CN111018391A - Modified stone coal tailings and preparation method and application thereof - Google Patents
Modified stone coal tailings and preparation method and application thereof Download PDFInfo
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- CN111018391A CN111018391A CN201911067139.7A CN201911067139A CN111018391A CN 111018391 A CN111018391 A CN 111018391A CN 201911067139 A CN201911067139 A CN 201911067139A CN 111018391 A CN111018391 A CN 111018391A
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- stone coal
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention relates to modified stone coal tailings and a preparation method and application thereof, wherein the modified stone coal tailings are prepared by adding water into a modifier and stone coal tailings, stirring and mixing uniformly, and then aging for 5-20 days. The effective components of the modifier mainly comprise calcium-based alkaline components, such as quicklime, slaked lime, carbide slag, cement ash, white mud or other calcium-based alkaline substances, and a small amount of a composite functional chelating agent is added. The modification mechanism of the method is that calcium-based alkaline substances and the composite functional chelating agent react with soluble vanadium existing in most vanadate anions and a small amount of metal vanadium cations in the stone coal tailings under alkaline conditions to generate stable calcium vanadate and metal chelate, so that the degree of chemical reaction of the soluble vanadium in cement hydration under alkaline conditions is reduced, the influence of the stone coal tailings on the cement hydration process and the setting time is further reduced, and the early strength of the cement is improved.
Description
Technical Field
The invention relates to the technical field of cement building materials, in particular to modified stone coal tailings and a manufacturing method and application thereof.
Background
The stone coal is generated in old stratum and is formed by transforming biological remains such as bacteria and algae under the actions of sapropelation and coalification in shallow sea environment. Besides silicon and carbon hydrogen elements, the stone coal also contains various associated elements such as vanadium, molybdenum, nickel, uranium, silver, noble metals and the like, wherein the relative content of vanadium is rich, the grade of vanadium pentoxide is generally 0.3-1.0%, and meanwhile, the stone coal has a certain heat value of 3.5-10.5 MJ/kg and is a low-heat-value fuel. The most important purpose is to extract vanadium by roasting and leaching, and then the vanadium is used as fuel, tailings such as vanadium slag generated after vanadium is extracted from stone coal and bottom slag generated after stone coal is combusted (generally called stone coal tailings) are generated in the utilization processes.
At present, the main use of stone coal tailings as raw materials of building materials is utilized, and the problem of obviously prolonging the cement setting time generally exists in the process of utilizing the stone coal tailings as cement admixture in cement plants, thereby influencing the quality stability of cement and limiting the utilization rate of the cement. The stone coal tailings such as vanadium slag can prolong the cement setting time, but the reason analysis, action mechanism and modification research of the stone coal tailings on cement retardation are not found. According to the invention, the special modifier is prepared according to the action mechanism of the stone coal tailings on the cement retarding, so that the influence of the stone coal tailings on the cement performance is reduced, and the utilization rate of solid waste resources in the cement production is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing modified stone coal tailings serving as a cement admixture and a preparation method thereof, the modified stone coal tailings prepared by the method can solve the problems of long cement setting time and low early strength of the stone coal tailings serving as the admixture, and compared with original stone coal tailings, when the mixing amount of the stone coal tailings in cement is 10% and 30%, the cement setting time can be respectively shortened by more than 30 minutes and 80 minutes, and the 1-day compressive strength of the cement can be improved by more than 1 MPa.
The invention adopts the following technical scheme:
the modified stone coal tailings are prepared by adding water into a modifier and stone coal tailings, uniformly stirring, and aging for 5-20 days.
Preferably, the stone coal tailings are vanadium-containing tailings.
Further preferably, the vanadium-containing tailings are stone coal vanadium extraction tailings, stone coal fuel combustion tailings, or vanadium-containing steel slag or the like.
Preferably, the modifier is prepared from a calcium-based alkaline component and a composite functional chelating agent in a weight ratio of (50-20) to (1-3). The modification mechanism is that the soluble vanadium mainly containing vanadate anions in the stone coal tailings reacts with the soluble vanadium mainly containing vanadate anions under alkaline conditions to generate insoluble calcium vanadate, and stabilization pretreatment is carried out, so that the reaction degree of the soluble vanadium in the stone coal tailings in cement hydration is reduced, and the influence of the soluble vanadium on the cement hydration process and the setting time is further reduced. The calcium formate and the aminodithioformate are compounded to mainly improve the early activity of the stone coal tailings as a cement admixture.
Further preferably, the calcium-based alkaline component includes quicklime, slaked lime, carbide slag, waste water sludge ash, or other calcium-based alkaline substance.
Further preferably, the composite functional chelating agent is prepared by compounding dithiocarbamate and calcium formate according to the mass ratio of (1-3) to (1-3).
The preparation method of the modified stone coal tailings comprises the following steps:
step 1: uniformly stirring the modifier and the stone coal tailings to obtain a material I;
step 2: adding water into the material I, and uniformly stirring to obtain a material II;
and step 3: and aging the material II for 5-20 days to finish the preparation of the modified stone coal tailings.
Preferably, in the step 1, the formula of the modifier and the stone coal tailings comprises 1-5 parts by weight of the modifier and 95-99 parts by weight of the stone coal tailings.
Further preferably, in the step 2, the water added into the material I is 1-5 times of the weight of the modifier.
The modified stone coal tailings or the modified stone coal tailings prepared by the method can be used as a mixed material of various cements with different strength grades.
The invention has the following beneficial effects:
1. the invention is based on the action mechanism of stone coal tailings on cement retarding (namely vanadium dissolved out of stone coal tailings compresses double electron layers of cement hydration particles at the initial stage of cement hydration under alkaline condition, and insoluble Ca is formed3(VO4)2Not only consume Ca2+And OH-Ionic, simultaneously poorly soluble Ca3(VO4)2The calcium-based alkaline matter and the composite functional chelating agent are respectively reacted with soluble vanadium existing in most of vanadate anions and a small amount of metal vanadium cations in the stone coal tailings under alkaline conditions to generate stable calcium vanadate and metal chelate, so that the degree of chemical reaction of the soluble vanadium in the cement hydration under alkaline conditions is reduced, the influence of the soluble vanadium on the cement hydration process and the setting time is further reduced, and the early strength of the cement is improved.
2. When the prepared modified stone coal tailings are used as a cement admixture, when the mixing amount of the stone coal tailings in cement is 10% and 30%, compared with the original stone coal tailings, the cement setting time can be respectively shortened by more than 30 minutes and 80 minutes, the 1-day compressive strength of the cement can be improved by more than 1MPa, the cement quality and the stability can be effectively improved, and the utilization rate of the stone coal tailings as the cement admixture is increased.
3. The prepared modified stone coal tailings can be fully utilized in all large cement production enterprises, the negative effects of land occupation and environment pollution caused by stone coal tailings stacking are reduced, and the environmental protection benefit is remarkable.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
And (3) uniformly mixing 50 parts of quicklime, 1 part of aminodithioformate and 1 part of calcium formate as a modifier to prepare the modified stone coal tailings. The method comprises the following specific steps:
1) adding the modifier and the stone coal tailings into a uniformly mixing device according to the mass percentage of 1% and 99%;
2) adding water with the mass of 4% of the material into the blending device, and stirring and blending uniformly;
3) aging the uniformly stirred materials for 5 days and 15 days to finish the preparation of the modified stone coal tailings.
When the undisturbed stone coal tailings and the prepared modified stone coal tailings are respectively used as 32.5-grade and 42.5-grade cement mixing materials, the cement performance comparison conditions are shown in table 1:
the component proportion of the cement admixture is simply introduced (32.5-grade cement is 58% of clinker, 5% of gypsum, 22% of limestone powder and 15% of stone coal cinder, and 42.5-grade cement is 78% of clinker, 5% of gypsum, 7% of limestone powder and 10% of stone coal cinder)
TABLE 1 Cement Performance comparison of stone coal tailings as admixtures
From the data in the above table 1, it can be seen that, compared with the original stone coal tailings, when the modified stone coal tailings are used as a cement admixture, the retardation of the modified stone coal tailings on cement is improved, when the mixing amount of the stone coal tailings is 10% and 15%, the setting time of the cement is respectively shortened by more than 30 and 40 minutes, and the compressive strength is improved by 1MPa in 1 day.
Example 2
And uniformly mixing 30 parts of hydrated lime, 1 part of dithiocarbamate and 1 part of calcium formate as a modifier to prepare the modified stone coal tailings. The method comprises the following specific steps:
1) adding the modifier and the stone coal tailings into a uniformly mixing device according to the mass percentage of 3% and 97%;
2) adding water with the mass of 6% of the material into the blending device, and stirring and blending uniformly;
3) aging the uniformly stirred materials for 5 days and 20 days to finish the preparation of the modified stone coal tailings.
When the undisturbed stone coal tailings and the prepared modified stone coal tailings are respectively used as 32.5-grade and 42.5-grade cement mixing materials, the cement performance comparison conditions are shown in table 2:
the component proportion of the cement admixture is simply introduced (the proportion of 32.5-grade cement is 58 percent of clinker, 5 percent of gypsum, 7 percent of limestone powder and 30 percent of stone coal cinder, and the proportion of 42.5-grade cement is 78 percent of clinker, 5 percent of gypsum, 2 percent of limestone powder and 15 percent of stone coal cinder).
TABLE 2 Cement Performance comparison of stone coal tailings as admixtures
From the data in the above table 2, it can be seen that, compared with the original stone coal tailings, when the modified stone coal tailings are used as a cement admixture, the retardation of the modified stone coal tailings on cement is improved, when the stone coal tailings are mixed in an amount of 15% and 30%, the setting time of the cement is respectively shortened by more than 40 and 80 minutes, and the strength of the cement is improved in 1 day.
Example 3
And (3) uniformly mixing 20 parts of cement ash, 1 part of dithiocarbamate and 1 part of calcium formate to serve as a modifier to prepare the modified stone coal tailings. The method comprises the following specific steps:
1) adding the modifier and the stone coal tailings into a uniformly mixing device according to the mass percentage of 5% and 95%;
2) adding water accounting for 5% of the mass of the materials in the uniformly mixing device, and uniformly mixing the materials;
3) aging the uniformly stirred materials for 5 days and 10 days to finish the preparation of the modified stone coal tailings.
When the undisturbed stone coal tailings and the prepared modified stone coal tailings are respectively used as 32.5-grade and 42.5-grade cement admixture, the cement performance comparison conditions are shown in table 3:
the component proportion of the cement admixture is simply introduced (32.5-grade cement is 58% of clinker, 5% of gypsum, 17% of limestone powder and 20% of stone coal cinder, and 42.5-grade cement is 78% of clinker, 5% of gypsum, 5% of limestone powder and 12% of stone coal cinder)
TABLE 3 comparison of cement properties when stone coal tailings are used as admixture
From the data in the above table 3, it can be seen that, compared with the original-state stone coal slag, when the modified stone coal slag is used as a cement admixture, the retardation of the modified stone coal slag on cement is improved, the setting time of the cement is obviously shortened, and the early strength of the cement in 1 day is improved.
Comparative example 1
The modifier was cement ash alone, and the other examples were the same as example 3. The cement properties are shown in Table 4:
TABLE 4 Cement Performance comparison of stone coal tailings as admixtures
It can also be seen from the data in table 4 above that, compared with the original-state stone coal cinder, when the modified stone coal cinder is used as a cement admixture, the cement setting time is obviously shortened, but the shortening effect is slightly lower than that of example 3, and the early strength of the cement is not obviously increased.
Comparative example 2
The modifier was only complex functional chelator (1 part dithiocarbamate and 1 part calcium formate), otherwise as in example 3. The cement properties are shown in Table 5:
TABLE 5 Cement Performance comparison of stone coal tailings as admixtures
From the data in table 5 above, it can be seen that, compared with the original-state stone coal slag, when the modified stone coal slag is used as a cement admixture, the cement setting time is slightly shortened, but the shortening is not obvious, and the 1d early compressive strength is obviously increased, but the increasing effect is slightly lower than that of the example 3.
Comparative example 3
The same procedure as in example 3 was repeated except that 20 parts of the cement ash and 1 part of the dithiocarbamate were used as a modifier to prepare a modified stone coal tailings. The cement properties are shown in Table 6:
TABLE 6 comparison of cement properties when stone coal tailings are used as admixture
From the data in table 6, it can be seen that, compared with the original-state stone coal cinder, when the modified stone coal cinder is used as a cement admixture, the cement setting time is obviously shortened, which is equivalent to the effect of example 3, but the early strength of the cement is not obviously increased.
Comparative example 4
The same procedure as in example 3 was repeated except that 20 parts of cement ash and 1 part of calcium formate were used as modifiers to prepare modified stone coal tailings.
The cement properties are shown in Table 7:
TABLE 7 comparison of cement properties when stone coal tailings are used as admixture
It can be seen from the data in table 7 above that, compared with the original-state stone coal slag, when the modified stone coal slag is used as a cement admixture, the compressive strength of the cement at the early stage of 1d is obviously increased, the setting time of the cement is also obviously shortened, but the setting time shortening effect is slightly lower than that of the example 3.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, and any modifications, equivalents, improvements and the like made without departing from the technical scope of the present invention as set forth in the claims should be considered within the scope of the present invention.
Claims (10)
1. The modified stone coal tailings are characterized in that the modified stone coal tailings are prepared by adding water into a modifier and stone coal tailings, uniformly stirring, and aging for 5-20 days.
2. The modified stone coal tailings of claim 1, wherein the stone coal tailings are vanadium-containing tailings.
3. The modified stone coal tailings of claim 2, wherein the vanadium-containing tailings are stone coal vanadium extraction tailings, stone coal fuel combustion tailings, or vanadium-containing steel slag or others.
4. The modified stone coal tailings as claimed in claim 1, wherein the modifier is prepared from a calcium-based alkaline component and a composite functional chelating agent in a weight ratio of (50-20) to (1-3).
5. The modified stone coal tailings of claim 4 wherein the calcium-based alkaline component comprises quicklime, slaked lime, carbide slag, waste sludge ash, or other calcium-based alkaline material.
6. The modified stone coal tailings of claim 4, wherein the composite functional chelating agent is prepared by compounding dithiocarbamate and calcium formate according to a mass ratio of (1-3) to (1-3).
7. The method for preparing the modified stone coal tailings of any one of claims 1 to 6, wherein the method comprises the following steps:
step 1: uniformly stirring the modifier and the stone coal tailings to obtain a material I;
step 2: adding water into the material I, and uniformly stirring to obtain a material II;
and step 3: and aging the material II for 5-20 days to finish the preparation of the modified stone coal tailings.
8. The method as claimed in claim 7, wherein in the step 1, the modifier and the stone coal tailings are formulated according to the following weight parts of 1-5 parts of modifier and 95-99 parts of stone coal tailings.
9. The method as claimed in claim 7, wherein in the step 2, the material I is added with water 1-5 times of the weight of the modifier.
10. The modified stone coal tailings as claimed in any one of claims 1 to 6 or prepared by the method as claimed in any one of claims 7 to 9 can be used as a mixed material for various types of cement with different strength grades.
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Application publication date: 20200417 |