CN115572082A - Method for producing clinker-free cement by using large-amount lepidolite residues - Google Patents

Method for producing clinker-free cement by using large-amount lepidolite residues Download PDF

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Publication number
CN115572082A
CN115572082A CN202211334248.2A CN202211334248A CN115572082A CN 115572082 A CN115572082 A CN 115572082A CN 202211334248 A CN202211334248 A CN 202211334248A CN 115572082 A CN115572082 A CN 115572082A
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lepidolite
slag
residues
free cement
cement
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邓葆军
刘华峰
刘凯
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Jiangxi Yongxing Special Steel New Energy Technology Co ltd
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Jiangxi Yongxing Special Steel New Energy Technology Co ltd
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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
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • 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 producing clinker-free cement by using large-amount lepidolite residues, belonging to the technical field of industrial residue utilization and cement building materials. According to the invention, 35-45% of lepidolite slag, 25-35% of steelworks slag, 15-25% of steelworks steel slag and 5-8% of gypsum are weighed according to the mass percentage, then the weighed lepidolite slag, steelworks steel slag and gypsum are uniformly mixed, and grinding aid is added for grinding to obtain clinker-free cement. The cement produced by the method has high strength and stable performance, reduces the production cost, simultaneously treats a large amount of waste lepidolite residues for the society, and has good economic and social benefits; calculated according to the fact that 100 ten thousand tons of cement produced per year is doped with 40% of lepidolite residues, 40 ten thousand tons of lepidolite residues can be consumed, land resources occupied by stacking or burying the lepidolite residues are greatly saved, and environmental protection pressure is reduced.

Description

Method for producing clinker-free cement by using large-amount lepidolite residues
Technical Field
The invention belongs to the technical field of industrial waste residue utilization and cement building materials, and particularly relates to a method for producing clinker-free cement by using high-content lepidolite residues.
Background
With the development of new energy technology, the adoption of lithium ion batteries as a power source instead of fuel oil has become a global consensus and trend. The main raw material of the lithium ion battery is lithium carbonate, and the lithium carbonate accounts for more than half of the total source of the lithium carbonate extracted from the lepidolite. However, when lithium carbonate is extracted using lepidolite ore, 18 to 20 tons of waste slag are generated per one ton of lithium carbonate produced. At present, in China, nearly millions of tons of waste residues are generated every year only by extracting lithium carbonate from lepidolite, and how to treat and digest the waste residues is an important task of each lithium carbonate manufacturer.
Through detection, the activity of the lepidolite slag is stronger than that of the fly ash, so that most of lithium carbonate plants are connected with cement plants at present, and the lepidolite slag is provided for the cement plants to be used as a mixed material. However, because the water content of the waste residue is higher and reaches 18-22%, the use amount of the waste residue in a cement plant is limited, and the mixing amount is only about 3-5%, so that a large amount of waste residue in a plurality of lithium carbonate plants cannot be digested and is limited by environmental protection departments for production; the preparation of clinker-free cement by roasting lepidolite slag by a sulfate method has not been reported yet.
Disclosure of Invention
Aiming at the problems in the background art, the invention utilizes the advantage that the lepidolite slag has higher activity to compound with other materials, and can produce the clinker-free cement. The cement produced by the invention does not need clinker, has high strength and stable performance, reduces the production cost, simultaneously treats a large amount of industrial waste residues for the society, and has good economic and social benefits.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
the invention provides a method for producing clinker-free cement by using large-amount lepidolite residues, which comprises the following steps:
step 1): weighing 35-45% of lepidolite slag, 25-35% of steel mill slag, 15-25% of steel mill slag and 5-8% of gypsum according to mass percentage for later use;
step 2): and uniformly mixing the weighed lepidolite slag, steelworks slag and gypsum, and adding a grinding aid for grinding to obtain the clinker-free cement.
Preferably, the lepidolite slag in the step 1) is waste slag generated by extracting lithium carbonate from lepidolite ore through water leaching after roasting.
Because the lepidolite slag is roasted at 900-1050 ℃ and then water-quenched, the crystal lattices of the main components of silicon dioxide and aluminum oxide in the slag are transformed, and the crystal dense state is transformed into the amorphous active state. According to the component analysis, the main components of the lepidolite residue are active silicon dioxide and aluminum oxide, and the lepidolite residue is biased to calcined kaolin, so that the lepidolite residue is an active material with high volcanic ash property. In the hydration process of the lepidolite slag powder, the active silicon dioxide and the alumina can perform secondary hydration reaction with calcium hydroxide separated from other materials such as steel slag, slag and the like during hydration, and calcium aluminosilicate cementing materials are generated under the blending of calcined gypsum to form clinker-free cement.
Preferably, the lepidolite slag contains SiO as a main component 2 、Al 2 O 3 、Fe 2 O 3 、CaO、K 2 O、Na 2 O、SO 3 (ii) a Wherein SiO is 2 38 to 45 percent of Al in the total mass ratio 2 O 3 Accounting for 19 to 24 percent of the total mass ratio.
Preferably, the lepidolite slag and the steelworks slag in the step 2) are dried and water is controlled to be not more than 2% before being mixed.
Preferably, the steel slag of the steel mill in the step 2) is crushed and deironized before being mixed.
Preferably, the gypsum in the step 2) is crushed and roasted before being mixed; the roasting is carried out for 1 hour at the temperature of 850-950 ℃.
Preferably, the grinding aid is one or more of alcohol amine, polycarboxylic acid and formate.
Preferably, the addition amount of the grinding aid is one ten thousandth to two thousandth of the total mass of the lepidolite slag, the steelworks steel slag and the gypsum.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for producing clinker-free cement by using large-amount lepidolite residues, the produced cement has high strength and stable performance, the production cost is reduced, a large amount of waste lepidolite residues are treated for the society, and the economic and social benefits are good. Calculated by mixing 40% of lepidolite slag into 100 million tons of cement produced every year, 40 million tons of lepidolite slag can be consumed, land resources occupied by stacking or burying the lepidolite slag are greatly saved, and the environmental protection pressure is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experiment of the invention adopts waste lepidolite slag generated by extracting lithium carbonate from lepidolite ore by water leaching after roasting, and the main components and the content of the waste lepidolite slag are shown in table 1.
TABLE 1
Composition (A) SiO 2 Al 2 O 3 Fe 2 O 3 CaO K 2 O Na 2 O SO 3 Loss
Ratio of (a)/% 40.2 20.9 2.3 9.5 1.2 1.0 4.7 2.8
Example 1
1. Drying the lepidolite slag and the steel mill slag until the water content is not more than 2%; crushing steel factory steel slag into fine particles with the particle size not more than 3 millimeters, and removing iron by using an iron remover with the magnetic strength of 1T; crushing gypsum into particles with the particle size not more than 10 mm, and roasting for 1 hour at 900 ℃.
2. 3500 g of lepidolite slag powder, 3200 g of steel mill slag powder, 2500 g of steel mill steel slag powder and 800 g of calcined gypsum which are obtained by the treatment are taken and evenly mixed, then 1 g of polycarboxylic acid and polyalcohol amine are taken respectively, atomized and sprayed on the mixed powder, and the mixture is ground for 30 minutes by a 500 x 500 test mill and sieved and ground for 10 minutes to prepare the clinker-free cement powder.
The cement mortar molding and strength test were carried out according to the ISO method, and the results are shown in Table 2. Wherein, the mass percentage of the grinding aid is calculated by the total weight of other raw materials (the same below).
TABLE 2
Figure BDA0003914171410000041
Example 2
1. Drying the lepidolite slag and the steel mill slag until the water content is not more than 2%; crushing steel factory steel slag into fine particles with the particle size not more than 3 millimeters, and removing iron by using an iron remover with the magnetic strength of 1T; crushing gypsum into particles with the particle size not more than 10 mm, and roasting at 850 ℃ for 1 hour.
2. Taking 4500 g of lepidolite slag powder, 3500 g of steel mill slag powder, 1500 g of steel mill steel slag powder and 500 g of calcined gypsum obtained by the treatment, uniformly mixing the lepidolite slag powder, the steel mill steel slag powder and the calcined gypsum, then taking 1 g of polycarboxylic acid and polyalcohol amine respectively, atomizing, spraying the atomized mixture on the mixed powder, grinding the mixture for 30 minutes by using a 500 x 500 test mill, and sieving and grinding the mixture for 10 minutes to obtain the clinker-free cement powder.
The cement mortar molding and strength test were carried out according to the ISO method, and the results are shown in Table 3.
TABLE 3
Figure BDA0003914171410000051
Example 3
1. Drying the lepidolite slag and the steel mill slag until the water content is not more than 2%; crushing steel factory steel slag into fine particles with the particle size not more than 3 millimeters, and removing iron by using an iron remover with the magnetic strength of 1T; crushing gypsum into particles with the particle size not more than 10 mm, and roasting at 900 ℃ for 1 hour.
2. And uniformly mixing 3800 g of lepidolite slag powder, 3500 g of steel mill slag powder, 1900 g of steel mill slag powder and 800 g of calcined gypsum obtained by the treatment, then taking 1 g of polycarboxylic acid and polyalcohol amine respectively, atomizing, spraying on the mixed powder, grinding for 30 minutes by using a 500 x 500 test mill, and sieving and grinding for 10 minutes to obtain clinker-free cement powder.
The cement mortar molding and strength test were carried out by the ISO method, and the results are shown in Table 4.
TABLE 4
Figure BDA0003914171410000052
Example 4
1. Drying the lepidolite slag and the steel mill slag until the water content is not more than 2%; crushing steel factory steel slag into fine particles with the particle size not more than 3 millimeters, and removing iron by using an iron remover with the magnetic strength of 1T; crushing gypsum into particles with the particle size of not more than 10 mm, and roasting for 1 hour at 950 ℃.
2. And (3) uniformly mixing 4200 g of lepidolite slag powder, 3400 g of steel mill slag powder, 1700 g of steel mill slag powder and 700 g of calcined gypsum obtained by the treatment, then taking 1 g of polycarboxylic acid and polyalcohol amine respectively, atomizing, spraying on the mixed powder, grinding for 30 minutes by using a 500 x 500 test mill, and sieving and grinding for 10 minutes to obtain the clinker-free cement powder.
The cement mortar molding and strength test were carried out according to the ISO method, and the results are shown in Table 5.
TABLE 5
Figure BDA0003914171410000061
Comparative example 1
The formulation and strength of a conventional 32.5 grade cement are shown in table 6.
TABLE 6
Figure BDA0003914171410000062
Figure BDA0003914171410000071
Comparative example 2
The spodumene slag is adopted to replace the lepidolite slag to prepare the clinker-free cement:
the main components and contents of the spodumene slag used are shown in table 7.
TABLE 7
Composition (I) SiO 2 Al 2 O 3 Fe 2 O 3 CaO K 2 O Na 2 O SO 3 Loss
Ratio of (a)/% 54.8 24.1 0.9 10.5 0.4 0.3 8.6 6.8
1. Drying the spodumene slag and the steel mill slag until the water content is not more than 2%; crushing the steel slag of the steel mill into fine particles with the particle size not more than 3 mm, and removing iron by using an iron remover with the magnetic strength of 1T.
2. 3500 g of spodumene slag powder, 3200 g of steel mill slag powder, 2500 g of steel mill steel slag powder and 800 g of gypsum which are obtained by the treatment are taken and evenly mixed, then 1 g of polycarboxylic acid and polyalcohol amine are taken respectively, atomized and sprayed on the mixed powder, and the powder is ground for 30 minutes by a 500 x 500 test mill and sieved and ground for 10 minutes to obtain the clinker-free cement powder.
The cement mortar molding and strength test were carried out according to the ISO method, and the results are shown in Table 8.
TABLE 8
Figure BDA0003914171410000072
In conclusion, the clinker-free cement produced by the large-doped lepidolite slag powder has high early strength and the later strength far exceeds the strength requirement of 32.5-grade cement. Under the condition of the same proportion, the spodumene slag is used for replacing the lepidolite slag, although the strength standard of 32.5-grade cement can be achieved, the early strength and the later strength of the spodumene slag are not the same as the strength of the lepidolite slag with the same proportion, which is probably because the different contents of the two materials further cause the difference of the effects in the hydration reaction. The clinker-free cement produced by the large-doped lepidolite slag powder has high early strength, and the later strength far exceeds the strength requirement of 32.5-grade cement. The technology of the invention treats a large amount of industrial wastes of lepidolite slag and steel slag for society, and has good economic and social benefits.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in greater detail and detail, but not intended to limit the invention. It should be understood that various changes and modifications can be made by those skilled in the art, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the invention should be included in the scope of the invention.

Claims (8)

1. A method for producing clinker-free cement by using large-amount lepidolite residues is characterized by comprising the following steps:
step 1): weighing 35-45% of lepidolite slag, 25-35% of steelworks slag, 15-25% of steelworks steel slag and 5-8% of gypsum for later use according to the mass percentage;
step 2): and uniformly mixing the weighed lepidolite residues, steel mill slag, steel mill steel slag and gypsum, adding a grinding aid, and grinding to obtain clinker-free cement.
2. The method for producing clinker-free cement by using the high-volume lepidolite slag according to claim 1, wherein the lepidolite slag in the step 1) is waste slag generated by water leaching lithium carbonate after roasting lepidolite ore.
3. The method for producing clinker-free cement using the lepidolite slag as claimed in claim 2, wherein the lepidolite slag comprises a major component of SiO 2 、Al 2 O 3 、Fe 2 O 3 、CaO、K 2 O、Na 2 O、SO 3 (ii) a Wherein SiO is 2 38 to 45 percent of Al in the total mass ratio 2 O 3 Accounting for 19 to 24 percent of the total mass ratio.
4. The method for producing clinker-free cement by using the highly doped lepidolite slag as claimed in claim 1, wherein the lepidolite slag and the steelworks slag in step 2) are dried before being mixed until the moisture content is not more than 2%.
5. The method for producing clinker-free cement by using the lepidolite residue with large content according to claim 1, wherein the steel mill steel slag in the step 2) is crushed and deironized before being mixed.
6. The method for producing clinker-free cement by using the highly-doped lepidolite residues as claimed in claim 1, wherein the gypsum in step 2) is crushed and roasted before being mixed; the roasting is carried out for 1 hour at the temperature of 850-950 ℃.
7. The method for producing clinker-free cement by using the heavily doped lepidolite slag as claimed in claim 1, wherein the grinding aid is one or more compounds of alcohol amine, polycarboxylic acid and formate.
8. The method for producing clinker-free cement by using the highly doped lepidolite residue as claimed in claim 1, wherein the additive amount of the grinding aid is one ten thousandth to two thousandth of the total mass of the lepidolite residue, the steelworks slag, the steelworks steel slag and the gypsum.
CN202211334248.2A 2022-10-28 2022-10-28 Method for producing clinker-free cement by using large-amount lepidolite residues Pending CN115572082A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5755876A (en) * 1995-09-08 1998-05-26 Fmc Corporation Cement compositions for controlling alkali-silica reactions in concrete and processes for making same
CN101525217A (en) * 2009-04-21 2009-09-09 常州工程职业技术学院 Environmental-friendly clinker-free cement and preparation method thereof
CN106116189A (en) * 2016-06-28 2016-11-16 东南大学 A kind of no first-hand datum lithium slag composite gelled material
CN113072312A (en) * 2021-05-22 2021-07-06 江西南氏锂电新材料有限公司 Method for preparing cement from lithium slag
CN113845317A (en) * 2021-09-24 2021-12-28 广西源盛矿渣综合利用有限公司 Clinker-free solid waste system cement and manufacturing method thereof
CN114804684A (en) * 2022-01-17 2022-07-29 河北工业大学 Ultra-low carbon clinker-free cement and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5755876A (en) * 1995-09-08 1998-05-26 Fmc Corporation Cement compositions for controlling alkali-silica reactions in concrete and processes for making same
CN101525217A (en) * 2009-04-21 2009-09-09 常州工程职业技术学院 Environmental-friendly clinker-free cement and preparation method thereof
CN106116189A (en) * 2016-06-28 2016-11-16 东南大学 A kind of no first-hand datum lithium slag composite gelled material
CN113072312A (en) * 2021-05-22 2021-07-06 江西南氏锂电新材料有限公司 Method for preparing cement from lithium slag
CN113845317A (en) * 2021-09-24 2021-12-28 广西源盛矿渣综合利用有限公司 Clinker-free solid waste system cement and manufacturing method thereof
CN114804684A (en) * 2022-01-17 2022-07-29 河北工业大学 Ultra-low carbon clinker-free cement and preparation method and application thereof

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