CN113185154B - Method for preparing cement clinker by using rare earth tailings - Google Patents
Method for preparing cement clinker by using rare earth tailings Download PDFInfo
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- CN113185154B CN113185154B CN202110033472.7A CN202110033472A CN113185154B CN 113185154 B CN113185154 B CN 113185154B CN 202110033472 A CN202110033472 A CN 202110033472A CN 113185154 B CN113185154 B CN 113185154B
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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
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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
- C04B7/36—Manufacture of hydraulic cements in general
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses a method for preparing cement clinker by utilizing rare earth tailings, which relates to the technical field of preparing cement clinker by utilizing rare earth tailings, and comprises the following steps: 1) Sorting and enriching rare earth minerals, fluorite and strontium barium minerals in the rare earth tailings to obtain re-sorted waste materials; 2) Mixing and grinding the re-selected waste material prepared in the step 1) and raw materials of cement raw materials, and uniformly mixing to obtain the raw materials of cement; 3) Calcining and cooling the cement raw material to obtain cement clinker; the method of the invention not only can utilize the components of calcium, iron, silicon and aluminum in the rare earth tailings as raw materials of cement raw materials, but also can use residual rare earth minerals, fluorite and strontium barium minerals as composite mineralizers to reduce the sintering temperature of clinker; therefore, the cement clinker prepared by utilizing the rare earth tailings can reduce the exploitation of natural cement raw materials, reduce the energy consumption for preparing the cement clinker and have good comprehensive effect.
Description
Technical Field
The invention relates to the technical field of cement clinker preparation by using rare earth tailings, in particular to a method for preparing cement clinker by using rare earth tailings.
Background
The reserves and the output of rare earth are at the top of the world in China, but the grade of rare earth ore is generally relatively low, a large amount of rare earth tailings are generated in the resource development and utilization process, and the tailings generated in the actual production can only be stockpiled and disposed due to the lack of a mature and effective tailing resource utilization technology at the present stage. The disposal mode of the tailings is the most common and universal mode for treating the tailings at present, but a plurality of defects are shown at present, a large amount of useful minerals in the tailings are not effectively recycled, a large amount of resources are wasted, meanwhile, the stacking of the tailings occupies land, and the leakage of the tailing wastewater and the transportation of harmful substances in the tailings through water flow, wind power and the like cause great negative effects on the surrounding ecological environment. Therefore, a resource utilization technology capable of consuming the rare earth tailings in a large scale is urgently needed.
The rare earth tailings mainly comprise chemical elements such as silicon, aluminum, iron, calcium and the like, are similar to the composition of most building materials, and provide a precondition for the wide application of the rare earth tailings in the building material industry. At present, a lot of researches are made on resource utilization of rare earth tailings in building materials. For example, wang Yongqing and the like, aiming at the difficult problem of slurry dispergation of rare earth tailings in the preparation of building ceramics, the research on improving the fluidity of rare earth tailings slurry by adding a proper dispergator makes the rare earth tailings slurry meet the technological requirements of preparing building ceramics. Xu Jing and the like, which are prepared by taking rare earth tailings as main raw materials through a sintering method, have the water absorption rate of 34.19 percent, the apparent porosity of 55.51 percent, the compressive strength of 3.62MPa and the volume density of 1.23g/cm 3 The sintered ceramsite of (2). However, the rare earth tailings for preparing the building materials have the problems of limited market capacity, low scale effect and the like. In addition, the electronic structure of the rare earth elements in the rare earth tailings has special characteristics, so that the rare earth elements can generate more dislocations and defects when being used for developing the catalyst, and can also play a role of combined promotion with other raw materials to optimize the surface structure of the catalyst, so that the performance of the catalyst is improved. For example, yu Xiujin and the like utilize the residue of rare earth tailings after precious and heavy rare earth extraction as a main raw material, and additives such as magnesium oxide and the like are added to develop an FA401 ammonia synthesis catalyst with low temperature, high activity and excellent heat resistance, so that various performances of the catalyst are obviously improved, the catalyst is an effective novel ammonia synthesis catalyst for improving the overall economic benefit of an ammonia plant, and a theoretical basis is provided for further research and development of a novel catalyst with low cost and high performance. Wei Kemei, etc. developed a low-cost three-way catalyst for automobile exhaust, which uses a home-made cordierite honeycomb ceramic modified by rare earth tailings and transition metal oxides as a first carrier, a modified alumina coating as a second carrier, and metals of Pt, rh and Pd as active components, and a three-way purifier made of the catalyst, a cushion layer and a shell can be used for purifying automobile exhaust. However, in comparison with building materials, catalysisThe market capacity of the agent is lower, and the stockpiling amount of the rare earth tailings cannot be reduced on a large scale.
The Sichuan rare earth resources are mainly distributed in the Minning county and the Delhang county of Liangshan, have the characteristics of good large-scale mining conditions, coarse mineral crystal particles, easy grinding, easy selection, easy smelting and easy separation, and are important rare earth producing areas in China. However, through years of development and utilization, the stockpiling amount of the Sichuan rare earth tailings is also huge. Research shows that the rare earth tailings in the area mainly contain chemical components such as silicon, aluminum, iron, calcium and the like which are highly similar to cement components, and a small amount of rare earth, fluorite, strontium barium and the like which are beneficial to forming cement clinker. Therefore, when the cement raw meal is prepared, part of the rare earth tailings are used as silicon, aluminum, iron and calcium raw materials and mineralizers, so that the feasibility is high. In view of the current situation that the demand of infrastructure on cement is huge, the cement clinker fired by the rare earth tailings can be massively consumed and the solid waste capacity can be realized, and the method has important significance on the green sustainable development of the Sichuan rare earth industry. Meanwhile, from the perspective of cement industry, cement is produced by utilizing various solid wastes, so that the use amount of traditional mineral resources can be reduced, the cyclic utilization of the solid waste resources is facilitated, the economic value of the solid waste resources is further improved, and the method has great significance for the sustainable development of the cement industry.
In conclusion, the rare earth tailings are difficult to utilize as resources. In comparison, the rare earth tailings used as the cement clinker have the characteristics of simple process, large dosage and the like, and are an important technical path for reducing the quantity of the cement clinker.
Therefore, the research of the rare earth tailings mixed with the calcined cement clinker is focused, which is beneficial to relieving the environmental pressure of stacking the rare earth tailings and reducing the development of natural mineral resources, and has important environmental significance for sustainable development of the rare earth tailings.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing cement clinker by using rare earth tailings, which can relieve the environmental pressure of stacking of the rare earth tailings, reduce the development of natural mineral resources and has important environmental significance for sustainable development of the rare earth tailings.
The purpose of the invention is realized by the following technical scheme:
a method for preparing cement clinker by utilizing rare earth tailings comprises the following steps:
1) Sorting and enriching rare earth minerals, fluorite and strontium barium minerals in the rare earth tailings to obtain re-sorted waste materials;
2) Mixing and grinding the re-selected waste material prepared in the step 1) and raw materials of cement raw materials, and uniformly mixing to obtain the raw materials of cement;
3) Calcining and cooling the cement raw material obtained in the step 2) to obtain cement clinker.
Further, the mass percentage of rare earth minerals, fluorite minerals and strontium barium minerals in the recleaning waste is less than or equal to 6%.
Further, the SiO in the recleaning waste material 2 、Fe 2 O 3 、Al 2 O 3 And CaO in a mass percentage of 70-90%.
Further, the values of the cement clinker prepared by the recleaning waste are as follows: the lime saturation coefficient KH is 0.88-0.92, the silicon ratio SM is 2.4-2.6, and the aluminum ratio IM is 1.2-1.8.
Further, the step of sorting and enriching in the step 1) is specifically as follows: and (3) separating and enriching rare earth minerals, fluorite and strontium-barium minerals in the rare earth tailings by gravity separation, flotation and magnetic separation.
Further, in the step 2), the mass percentage of the reselected waste in the cement raw meal is 0.1-20%.
Further, the cement raw meal in the step 2) needs to be crushed in advance, and then is mixed with the reselected waste for grinding.
Further, the raw materials of the cement in the step 2) comprise limestone, shale and pyrite cinder.
Further, in the step 2), the cement raw materials comprise the following components in parts by weight: 70-85 parts of limestone, 0.1-20 parts of recleaning waste, 14-24 parts of shale and 0-5 parts of pyrite cinder. The method for preparing the cement clinker by utilizing the rare earth tailing recleaning waste comprises the following steps: crushing 70-85 parts of lime, then feeding the crushed lime, 0.1-20 parts of recleaning waste, 0-5 parts of pyrite cinder and 14-24 parts of shale into a ball mill to finish grinding and homogenization to obtain a cement raw material doped with rare earth tailings, and calcining the obtained raw material at high temperature and rapidly cooling to obtain a cement clinker product.
Further, in the step 3), the cement raw materials are sequentially preheated, pre-decomposed and calcined under the high-temperature condition, and finally cooled to prepare the cement clinker.
Further, in the step 3), preheating and pre-decomposition of the cement raw materials are completed at 850-950 ℃, the preheating and pre-decomposition time is 30min, the time is the optimal time, and the specific range value can be adaptively adjusted according to the consumption of the raw materials to be treated and the actual situation. The calcination is completed at 1350-1450 ℃ for 15-45min.
The invention provides a method for preparing cement clinker by directly preparing and burning cement clinker by using rare earth tailings or by using recleaning waste materials obtained after rare earth tailings are used for sorting rare earth minerals, fluorite and strontium-barium minerals. The method aims to utilize the silicon-aluminum-iron-calcium components mainly contained in the rare earth tailings and exert the functions of promoting the decomposition of calcium carbonate and reducing the formation temperature of cement clinker by using the rare earth minerals, fluorite and strontium-barium minerals, thereby realizing the efficient utilization of the rare earth tailings. The qualified portland cement clinker can be successfully fired within the range that the rare earth tailings or the recleaning waste accounts for 0.1-20% of the cement raw materials.
The invention has the beneficial effects that:
1. the invention provides a method for preparing portland cement clinker by utilizing rare earth tailings ingredients, aiming at the fact that the rare earth tailings contain silicon, aluminum, calcium and iron raw materials required by cement raw materials and have the characteristic of a composite mineralizer. Compared with conventional mineralizing agents such as rare earth minerals, fluorite, strontium barium minerals and the like, the main elements (calcium iron silicon aluminum and the like) in the rare earth tailings are constituent elements of cement clinker, and the cement clinker prepared by sintering the rare earth tailings not only can reduce the using amount of traditional raw materials, but also has a composite mineralization function. From experimental results, the cement clinker fired in the range of 0.1-20% of the rare earth tailing recleaning waste in the cement raw meal can reach the national quality standard of the universal cement clinker.
2. The method related by the invention is obviously different from the method of using rare earth waste residue to mix and burn cement clinker, the rare earth tailings are a large amount of solid wastes produced by mining under natural conditions or obtained by enriching rare earth minerals under mild conditions, all components in the rare earth tailings are not calcined or chemically treated, the rare earth waste residue is the residual solid waste after extracting rare earth, the content of the rare earth is very low, the symbiotic minerals can be in an amorphous state, and the difference of the two in physical and chemical properties is large; in addition, the rare earth tailings related to the method are solid wastes containing various mineralizers, and are significantly different from the composite mineralizers obtained by manually blending ingredients in other schemes; in general, the method is innovative compared with the prior art in the selection of raw materials.
3. The method has the advantages of simple process, good large-scale effect, strong operability and the like, provides a new idea for the efficient utilization of the rare earth tailings, and solves the problem that the rare earth tailings cannot be utilized in large quantities for a long time.
Drawings
FIG. 1 is a process flow diagram of a method for preparing cement clinker by using rare earth tailings.
Detailed Description
The technical solution in the embodiments of the present invention will be fully described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, fall within the scope of protection of the present invention.
The embodiment is a method for preparing cement clinker by utilizing rare earth tailings, and a sample is rare earth tailings in a Sichuan German Chang continental slot. Firstly, rare earth minerals, fluorite and strontium barium minerals are enriched and recovered through the processes of gravity separation, flotation, magnetic separation and the like, and rare earth tailing recleaning waste is obtained. Secondly, the cement raw material prepared by the recleaning waste comprises the following components in parts by weight: 70-85 parts of limestone, 0.1-20 parts of reselected waste, 14-24 parts of shale and 0-5 parts of pyrite cinder. Wherein the rare earth tailings contain SiO 2 、Fe 2 O 3 、Al 2 O 3 And 70-90% of CaO; the cement clinker rate value is: the lime saturation coefficient KH is0.92-0.96, the silicon ratio SM is 2.0-2.4, and the aluminum ratio IM is 2.0-2.4.
The method for preparing and burning the cement clinker by utilizing the rare earth tailings and the recleaning waste comprises the following steps: after 73-75 parts of limestone is crushed, the crushed limestone and 2.5-10 parts of rare earth tailings are mixed with the waste, 14-21 parts of shale and 2.5 parts of sulfuric acid residue and then the mixture is put into a ball mill to complete ball milling and homogenization, thus obtaining the cement raw material. Then calcining the cement raw material at 950 ℃ for 30 minutes to complete preheating and predecomposition, then immediately transferring the cement raw material into a 1400 ℃ high-temperature furnace to calcine for 30 minutes, and rapidly cooling the calcined sample to obtain a cement clinker product.
The invention will now be described in more detail by way of example: the method takes the recleaning waste after the comprehensive utilization of the Deshang continental slot rare earth tailings as a research object, and SiO in the rare earth tailings 2 、Fe 2 O 3 、Al 2 O 3 The chemical components related to CaO and the cement clinker account for 75.99 percent, and are highly similar to the composition of the cement clinker. The tailings further contain 5.84% of fluorite, a small amount of sulfate minerals such as celestite, barite, strontium barium, and the like, and a small amount of rare earth minerals such as bastnaesite, monazite, and the like. These minerals are all common cement clinker mineralizers. The chemical composition of the other materials used is shown in table 1.
TABLE 1 analysis of main chemical elements of respective raw materials
| Name (R) | Loss | SiO 2 | Fe 2 O 3 | Al 2 O 3 | CaO | MgO | SO 3 |
| Rare earth tailings | 6.01 | 49.88 | 4.49 | 11.75 | 9.87 | 1.73 | 0.16 |
| Limestone | 41.00 | 4.22 | 1.55 | 0.76 | 51.25 | 0.67 | - |
| Sulfuric acid slag | 6.96 | 21.43 | 29.07 | 7.36 | 23.68 | 6.22 | 3.08 |
| Shale | 11.61 | 58.77 | 5.60 | 13.97 | 4.36 | 1.54 | 0.18 |
The concrete examples are proportioned according to the formula shown in the table 2, and the three-rate values of the raw meal are ensured to be in the range of KH =0.89-0.91, SM =2.51-2.52, IM =1.67-1.68 and the doping amount of the rare earth tailings is 2.5-10%. The specific formulation is shown in table 2. The raw materials are ground and homogenized by a ball mill and mixed with rare earth tailings to obtain cement raw materials, the raw materials are calcined for 30 minutes in a high-temperature furnace at 1400 ℃ after being pressurized and formed, and the raw materials are immediately taken out and rapidly cooled after the calcination is finished to obtain the cement clinker.
Table 2 ingredients recipe (%)
| Scheme(s) | Rare earth tailings recleaning waste material | Limestone | Sulfuric acid slag | Shale |
| Example 1 | 2.5 | 74.5 | 2.5 | 20.5 |
| Example 2 | 5.0 | 74.0 | 2.5 | 18.5 |
| Example 3 | 7.5 | 73.8 | 2.5 | 16.2 |
| Example 4 | 10.0 | 73.3 | 2.5 | 14.2 |
By adopting the technical scheme, the physical and chemical indexes of the fired cement clinker are shown in Table 3. As can be seen from Table 3, after the reasonable blending of the above scheme, the free calcium oxide content of each group of clinker is less than 1.5%, and the compressive strength of 3 days, 7 days and 28 days is respectively greater than 31MPa, 40MPa and 49MPa. Overall, the cement clinker has excellent properties.
TABLE 3 main performance indexes of cement clinker in examples
| Scheme(s) | f-CaO/％ | 3 days compression resistance/Mpa | 7 days compression resistance/Mpa | 28 days compression resistance/Mpa |
| Example 1 | 0.24 | 36.05 | 44.28 | 57.93 |
| Example 2 | 0.17 | 37.86 | 46.20 | 59.82 |
| Example 3 | 0.14 | 37.60 | 46.64 | 59.85 |
| Example 4 | 0.21 | 31.57 | 40.23 | 49.26 |
The embodiment of the invention has the following two effects: (1) The main components of the rare earth tailings are silicon, aluminum, iron, calcium and other cement-related components, so that the addition of the calcined cement clinker can reduce the exploitation of limestone, shale and iron ore, and is an effective way for utilizing the rare earth tailings in a large scale. Moreover, compared with natural resources, the rare earth tailings do not need to be crushed, and the processing cost is relatively lower. (2) The method for preparing cement clinker by using mineralizer is not only an advanced concept of low-temperature calcination and energy conservation, but also an important means for improving the yield and quality of clinker. However, the direct use of mineralizers such as rare earth minerals, fluorite, strontium barium minerals, etc. is costly and brings advantages that are not sufficient to translate directly into economic effects. The rare earth tailings contain a small amount of fluorite, sulfate minerals and rare earth minerals, and are a cheap composite mineralizer. Therefore, the rare earth tailings mixed with the cement clinker have good economic effect and environmental protection effect.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (2)
1. The method for preparing the cement clinker by using the rare earth tailings is characterized by comprising the following steps of:
1) Rare earth minerals, fluorite and strontium-barium minerals in rare earth tailings containing fluorite and strontium-barium are separated and enriched to obtain re-selection waste, the rare earth tailings are rare earth tailings of a Sichuan Delhang land slot, the mass percentage of the rare earth minerals, the fluorite minerals and the strontium-barium minerals in the re-selection waste is less than or equal to 6%, and SiO in the re-selection waste is 2 、Fe 2 O 3 、Al 2 O 3 And CaO in a mass percent of 70-90% respectively;
2) Mixing and grinding the reselected waste prepared in the step 1) and a raw cement material, and uniformly mixing to obtain a raw cement material containing the reselected waste, wherein the raw cement material containing the reselected waste comprises the following components in parts by weight: 73.3 to 74.5 portions of limestone, 2.5 to 10 portions of recleaning waste, 14.2 to 20.5 portions of shale and 2.5 portions of pyrite cinder; the values of the cement clinker prepared by the recleaning waste are as follows: the lime saturation coefficient KH is 0.89-0.91, the silicon rate SM is 2.51-2.52, and the aluminum rate IM is 1.67-1.68;
3) Calcining the cement raw material containing the recleaning waste obtained in the step 2) at 950 ℃ for 30min to complete preheating and predecomposition, and calcining at 1400 ℃ for 30min to complete calcination to obtain cement clinker.
2. The method for preparing cement clinker by using rare earth tailings as claimed in claim 1, wherein the step of sorting and enriching in the step 1) is specifically as follows: and (3) separating and enriching rare earth minerals, fluorite and strontium-barium minerals in the rare earth tailings by gravity separation, flotation and magnetic separation.
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| CN115340305B (en) * | 2022-05-30 | 2023-12-05 | 嘉华特种水泥股份有限公司 | Silicate cement for low-aluminum-acid tricalcium communication prepared from rare earth tailings and preparation method thereof |
| CN115010388B (en) * | 2022-07-15 | 2023-04-14 | 浙江红狮环保股份有限公司 | Method for firing cement clinker by using mixed solid waste |
| CN115557720A (en) * | 2022-10-28 | 2023-01-03 | 安徽海螺制剂工程技术有限公司 | Cement clinker mineralization reinforcing agent |
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