CN113277759A - Titanium slag-based solid waste cementing material and preparation method thereof - Google Patents
Titanium slag-based solid waste cementing material and preparation method thereof Download PDFInfo
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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
- C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
- C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
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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
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing 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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Abstract
The invention discloses a titanium slag-based solid waste cementing material and a preparation method thereof, wherein the titanium slag-based solid waste cementing material comprises the following raw materials in percentage by weight: titanium slag-based material: 70-80%, gypsum: 15-25%, cement clinker: 2.5 to 7.5 percent. The preparation method is simple, and the used materials are independently or mixed and ground according to different classifications of different grindability differences, and then are mixed and stirred. The gel material is prepared from the raw materials, wherein a titanium-containing slag-based material is used as a main component, and is matched with cement clinker and gypsum to form the gel material, so that the gel material can effectively and comprehensively utilize a large amount of high-titanium-containing slag and industrial byproduct gypsum resources produced by iron and steel enterprises in Panzhihua, Leshan Sand Bay and other places in the southwest region, can meet the application requirements of most conventional projects, and can also be used in construction environments with abundant tunnel geothermal energy.
Description
Technical Field
The invention relates to a titanium slag-based solid waste cementing material and a preparation method thereof, in particular to a multi-component synergetic solid waste cementing material for engineering prepared by using titanium slag and a preparation method thereof, belonging to the technical field of concrete materials.
Background
The high titanium slag (hereinafter referred to as titanium slag) mainly contains titanium pyroxene, perovskite, barite, spinel, etc., and contains CaO and SiO as main components2 、TiO2、Al2O3MgO, the melt of which consists essentially of the basic ion Ca2+,Mg2+,O2-,Ti2+,Ti3+And composite anion SiO4 2-,AlO4 -,TiO3 2-Composition of, wherein Ca2+Has a significant impact on slag properties. Due to TiO2Is a good crystal nucleus forming agent, Ca in titanium slag2+Predominantly with TiO3 2-Form perovskite, unlike ordinary blast furnace slag with SiO4 2-、AlO4 -The anion forms hydration active substances such as melilite, calcium silicate and the like. The generation of the minerals reduces the capability of forming reverse glass by leading an active ingredient CaO in the slag to enter into the glass body, improves the crystallization property of the slag, enables the slag structure to be more compact, and reduces the hydration activity of the slag, so that the titanium slag has the defects of stable structure, difficult activation, poor grindability, low activity and the like in the cement, and restricts the application of the titanium slag in the field of building materials. In a large amount of industrial waste residues in the metallurgical industry in the southwest region, titanium slag is discharged by more than ten million tons every year, cannot be applied to cement and concrete in a large scale, namely, is used or needs to be used, is small in use and addition proportion, and basically plays a filling role in concrete.
The prior patent document EP3081546A1 discloses a high-hardness high-belite sulfurThe quick-hardening high belite calcium sulphoaluminate cement prepared by mixing and grinding the cement clinker, the anhydrite and the granulated blast furnace slag has the advantages of quick setting and hardening, high early strength, high 28-day high compressive strength reaching 79-81MPa and good working performance. 0.1-0.3% of Li can be doped2CO3Shortening setting time and improving early strength, citric acid can be added to prolong setting time and improve later strength. The clinker proportion of the quick-hardening high belite sulphoaluminate cement used for grinding cement is 26-97%, gypsum is 3-19%, and GBF slag is 0-55%, the clinker proportion is high, and the strength is mainly determined by cement clinker minerals, and the cement clinker minerals are cooperated with the gypsum and the GBF slag for hydration reaction.
The prior patent document CN108083671A discloses a granulated blast furnace slag excitant, which can effectively excite the activity of granulated blast furnace slag after the combination of gypsum and high belite sulphoaluminate cement clinker with specific mixture ratio, fully play the contribution of the granulated blast furnace slag to the early and later mechanical properties of cement, greatly promote the hydration hardening speed of the cement, further improve the early strength and the later strength, especially the breaking strength, and in addition, the generated fine crystalline ettringite fills pores of cement slurry to form a compact matrix, thereby ensuring that the cement concrete has excellent impermeability and durability.
Based on the above situation, it can be known that in the prior art, EP3081546a1 uses high belite sulphoaluminate clinker with specific mineral composition as a main component, gypsum and slag are added to prepare the cementing material, and the use amount of solid wastes is not high enough. CN108083671A researches the excitation of active slag to prepare an excitant, and the activity of granulated blast furnace slag is effectively excited by special cement clinker and gypsum in proper proportion, so that the influence of the excitant on the cement performance is improved, and the aim of improving the flexural strength and the compressive strength of the cement is fulfilled. But the titanium-doped slag, the fly ash and other solid waste applications are less involved; the influence of the environmental temperature on the cementing material is less. In tunnel engineering, the problems of high buried depth and high terrestrial heat caused by the tunnel engineering have special requirements on the cementing material. Therefore, the titanium slag-based solid waste cementing material is researched and developed, the solid waste utilization rate is high, the application of most conventional engineering is met, the material characteristics are combined, and the titanium slag-based solid waste cementing material can be used in a construction environment with abundant tunnel geothermal energy.
Disclosure of Invention
The invention aims to provide a titanium slag-based solid waste cementing material, which takes titanium-containing slag-based materials as main components, is matched with cement clinker and gypsum to form a cementing material, can realize effective comprehensive utilization of a large amount of high-titanium-containing slag and industrial byproduct gypsum resources produced by iron and steel enterprises such as Panzhihua and Leshan Bay in southwest region, and can be used in construction environments with abundant tunnel geothermal energy besides meeting most of conventional engineering applications.
The other purpose of the invention is to provide a titanium slag-based solid waste cementing material and a preparation method thereof, wherein the used materials are subjected to single or mixed grinding according to different classifications of the difference of grindability, and then are mixed and stirred. The cement can be produced smoothly by common cement enterprises.
The invention is realized by the following technical scheme: the titanium slag-based solid waste cementing material is characterized in that: the composite material comprises the following raw materials in percentage by weight:
titanium slag-based material: 70-80 percent of the total weight of the mixture,
gypsum: 15 to 25 percent of the total weight of the mixture,
cement clinker: 2.5 to 7.5 percent.
The titanium slag-based material is a mixture of granulated blast furnace slag, modified electrolytic manganese slag, titanium slag, fly ash, silicomanganese slag and the like.
According to weight percentage, in the titanium slag-based material, the content of the granulated blast furnace slag is not less than 30 percent, the content of the modified electrolytic manganese slag is 0-10 percent, and the rest content is titanium slag, fly ash, silicomanganese slag and the like which are mixed in any proportion.
The granulated blast furnace slag meets the requirements of the GB/T203 granulated blast furnace slag for cement.
The titanium slag is a melt containing silicate and aluminosilicate obtained in the process of smelting pig iron in a blast furnace, and TiO is quenched into granules2Slag with a content of more than 10%.
The titaniumThe specific surface area of the slag-based material is more than or equal to 420m2/kg。
The gypsum is at least one selected from natural anhydrite, desulfurized gypsum and phosphogypsum.
The desulfurization gypsum and the phosphogypsum are both modified gypsum obtained under the conditions that the ignition temperature is 650 plus 850 ℃ and the heat preservation time is more than 20 minutes.
The cement clinker is high belite sulphoaluminate clinker, and can be produced by using a common cement kiln at present according to the requirements of target chemical composition and mineral components, and the calcination temperature of a calcination zone during clinker calcination is usually 1300-1350 ℃.
The specific surface area of the gypsum and the cement clinker is more than 420m2/kg。
The preparation method of the titanium slag-based solid waste cementing material comprises the steps of uniformly mixing the ground titanium slag-based material, gypsum and cement clinker according to the proportion to obtain the cementing material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention carries out development research on titanium slag and other solid wastes in a targeted manner in the development application of solid waste resources, the used materials are granulated blast furnace slag, titanium slag, silicomanganese slag, modified electrolytic manganese slag, fly ash, gypsum, cement clinker and the like with the content of less than 10 percent, and the used gypsum is anhydrite which can be replaced by modified desulfurized gypsum and modified phosphogypsum, so the consumption of the solid waste of the cementing material can be more than 90 percent, the carbon emission is low, and the invention has a positive effect on the comprehensive utilization of resources, particularly the treatment of a large amount of titanium slag with higher titanium oxide and industrial byproduct gypsum resources and the like produced by steel enterprises such as Panzhihua, Leshan Bay and the like in southwest area at present, and has good economic benefit and social benefit. According to the characteristics, the cementing material can also be used in a tunnel engineering under a higher temperature environment.
(2) The gelled material provided by the invention takes granulated blast furnace slag, titanium slag, fly ash, modified electrolytic manganese slag, silicomanganese slag and the like as main components, and is matched with special cement clinker and anhydrite (or modified desulfurized gypsum and modified phosphogypsum), so that the prepared gelled material has the main hydration product of AFt, basically has no C-S-H gel, is stable in hydrate at normal temperature and physical properties, has the characteristics of high breaking strength, good corrosion resistance, low hydration heat, good volume stability and the like, and meets the requirements of a large number of engineering applications.
(3) The components of the invention can be used with titanium slag-based materials in larger mixing amounts. Wherein the titanium slag comprises CaO and SiO as main components2、TiO2、Al2O3MgO, the melt of which consists essentially of the basic ion Ca2+，Mg2+，O2-，Ti2+，Ti3+And composite anion SiO4 2-，AlO4-，TiO3 2-And (4) forming. Wherein Ca2+Has a significant impact on slag properties. Due to TiO2Is a good crystal nucleus forming agent, Ca in titanium slag2+Predominantly with TiO3 2-Form perovskite, unlike ordinary blast furnace slag with SiO4 2-、AlO4-The anion forms hydration active substances such as melilite, calcium silicate and the like. The generation of the minerals reduces the capability of forming reverse glass by leading active ingredient CaO in the slag to enter into the glass body, and improves the crystallization property of the slag to ensure that the slag structure is more compact, thereby reducing the hydration activity of the slag, so that the perovskite has a more stable structure in the cement and is difficult to activate, and the application of the perovskite in the field of building materials is restricted. Under the condition of normal-temperature curing, the surface of the titanium slag is not corroded basically, and it can be seen that the activity of the titanium slag under the condition of normal temperature is difficult to be excited, but under the condition of higher-temperature curing, the microstructure of the doped titanium slag is much denser than that of normal-temperature curing. As can be seen from the test strength test, under the curing condition of 20-60 ℃, the strength at the early stage (3 days and 7 days) and the strength at the later stage (28 days, 60 days and 180 days) are increased along with the increase of the curing temperature, and the strength is equal to the strength at 28 days at the curing temperature of 80 ℃. There is no obvious difference in the type of hydration product, but the amount of hydration product varies, thus affecting the degree of densification of the microstructure. The electrolytic manganese slag is industrial solid waste produced by treating manganese carbonate ore powder with sulfuric acid solution to electrolyze manganese metal, and sulfate thereofThe ammonia nitrogen and manganese have higher concentration, and the appearance of the ammonia nitrogen and manganese is black fine particles which are hardened after precipitation. The mineral components mainly comprise dihydrate gypsum, quartz, etc. The electrolytic manganese slag contains more ammonia substances, and can generate a large amount of ammonia gas to bring great difficulty to use in an alkaline gelling system, and the modified electrolytic manganese slag is the slag obtained by burning the electrolytic manganese slag at a proper temperature (600-800 ℃); fly ash is fine ash collected from flue gas generated after coal combustion, and is main solid waste discharged from coal-fired power plants. The silicomanganese slag is a solid waste produced by smelting silicomanganese alloy.
(4) The hydration product ettringite of the concrete prepared by the cementing material has dehydration phenomenon at the temperature of 132-150 ℃, the strength is reduced, but the strength can be recovered after water return. The tunnel geothermal temperature is usually below 80 ℃, so the solid waste cementing material can meet the use requirement of a tunnel in a higher temperature environment.
(5) When the hydration reaction of the cementing material is carried out, as the concentration and alkalinity of each ion in the hydration environment are proper, the generation of ettringite is quicker, the ion dissolution speed in the glass body is also accelerated, ettringite particles formed after the dissolution ions in the glass body participate in the reaction are filled into the framework of unreacted ions and are mutually wrapped and interpenetrated to form a compact structure, so that the early strength and the later strength are much higher than those of other industrial waste residue activated cementing materials, the setting and hardening time is greatly shortened, and the later strength has excellent performance.
In conclusion, the cementing material produced by the invention takes the titanium slag-based material as the main material, wherein the use of high-doped titanium slag, fly ash, electrolytic manganese slag, silicomanganese slag and the like is involved, anhydrite or modified desulfurized gypsum (and modified phosphogypsum) and high belite sulphoaluminate clinker are matched as the exciting agent, the use mode that the existing titanium slag and the like are only used as the filler is changed, the titanium slag-based material which is reasonably matched and combined can be used in high doping amount under the action of the exciting agent, and better heat-resistant effect can be obtained while the comprehensive utilization rate of the resources such as the titanium slag and the like is realized, so that the cementing material can not only meet the conventional engineering, but also can be used in construction environments with richer geothermal heat, such as tunnel engineering and the like.
Tests prove that compared with other cement with less clinker or no clinker, the strength values of the cementing material in 3 days and 28 days are nearly doubled under the condition of the same amount of industrial waste residues. The hydration heat is low, the hydration heat in 7 days is only about 172J/g, and is far lower than that of other varieties of cement. The sulfate erosion resistance is strong, and the sulfate erosion resistance coefficients of 7 days, 28 days and 60 days of precuring are 0.98, 1.07 and 1.3 respectively. The test piece is cured at the temperature of 20 ℃, 40 ℃, 60 ℃ and 80 ℃, the strength of the test piece is increased along with the increase of the curing temperature in 7 days and 28 days, the strength of 60 ℃ in 180 days is increased by about 10 percent compared with the strength of 20 ℃, and the strength of 60 ℃ in 360 days is basically equal to the strength of 60 ℃ in 180 days. The strength at 80 ℃ is basically equal to that at 60 ℃ in 360 days. The test shows that the thermally activated part of the titanium slag is hydrated at higher temperature, so that the hydrated product is more compact, and the strength of the titanium slag at each age is improved.
Drawings
FIG. 1 is a diagram comparing the X-ray diffraction patterns of the cementing material hydration product with granulated blast furnace slag and titanium slag.
FIG. 2 is a 3-day hydrate phase diagram of the gel material of the invention.
FIG. 3 is a 90-day hydrate phase diagram of the gel material of the present invention.
FIG. 4 is an electron micrograph of hydrates (28 days 20 ℃) of the cement according to the invention.
FIG. 5 is an electron micrograph of hydrates (28 days 60 ℃) of the cementitious material according to the invention.
FIG. 6 is an electron micrograph of hydrates (60 days at 60 ℃) of the cementitious material according to the invention.
As can be seen from figure 1, the hydration product ettringite is obtained after the titanium slag-based solid waste material which can not be hydrated independently is activated by the activating material, and as can be seen from figures 2 and 3, as the hydration time increases, the gypsum continuously participates in the reaction until the gypsum basically disappears, and the amount of the ettringite continuously increases. As can be seen from fig. 4 to 6, the hydrate is more dense with increasing curing age and curing temperature.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is to be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention claimed, and unless otherwise defined, 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 prior patent documents EP3081546a1 and CN108083671A all describe that the cement properties, such as acceleration of the hydration hardening speed, increase of early and later strength, etc., can be effectively improved by using high belite sulphoaluminate system clinker and (hard) gypsum as an activator for activating the activity of granulated blast furnace slag. In the patent document EP3081546A1, the fast-hardening high belite sulphoaluminate cement clinker proportion is 26-97%, the gypsum is 3-19%, and the GBF slag is 0-55%, the clinker proportion is high, and the strength is exerted mainly by the cement clinker minerals as main components and the hydration reaction of the gypsum and the GBF slag. CN108083671A is mainly used for preparing an excitant aiming at granulated blast furnace slag, so that super-sulfate cement with excellent performance is obtained. The research on the synergy of other solid wastes such as titanium slag, fly ash, electrolytic manganese slag, silicomanganese slag and the like and the hydration at different curing temperatures is not carried out.
On the basis, the invention introduces solid wastes such as titanium slag, fly ash, electrolytic manganese slag, silicon manganese slag and the like to be matched with granulated blast furnace slag for use. By doping titanium slag and the like, the use effect of the cementing material can be improved, the excitation effect of granulated blast furnace slag in the cement system is excellent, and the high-level physical strength is still maintained after the titanium slag and the fly ash are highly doped. Experiments prove that the hydration mechanism of the cementing material is different from that of the traditional cementing material, the hydration is carried out in a low-alkali environment, and the hydration products such as calcium silicate hydrate and calcium hydroxide are almost not generated through thermogravimetry and X-ray diffraction analysis. As the hydration time progresses, the amount of calcium sulfate decreases until it disappears, and the amount of hydrate ettringite increases, as shown in fig. 1 to 3. The ettringite is fibrous under the observation of an electron microscope, hydrate is compact, and unhydrated substances gradually become little. Along with the improvement of the maintenance temperature and the increase of the maintenance age, the titanium slag part gradually disintegrates to participate in hydration, and the strength has the performance of great increase, especially the early strength. As can be seen from fig. 4 to 6, the hydrate is more dense with increasing curing age and curing temperature.
The hydration product of the cementing material is mainly ettringite (AFt), the hydration product can be dehydrated at the temperature of 132-150 ℃ to cause crystal transformation, and the ettringite (Aft) is basically stable in the temperature range of less than 100 ℃. Researches show that even after dehydrated ettringite (AFt + AFm) returns water, the physical strength of a test piece can be continuously maintained and even slightly increased, which is one of important characteristics of the cement hydrate. The test piece is placed in an environment of 80 ℃ for 180 days and 360 days, the retention of the physical strength is good, and in addition, the ettringite is used as the cementing material of the main hydration product, so that the test piece has better performance on the bonding strength of a matrix and an aggregate, and the later-stage flexural strength and the anti-permeability strength are high.
The following examples are provided to illustrate specific embodiments of the present invention, and it is understood that the scope of the present invention is not limited to the following examples.
Examples 1 to 12:
mainly relates to a titanium slag-based solid waste cementing material, and the raw material preparation is carried out according to the following table 1.
Table 1 raw material preparation table
In the raw material configuration table, the granulated blast furnace slag is the slag meeting the requirements of the GB/T203 granulated blast furnace slag for cement; the titanium slag is a melt containing silicate and aluminosilicate obtained in the process of smelting pig iron in a blast furnace, and TiO is quenched into particles2Slag with a content of more than 10%; the modified desulfurization gypsum and the modified phosphogypsum are modified gypsum obtained under the conditions that the firing temperature is 650 plus 850 ℃ and the heat preservation time is more than 20 minutes; high belite sulfurThe main minerals in the aluminate clinker include: c4A3 
、C2S、C4AF、CaSO4 、CT and f-CaO, the weight percentage of the mineral composition is as follows: c4A3 
20-40%、C2S 35-50%、C4AF 1-10%、CaSO42-24% and f-CaO 1-7%. The clinker comprises the following chemical components in percentage by weight: 48-55% of calcium oxide, 12.2-19.2% of silicon dioxide, 11.5-20% of aluminum oxide, 0.3-3.3% of ferric oxide and 12-17% of sulfur trioxide. Wherein, C4A3 
Is anhydrous calcium sulphoaluminate, C2S is dicalcium silicate, C4AF is tetracalcium aluminoferrite, CaSO4Calcium sulfate, f-CaO, free calcium oxide, and CT, perovskite.
It should be noted that, besides the raw materials mentioned in the above examples, some additional chemical agents, such as carbonate, citric acid, nitrite, etc., can be optionally added to the cement material of the present invention to improve the properties of the material, such as setting time, early strength, etc.
Example 13:
the embodiment mainly relates to a preparation method of a titanium slag-based solid waste cementing material, which specifically comprises the following steps:
s1: the raw materials adopted by the titanium slag-based material are dried and ground, and the used materials can be singly or mixed and ground according to actual conditions by considering the inconsistency of the grindability of the materials, such as granulated blast furnace slag, titanium slag, silicomanganese slag and the like are ground according to a proper proportion, the fly ash and the modified electrolytic manganese slag can be mixed and ground according to a proper proportion, and the gypsum and the clinker are mixed and ground according to a proper proportion. The specific surface area of the ground titanium slag base material is required to be more than 420m2/kg(ii) a Grinding gypsum and cement clinker to specific surface area greater than 420m2/kg。
S2: and fully mixing the ground materials by using mixing equipment according to a proportion to obtain the required cementing material.
In a specific embodiment, when the cementitious material of embodiment 5 is prepared, the granulated blast furnace slag, the titanium slag and the fly ash are mixed according to a certain proportion and then ground, so that the specific surface area of the ground titanium slag base material is controlled to 425 m2In terms of/kg. Mixing the modified desulfurized gypsum, the modified phosphogypsum and the high belite sulphoaluminate clinker in proportion, and then grinding the mixture until the specific surface area is 455 m2In terms of/kg. And then fully mixing the ground materials by using mixing equipment according to a proportion to obtain the cementing material.
The following tests were carried out on one of the titanium slag-based solid waste gelled materials obtained in examples 1 to 12 above:
the flexural strength and compressive strength of the cementing materials 3d, 7d, 28d, 180d and 360d were tested according to GB/T17671 1999 in Cement mortar Strength testing method (ISO method) at different experimental temperatures of 20 ℃, 40 ℃, 60 ℃ and 80 ℃, respectively as shown in the following Table 2.
TABLE 2 flexural and compressive strength data of cementitious materials at different temperatures
The hydration heat of the cementing material in 3 days, 7 days and 28 days is tested according to a method for measuring hydration heat of cement GB/T12959-2008, and the sulfate corrosion resistance coefficients of the material in 7 days, 28 days and 60 days are tested according to a method for testing sulfate corrosion resistance of cement GB/T749-2008, and are respectively shown in the following table 3.
TABLE 3 hydration Heat and sulfate erosion coefficient data for cementitious materials
In summary, tests prove that the cementing material has the following advantages: (1) the later-period breaking strength is obviously higher than that of other varieties of cement; (2) low hydration heat and small shrinkage; (3) the microstructure is compact, and the impermeability is good; (4) the corrosion resistance to sulfate is higher than 1.0; (5) the alkalinity of hydration products is low; (6) economical, low-carbon and environment-friendly.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The titanium slag-based solid waste cementing material is characterized in that: the composite material comprises the following raw materials in percentage by weight:
titanium slag-based material: 70-80 percent of the total weight of the mixture,
gypsum: 15 to 25 percent of the total weight of the mixture,
cement clinker: 2.5 to 7.5 percent.
2. The titanium slag-based solid waste cementitious material according to claim 1, characterized in that: the titanium slag-based material is a mixture of granulated blast furnace slag, modified electrolytic manganese slag, titanium slag, fly ash, silicomanganese slag and the like.
3. The titanium slag-based solid waste cementitious material according to claim 2, characterized in that: according to weight percentage, in the titanium slag-based material, the content of the granulated blast furnace slag is not less than 30 percent, the content of the modified electrolytic manganese slag is 0-10 percent, and the rest content is titanium slag, fly ash and silicomanganese slag mixed in any proportion.
4. The titanium slag-based solid waste cementitious material according to claim 2, characterized in that: the titanium slag is a melt containing silicate and aluminosilicate obtained in the process of smelting pig iron in a blast furnace, and TiO is quenched into granules2Slag with a content of more than 10%.
5. The titanium slag-based solid waste cementitious material according to claim 1, characterized in that: the specific surface area of the titanium slag-based material is more than or equal to 420m2/kg。
6. The titanium slag-based solid waste cementitious material according to claim 1, characterized in that: the gypsum is at least one selected from natural anhydrite, modified desulfurized gypsum and modified phosphogypsum.
7. The titanium slag-based solid waste cementitious material according to claim 6, characterized in that: the desulfurization gypsum and the phosphogypsum are both modified gypsum obtained under the conditions that the ignition temperature is 650 plus 850 ℃ and the heat preservation time is more than 20 minutes.
8. The titanium slag-based solid waste cementitious material according to claim 1, characterized in that: the cement clinker is high belite sulphoaluminate clinker.
9. The titanium slag-based solid waste cementitious material according to claim 1, characterized in that: the specific surface area of the gypsum and the cement clinker is more than 420m2/kg。
10. A preparation method of a titanium slag-based solid waste cementing material is characterized by comprising the following steps: the cementitious material is prepared by uniformly mixing the ground titanium slag-based material, gypsum and cement clinker according to the proportion of claim 1.
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