CN110627386A - Titanium slag cement and preparation method and application thereof - Google Patents
Titanium slag cement and preparation method and application thereof Download PDFInfo
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- CN110627386A CN110627386A CN201910926736.4A CN201910926736A CN110627386A CN 110627386 A CN110627386 A CN 110627386A CN 201910926736 A CN201910926736 A CN 201910926736A CN 110627386 A CN110627386 A CN 110627386A
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- titanium
- slag cement
- titanium 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
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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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- 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
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
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Abstract
The invention relates to the technical field of inorganic non-metallic materials, and discloses titanium slag cement and a preparation method and application thereof. The titanium slag cement contains titanium extraction tailings, an exciting agent, a reinforcing agent, an auxiliary reinforcing agent and an early strength agent; wherein the titanium extraction tailings contain 25-30 wt% of calcium oxide, 20-25 wt% of silicon dioxide, 5-10 wt% of titanium dioxide, 5-7 wt% of fixed carbon, 7-8 wt% of calcium chloride and magnesium chloride, 10-20 wt% of aluminum oxide and 5-10 wt% of magnesium oxide. The titanium slag cement is prepared by taking the titanium extraction tailings as a main raw material, the titanium slag cement has the characteristics of high strength and quick setting and hardening while the production cost of the titanium slag cement is reduced and the resource utilization rate is improved, and the performance index meets the index requirement of 325R grade of common portland cement, so that the titanium slag cement can be used for cement precast blocks, cement pavement bricks, mortar, roadbed water stabilization layers, soil solidification materials and temporary engineering.
Description
Technical Field
The invention relates to the technical field of inorganic non-metallic materials, in particular to titanium slag cement and a preparation method and application thereof.
Background
More than 700 million tons of titanium-containing blast furnace slag are generated every year by climbing steel, the research on the titanium extraction process of the titanium-containing blast furnace slag is currently carried out, and a large amount of titanium tailings are generated at the moment, so that environmental pollution and resource waste are inevitably caused if the titanium extraction tailings cannot be properly treated, and therefore, a resource utilization approach is needed to be taken to realize a green and clean development mode of the whole titanium-containing blast furnace slag titanium extraction process.
At present, a large amount of natural resource limestone is adopted for producing common portland cement, however, along with national mining limit control of natural resources and cement industry scale production limit, the price of portland cement is greatly increased year by year, and the profit space of building material enterprises is further reduced.
Disclosure of Invention
The invention aims to solve the problems of low utilization rate of titanium extraction tailings and high production cost of ordinary portland cement in the prior art, and provides titanium slag cement and a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a titanium slag cement comprising titanium extraction tailings, an activator, a reinforcing agent, an auxiliary reinforcing agent and an early strength agent;
wherein the titanium extraction tailings contain 25-30 wt% of calcium oxide, 20-25 wt% of silicon dioxide, 5-10 wt% of titanium dioxide, 5-7 wt% of fixed carbon, 7-8 wt% of calcium chloride and magnesium chloride, 10-20 wt% of aluminum oxide and 5-10 wt% of magnesium oxide.
Preferably, the titanium slag cement comprises 50-90 parts by weight of titanium extraction tailings, 5-20 parts by weight of excitant, 5-20 parts by weight of reinforcing agent, 0-5 parts by weight of auxiliary reinforcing agent and 0-5 parts by weight of early strength agent, based on 100 parts by weight of the total amount of the titanium slag cement.
Preferably, the activator is slaked lime.
Preferably, the reinforcing agent is desulfurized gypsum.
Preferably, the auxiliary enhancer is copperas.
Preferably, the early strength agent is calcium chloride and/or magnesium chloride.
The second aspect of the invention provides a preparation method of the titanium slag cement, which comprises the following steps:
(1) dry-mixing the titanium extraction tailings, the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent to obtain a mixture;
(2) and (3) aging and sealing and packaging the mixture obtained in the step (1).
Preferably, in the step (1), before the dry mixing, the method further comprises activating the titanium extraction tailings by ball milling, and crushing the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent.
The third aspect of the invention provides titanium slag cement prepared by the method.
The fourth aspect of the invention provides the application of the titanium slag cement in cement prefabricated blocks, cement pavement bricks, mortar, roadbed water stabilization layers, soil body solidification materials and temporary engineering.
The main raw materials of the titanium slag cement are tailings and fine powdery substances after titanium is extracted from titanium-containing blast furnace slag through high-temperature carbonization and low-temperature chlorination, wherein the glass state content of calcium silicate reaches over 90 percent, and the calcium silicate cement has good pozzolanic activity. The added excitant, reinforcing agent, auxiliary reinforcing agent and early strength agent are finely ground and uniformly mixed to obtain the titanium slag cement, the performance index of the titanium slag cement reaches the index requirement of 325R grade of ordinary portland cement, and the titanium slag cement has the characteristics of high strength, low cost and quick setting and hardening. The prepared titanium slag cement can be used independently or blended with common calcium silicate cement, has large resource amount and low cost, improves the utilization rate of titanium extraction tailings, reduces the production cost, and can be popularized and applied in the field of non-reinforced structure infrastructure.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides titanium slag cement in a first aspect, which contains titanium extraction tailings, an excitant, a reinforcing agent, an auxiliary reinforcing agent and an early strength agent;
wherein the titanium extraction tailings contain 25-30 wt% of calcium oxide, 20-25 wt% of silicon dioxide, 5-10 wt% of titanium dioxide, 5-7 wt% of fixed carbon, 7-8 wt% of calcium chloride and magnesium chloride, 10-20 wt% of aluminum oxide and 5-10 wt% of magnesium oxide.
Preferably, the titanium slag cement comprises 50-90 parts by weight of titanium-extracting tailings, 5-20 parts by weight of excitant, 5-20 parts by weight of reinforcing agent, 0-5 parts by weight of auxiliary reinforcing agent and 0-5 parts by weight of early strength agent, based on 100 parts by weight of the total weight of the titanium slag cement.
Preferably, the activator is slaked lime. Wherein, the content of the effective component calcium hydroxide in the slaked lime is more than 80 percent by weight, and the excitant can excite the silicate glass state with pozzolanic activity in the titanium extraction tailings to generate hydration reaction to form C-S-H gel. In the invention, the slaked lime is obtained by slaking quicklime.
In a preferred case, the reinforcing agent is desulfurized gypsum. Wherein, the content of the calcium sulfate dihydrate which is an effective component in the desulfurized gypsum is more than 80 percent by weight, and the reinforcing agent adopts the desulfurized gypsum with fibrous microstructure, thereby playing the roles of adjusting the setting time of the titanium slag cement and enhancing the integral strength.
In a preferred case, the auxiliary enhancer is copperas. Wherein, the content of the effective component ferrous sulfate heptahydrate in the copperas is more than 90%, and the auxiliary reinforcing agent can form long columnar iron ettringite in the hydration process of titanium slag cement, thereby playing the role of reinforcing the overall strength of the cement.
In a preferred case, the early strength agent is calcium chloride and/or magnesium chloride, and the early strength agent helps to improve the early strength of the set cement.
The second aspect of the invention provides a preparation method of the titanium slag cement, which comprises the following steps:
(1) dry-mixing the titanium extraction tailings, the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent to obtain a mixture;
(2) and (3) aging and sealing and packaging the mixture obtained in the step (1).
In a preferable case, in the step (1), before the dry mixing, the method further comprises performing ball milling activation on the titanium extraction tailings, and performing crushing treatment on the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent. The titanium extraction tailings are treated by a ball milling process to obtain titanium slag fine powder, and the specific surface area of the titanium slag fine powder is 400m2More than/kg, preferably 400-500m2Per kg, has better volcanic ash activity; after the excitant, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent are crushed, the granularity of the obtained fine powder is below 250 meshes. Wherein, the granularity of the fine powder obtained by crushing the excitant is below 200 meshes, and the crushing of the raw materials is beneficial to the full mixing and contact of the raw materials.
The third aspect of the invention provides titanium slag cement prepared by the method.
The fourth aspect of the invention provides the application of the titanium slag cement in cement prefabricated blocks, cement pavement bricks, mortar, roadbed water stabilization layers, soil body solidification materials and temporary engineering.
Compared with the ordinary Portland cement 325R, the titanium slag cement provided by the invention has the following advantages:
1) the raw materials are wide in source, low in price and easy to obtain, and metallurgical waste residue resources can be consumed;
2) the two-grinding and one-burning process is not needed, the production process is simple, the cost is lower, and the cost investment can be reduced;
3) can realize the high-efficient comprehensive utilization of titanium extraction tailings resources and meet the current circular economy policy requirements.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
The main chemical components and contents of the titanium extraction tailings used in examples 1 to 4 and comparative example 1 are shown in table 1.
TABLE 1
Main chemical composition | Calcium oxide | Silicon dioxide | Titanium dioxide | Aluminum oxide | Magnesium oxide | Fixed carbon | Calcium chloride | Magnesium chloride |
Content (%) | 28 | 25 | 6 | 13 | 9 | 6 | 6 | 2 |
Example 1
Uniformly mixing 80 parts by weight of titanium extraction tailings, 10 parts by weight of desulfurized gypsum, 5 parts by weight of slaked lime, 3 parts by weight of copperas, 2 parts by weight of calcium chloride and 1 part by weight of magnesium chloride by adopting a ball-milling dry mixing process to obtain a mixture, aging the mixture for 24 hours, and sealing and packaging to obtain titanium slag cement S1, wherein the performances of the titanium slag cement S1 are shown in Table 2. And ball milling activation is carried out on the titanium extraction tailings before dry mixing, and crushing treatment is carried out on the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent. After ball milling, the obtained titanium slag fine powder has a specific surface area of 405m2The method comprises the following steps of (1) crushing to obtain fine powder of slaked lime, copperas, calcium chloride and magnesium chloride, wherein the granularity of the fine powder of the slaked lime, the copperas, the calcium chloride and the magnesium chloride is below 250 meshes, and the granularity of the fine powder of the desulfurized gypsum is below 200 meshes; the slaked lime is obtained by slaking and reacting quicklime.
Example 2
And (2) uniformly mixing 50 parts by weight of titanium extraction tailings, 20 parts by weight of desulfurized gypsum, 20 parts by weight of slaked lime, 5 parts by weight of copperas and 5 parts by weight of calcium chloride by adopting a ball-milling dry mixing process to obtain a mixture, aging the mixture for 24 hours, and sealing and packaging to obtain titanium slag cement S2, wherein the performances of the titanium slag cement are shown in Table 2. And ball milling activation is carried out on the titanium extraction tailings before dry mixing, and crushing treatment is carried out on the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent. After ball milling, the specific surface area of the obtained titanium slag fine powder is 450m2The method comprises the following steps of (1) crushing to obtain fine powder of slaked lime, copperas and calcium chloride, wherein the granularity of the fine powder of the slaked lime, the copperas and the calcium chloride is below 250 meshes, and the granularity of the fine powder of the desulfurized gypsum is below 200 meshes; the slaked lime is obtained by slaking and reacting quicklime.
Example 3
Uniformly mixing 75 parts by weight of titanium extraction tailings, 10 parts by weight of desulfurized gypsum, 10 parts by weight of slaked lime, 3 parts by weight of calcium chloride and 2 parts by weight of magnesium chloride by adopting a ball-milling dry mixing process to obtain a mixture, aging the mixture for 24 hours, and compactingAnd (5) sealing and packaging to obtain the titanium slag cement S3 with the properties shown in Table 2. And ball milling activation is carried out on the titanium extraction tailings before dry mixing, and crushing treatment is carried out on the exciting agent, the reinforcing agent and the early strength agent. After ball milling, the obtained titanium slag fine powder has the specific surface area of 480m2The method comprises the following steps of (1) crushing to obtain fine powder of slaked lime, calcium chloride and magnesium chloride with the granularity of below 250 meshes and fine powder of desulfurized gypsum with the granularity of below 200 meshes; the slaked lime is obtained by slaking and reacting quicklime.
Example 4
And (2) uniformly mixing 80 parts by weight of titanium extraction tailings, 5 parts by weight of desulfurized gypsum, 15 parts by weight of slaked lime, 5 parts by weight of copperas and 5 parts by weight of magnesium chloride by adopting a ball-milling dry mixing process to obtain a mixture, aging the mixture for 24 hours, and sealing and packaging to obtain titanium slag cement S4, wherein the performances of the titanium slag cement are shown in Table 2. And ball milling activation is carried out on the titanium extraction tailings before dry mixing, and crushing treatment is carried out on the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent. After ball milling, the specific surface area of the obtained titanium slag fine powder is 440m2The method comprises the following steps of (1) crushing to obtain fine powder of slaked lime, copperas and magnesium chloride, wherein the granularity of the fine powder of the slaked lime, the copperas and the magnesium chloride is below 250 meshes, and the granularity of the fine powder of the desulfurized gypsum is below 200 meshes; the slaked lime is obtained by slaking and reacting quicklime.
Comparative example 1
The same procedure as in example 1 was repeated except that the titanium extraction tailings were changed to limestone, to obtain ordinary portland cement 325R, the properties of which are shown in table 2.
TABLE 2
The results in table 2 show that the titanium slag cement prepared by using the titanium extraction tailings as the main raw material has the characteristics of high strength and rapid setting and hardening while reducing the production cost of the titanium slag cement and improving the resource utilization rate, and the performance index meets the index requirement of 325R grade of common portland cement, so that the titanium slag cement can be used for cement precast blocks, cement pavement bricks, mortar, roadbed water stabilization layers, soil solidification materials and temporary engineering.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The titanium slag cement is characterized by comprising titanium extraction tailings, an excitant, a reinforcing agent, an auxiliary reinforcing agent and an early strength agent;
wherein the titanium extraction tailings contain 25-30 wt% of calcium oxide, 20-25 wt% of silicon dioxide, 5-10 wt% of titanium dioxide, 5-7 wt% of fixed carbon, 7-8 wt% of calcium chloride and magnesium chloride, 10-20 wt% of aluminum oxide and 5-10 wt% of magnesium oxide.
2. The titanium slag cement as claimed in claim 1, wherein the titanium slag cement comprises 50-90 parts by weight of titanium-extracting tailings, 5-20 parts by weight of excitant, 5-20 parts by weight of reinforcing agent, 0-5 parts by weight of auxiliary reinforcing agent and 0-5 parts by weight of early strength agent, based on 100 parts by weight of the total amount of the titanium slag cement.
3. The titanium slag cement according to claim 1 or 2, wherein said activator is slaked lime.
4. The titanium slag cement according to claim 1 or 2, wherein said reinforcing agent is desulfurized gypsum.
5. The titanium slag cement according to claim 1 or 2, wherein said auxiliary enhancer is copperas.
6. The titanium slag cement according to claim 1 or 2, wherein said early strength agent is calcium chloride and/or magnesium chloride.
7. A method for preparing titanium slag cement according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) dry-mixing the titanium extraction tailings, the exciting agent, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent to obtain a mixture;
(2) and (3) aging and sealing and packaging the mixture obtained in the step (1).
8. The method according to claim 7, wherein in the step (1), before the dry mixing, the method further comprises performing ball milling activation on the titanium extraction tailings, and performing crushing treatment on the excitant, the reinforcing agent, the auxiliary reinforcing agent and the early strength agent.
9. Titanium slag cement produced by the method of claim 7 or 8.
10. Use of the titanium slag cement according to any one of claims 1 to 6 or 9 in cement prefabricated blocks, cement road bricks, mortars, roadbed water stabilization layers, soil mass solidification materials and temporary works.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113233805A (en) * | 2021-06-10 | 2021-08-10 | 昆明理工大学 | Blast furnace titanium slag-based phosphate cement and application thereof |
CN115010391A (en) * | 2022-07-06 | 2022-09-06 | 西南科技大学 | Quick-setting alkali-activated titanium slag extraction cement and preparation method thereof |
CN115159881A (en) * | 2022-07-06 | 2022-10-11 | 西南科技大学 | Retarded alkali-activated titanium slag extracting cement and preparation method thereof |
CN115180841A (en) * | 2022-07-06 | 2022-10-14 | 西南科技大学 | Alkali-activated titanium slag extraction cement and preparation method thereof |
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CN109265115A (en) * | 2018-10-31 | 2019-01-25 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of inorganic gel and preparation method thereof |
CN109748566A (en) * | 2019-03-14 | 2019-05-14 | 攀钢冶金材料有限责任公司 | A kind of partition plate and preparation method thereof |
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CN108975784A (en) * | 2018-08-27 | 2018-12-11 | 攀钢集团攀枝花钢铁研究院有限公司 | It is a kind of non-burning brick and preparation method thereof |
CN109265115A (en) * | 2018-10-31 | 2019-01-25 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of inorganic gel and preparation method thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113233805A (en) * | 2021-06-10 | 2021-08-10 | 昆明理工大学 | Blast furnace titanium slag-based phosphate cement and application thereof |
CN115010391A (en) * | 2022-07-06 | 2022-09-06 | 西南科技大学 | Quick-setting alkali-activated titanium slag extraction cement and preparation method thereof |
CN115159881A (en) * | 2022-07-06 | 2022-10-11 | 西南科技大学 | Retarded alkali-activated titanium slag extracting cement and preparation method thereof |
CN115180841A (en) * | 2022-07-06 | 2022-10-14 | 西南科技大学 | Alkali-activated titanium slag extraction cement and preparation method thereof |
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