed material a, the mixed material a is added into a reduction roasting kiln through a screw feeder, air is introduced into the kiln, the temperature is raised to 1000 ℃, and the mixed material stays in the temperature interval for 120 min.
Step S2, 630kg of calcium chloride waste residues with the water content of 30% are weighed and evenly mixed with 50kg of quartz sand to form a mixed material B, the mass ratio of calcium chloride in the mixed material B to silicon dioxide in the quartz sand is 1.5:1, a reduction roasting product is directly added into a chlorination roasting kiln, the mixed material B is simultaneously added into the chlorination roasting kiln, the mass ratio of calcium chloride in the mixed material B to manganese monoxide in a reduction roasting product system is 1.8:1, air and natural gas are introduced into the chlorination roasting kiln to be used as fuel gas for combustion heating, the roasting temperature is controlled to be 800 ℃, and the retention time is 45 min.
Step S3 is to cool the chloridized roasted product, directly pour the chloridized roasted product into a water-cooled stirring tank at the kiln tail for water leaching, control the solid-to-solid ratio of slurry in the stirring tank to be 4:1, pump the slurry into a filter press through a slurry pump for water-slag separation and filtration, pump the water leaching solution filtered out at medium pressure into a heat exchange evaporation system for evaporation and crystallization, and obtain a product of manganese chloride crystals, wherein the water leaching slag phase after drying in this embodiment has a slight difference in the content of each component obtained through a chemical phase analysis method, but is limited by the low sensitivity of XRD analysis on the phase with low crystallinity, and the XRD pattern of the water leaching slag in this embodiment has no significant difference from that of embodiment 1, and can refer to the XRD pattern of the water leaching slag in embodiment 1.
Through detection, 87.26kg of manganese chloride with the purity of 95% is finally obtained in the embodiment, the recovery rate of manganese is 85.74% compared with the manganese content in electrolytic manganese slag, 1.4 tons of filter residue is obtained after water leaching slag is dried, and the main components of the filter residue comprise 47.05% of calcium silicate, 2.37% of silicon dioxide and 31.06% of calcium sulfate which can be directly used as cement building materials.
From the examples 1 to 3, the method provided by the invention has the advantages that the calcium chloride waste residues are cooperated to carry out manganese recovery on the manganese residues and the solid waste treatment is used as a resource treatment of the cement building material, so that the cost for separately treating the manganese residues and the calcium chloride waste residues is reduced, and the resource recycling of the metallurgical waste residues is improved.
Claims (10)
1. A manganese slag and calcium chloride waste residue resource treatment method is characterized in that: respectively roasting the manganese slag and the calcium chloride waste slag in sections for reduction chlorination reaction, and specifically comprises the following steps:
s1, mixing the manganese slag and the coal powder to form a mixed material A, adding the mixed material A into a rotary kiln, introducing air for reduction roasting, and reducing all high-valence manganese phases in the manganese slag into low-valence manganese phases by taking carbon in the coal powder as a reducing agent;
s2, mixing the calcium chloride waste residue and quartz sand to form a mixed material B, adding the mixed material B and the reduction roasting product obtained in the step S1 into a chlorination kiln, introducing gas and air to carry out chlorination roasting, converting water vapor in the calcium chloride waste residue and calcium chloride at high temperature in the kiln to form hydrogen chloride atmosphere, and chlorinating a low-valence manganese phase in the reduction roasting product in the hydrogen chloride atmosphere to obtain manganese chloride;
and S3, cooling the chloridized roasted product, then soaking in water, separating a water soaking solution and water soaking slag, wherein the water soaking solution is evaporated and crystallized to obtain manganese chloride, and the water soaking slag is dried to obtain calcium salt and silicon dioxide for the cement building material.
2. The method for recycling manganese slag and calcium chloride waste slag according to claim 1, wherein the calcium chloride waste slag is paste with a water content of 15-30%.
3. The manganese slag and calcium chloride waste residue resource treatment method according to claim 2, wherein in the step S1, the manganese slag and the coal powder are mixed according to the weight ratio of 5-10: 1.
4. The method for recycling manganese slag and calcium chloride waste slag as claimed in claim 3, wherein the mixing ratio of the calcium chloride waste slag and the quartz sand in step S2 is calculated according to the calcium content in the slag, and the mass ratio of calcium chloride in the mixed material B to silicon dioxide in the quartz sand is controlled to be 1.5-2: 1.
5. The manganese slag and calcium chloride waste residue resource treatment method according to claim 4, wherein the proportion of the mixed material B subjected to chlorination roasting and the reduction roasting product in the step S2 is calculated according to the content of manganese monoxide in the roasting reduction product, and the mass ratio of calcium chloride to manganese monoxide is controlled to be 1.5-2: 1.
6. The method for recycling manganese slag and calcium chloride waste slag according to claim 1, wherein the reduction roasting in the step S1 is carried out to raise the temperature to 800-1200 ℃ and stay for 60-150 min.
7. The method for recycling manganese slag and calcium chloride waste slag as claimed in claim 5, wherein the chlorination roasting in step S2 is performed by heating to 600-1000 ℃ and staying for 30-60 min.
8. The method for recycling manganese slag and calcium chloride waste slag according to claim 1, wherein the liquid-solid ratio of water leaching in the step S3 is 2-5: 1.
9. The method for recycling manganese slag and calcium chloride waste slag according to claim 8, wherein the water leaching process in the step S3 is performed in a water-cooled stirring tank at the tail of the kiln.
10. The method for recycling manganese slag and calcium chloride waste slag according to claim 9, wherein the water leaching solution is subjected to evaporative crystallization through heat exchange with high-temperature tail gas at the tail of a kiln.
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