CN108774043B - High-doping-ratio red mud building material - Google Patents
High-doping-ratio red mud building material Download PDFInfo
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- CN108774043B CN108774043B CN201810847445.1A CN201810847445A CN108774043B CN 108774043 B CN108774043 B CN 108774043B CN 201810847445 A CN201810847445 A CN 201810847445A CN 108774043 B CN108774043 B CN 108774043B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
- C04B28/32—Magnesium oxychloride cements, e.g. Sorel cement
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
The red mud building material with high doping ratio comprises red mud, chromium slag, light-burned magnesium powder, magnesium chloride brine and a water reducing agent; fly ash and a modifier; uniformly mixing the red mud raw material and the chromium slag, uniformly mixing the light-burned magnesium powder, the red mud and the chromium slag premix, adding the mixture into magnesium chloride brine, stirring for 2-5 min, adding a modifier, continuously stirring for 3min, and adding a water reducing agent; supplementing water to the red mud and chromium slag composite material raw material powder, fully stirring to obtain red mud magnesium gel composite material slurry, pouring the red mud magnesium gel composite material slurry into a mould, and demoulding to obtain the high-doping-ratio red mud building material. Under the condition of high-doping-ratio red mud, the red mud has excellent flexural strength, compressive strength and softening coefficient, and is suitable for most building environments. The problems of halogen return, frost and the like do not exist, and the requirements of various fields are met in various aspects such as roads, bridges, houses and the like. Thereby greatly utilizing the red mud and the chromium slag and reducing the environmental pollution caused by stacking the red mud and the chromium slag.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a high-doping-ratio red mud building material.
Background
The comprehensive treatment and utilization of red mud are a worldwide problem. In recent years, with the enhancement of environmental protection, the discharge condition of the red mud is greatly improved, but the problem of environmental pollution caused by the red mud cannot be fundamentally changed. The problem can be solved fundamentally only by realizing the resource utilization of the red mud.
Therefore, scholars at home and abroad make a great deal of research work on the comprehensive treatment of the red mud and make a lot of remarkable progress. However, the existing red mud recycling method has the defects of low red mud doping amount, low red mud utilization rate, high energy consumption and the like, and cannot consume a large amount of red mud. For example, the existing red mud is used as a building material, and is currently used as a standard support only according to the standards of other similar building materials. The market acceptance is low, so that the application of the product is limited, and the large-scale popularization is difficult. And compared with the existing cement, the cement has the advantages that the parameters such as compression resistance, folding resistance and the like can not meet corresponding requirements, so that the cement is not suitable for most of building materials. Therefore, how to reasonably utilize the red mud with high efficiency becomes a technical problem in the field.
Disclosure of Invention
The invention aims to overcome the defects of low red mud doping amount, low red mud utilization rate, high energy consumption, incapability of consuming a large amount of red mud and the like of the conventional red mud building material, and provides a red mud building material with high doping ratio, so that all performances of the red mud building material can reach the use standard.
The high-doping-ratio red mud building material is prepared from the following raw materials in parts by weight: 1200 parts of red mud, 1200 parts of chromium slag, 600 parts of light-burned magnesium powder, 672 parts of magnesium chloride brine and 4 parts of a water reducing agent; it is characterized by also comprising fly ash and a modifier; crushing the red mud, sieving the crushed red mud by a 30-mesh sieve to obtain a red mud raw material, and uniformly mixing the red mud raw material and the chromium slag to obtain a red mud and chromium slag premix; uniformly mixing light-burned magnesium powder with the red mud and chromium slag premix, adding the mixture into magnesium chloride brine, stirring for 2-5 min, adding a modifier, continuously stirring for 3min, and adding a water reducing agent to obtain red mud and chromium slag composite material raw material powder; supplementing water to the red mud and chromium slag composite material raw material powder to enable the mass ratio of the red mud and chromium slag composite material raw material powder to the water to be 100: 30-100: 50, fully stirring to obtain red mud magnesium gel composite material slurry, pouring the red mud magnesium gel composite material slurry into a mold, performing vibration molding, curing for 6-24 hours, demolding, and performing natural curing after demolding to obtain the high-doping-ratio red mud building material.
Wherein the modifier is a phosphoric acid modifier; the composite material also comprises 30 parts of phosphoric acid modifier and 60-360 parts of fly ash according to mass fraction.
The composite material also comprises 30 parts of phosphoric acid modifier and 180 parts of fly ash according to mass fraction.
Wherein, also comprises silicon powder; also comprises 20-100 parts of silicon powder by mass.
Wherein the modifier is a phosphoric acid modifier, a sodium citrate modifier and an oxalic acid modifier; the modified fly ash comprises, by mass, 4.98 parts of a phosphoric acid modifier, 15 parts of a sodium citrate modifier, 25.12 parts of an oxalic acid modifier and 30-150 parts of fly ash.
Wherein the modifier is a phosphoric acid modifier, a sodium citrate modifier and an oxalic acid modifier; the modified fly ash further comprises, by mass, 4.98 parts of a phosphoric acid modifier, 15 parts of a sodium citrate modifier, 25.12 parts of an oxalic acid modifier and 60 parts of fly ash.
Wherein the activity of the light-burned magnesium powder is 56.375 percent by adopting a hydration method.
The molar ratio of active magnesium oxide to magnesium chloride in the light-burned magnesium powder is 5: 1-9: 1, and the optimal molar ratio of active magnesium oxide to magnesium chloride in the light-burned magnesium oxide is 5: 1.
Wherein the pH value of the red mud is 12.23.
The invention has the following beneficial effects: under the condition of high-doping-ratio red mud, the red mud building material has excellent flexural strength, compressive strength and softening coefficient, and is suitable for most building environments. The problems of halogen return, frost and the like do not exist, and the requirements of various fields are met in various aspects such as roads, bridges, houses and the like. Thereby greatly utilizing the red mud and the chromium slag and reducing the environmental pollution caused by stacking the red mud and the chromium slag.
Drawings
FIG. 1 is a bar graph of 28-day flexural strength in example 1 of the present invention;
FIG. 2 is a bar graph of 28-day compressive strength in example 1 of the present invention;
FIG. 3 is a graph of 7-day softening coefficient data in example 1 of the present invention.
Detailed Description
Noun interpretation
(1) The light calcined magnesia in the invention refers to the magnesium hydroxide which is calcined at about 700-1000 ℃ and then discharges CO2Or H2The product obtained after O, the magnesium hydroxide is extracted from magnesite, brucite and sea water or brine.
(2) The active magnesium oxide in the invention refers to the average particle size of less than 2000 nm; the microscopic morphology is irregular particles or nearly spherical particles or flaky crystals; the activity expressed by citric acid (CAA value) is 12-25 s (the activity is higher when the value is smaller); the activity expressed by iodine absorption value is 80-120 (mgI/100 gMgO); the specific surface is 5-20 m3The specific volume is 6-8.5 mL/g.
(3) Detection method of flexural strength
Material testing machine: the relative error of the formula value of the tester is not more than +/-1%, the lower pressure plate is a spherical hinge support, and the expected maximum failure load is between 20% and 80% of the measuring range.
The experimental steps are as follows:
1) measuring the width and height dimensions of the experiment and recording;
2) and (3) placing the large surface of the sample on the lower support rod, wherein the distance between the two end surfaces of the sample and the lower support rod is the same, when the sample has cracks or depressions, the large surface is downward, and the sample is uniformly loaded at the speed of (50-150) N/s until the sample is broken, and recording the maximum load P.
3) And calculating the maximum bending strength of the data of the maximum load according to a bending formula, and recording.
The flexural strength (δ F) of each specimen was calculated by the following formula:
in the formula: deltaFNormal temperature flexural strength, Mpa;
Fmaxmaximum pressure applied to the sample, N
Ls-distance between lower edges, mm;
b-width of sample, mm;
h-height of the sample, mm.
The experimental results are expressed as the arithmetic mean Rf of the flexural strength.
(4) Detection method of compressive strength
1) Measuring the length and width of each experimental connecting surface or compression surface to 1 mm;
2) the sample is flatly placed in the center of the pressurizing plate, the loading is carried out perpendicular to the pressure-bearing surface, the loading is uniform and stable, the impact or vibration cannot occur, the loading speed is preferably (2-6) KN/s, and the maximum breaking load P is recorded until the sample is broken.
3) And calculating the maximum bending strength of the data of the maximum load according to a bending formula, and recording.
4) Calculation results and evaluation
Flexural strength (f) of each specimenc) Calculated as follows:
in the formula fc-compressive strength (Mpa); fmax-the maximum load (KN) at which the test piece is crushed;
a-bearing area (mm)2)
The experimental results are expressed as arithmetic mean and standard values of the flexural strength.
(5) Coefficient of softening
The concrete test method is that the test piece is cured for 28 days after being molded, the compressive strength Rco of one part of the test piece is tested, the other part of the test piece is completely immersed in water for 7 days, the test piece is taken out to wipe the water on the surface of the test piece to test the compressive strength Rcw, and the water resistance coefficient Kcn of the test piece is calculated according to the following formula:
Kcn＝Rcw/Rco
the softening coefficient ranges from 0 to 1, and the larger the value is, the better the water resistance of the material is. The magnitude of the softening coefficient is sometimes used as a basis for selecting a material. Important buildings or structures which are exposed to water or humid environments for a long time must be selected from materials having a softening coefficient of greater than 0.85. For materials with lighter or secondary structures subjected to moisture, the softening coefficient is preferably less than 0.70. Materials with a softening coefficient greater than 0.85 are generally considered to be water resistant materials.
(6) The raw materials of the invention are introduced as follows:
1) the red mud is from Sanmenxia aluminium industry Limited company hoped in Oriental China, the red mud used in the experiment passes through 30 meshes, the pH value is 12.23, the red mud type is Bayer process, and the chemical composition is shown in a table 1-1;
TABLE 1-1 chemical composition of Red mud (XRF)
2) The light-burned magnesia comes from Haicheng, Liaoning province, the calcining temperature is between 800 ℃ and 850 ℃, and the activity of the magnesia used in the experiment is 56.375 percent by adopting a hydration method through analysis;
3) the chromium slag adopted in the experiment is the chromium slag stockpiled in the Yi Ma city of Henan province;
4) the fly ash is selected from Henan Yi Ma electric fly ash
The silica fume is selected from Shandong Boken silicon materials, Inc
5) The defoamer tributyl phosphate is purchased from Tay chemical Co., Ltd in Sn-free market;
6) the water reducing agent is purchased from Shanxi Qin Shanxi Feng building materials Co.
The high-doping-ratio red mud building material is prepared from the following raw materials in parts by weight: 1200 parts of red mud, 1200 parts of chromium slag, 600 parts of light-burned magnesium powder, 672 parts of magnesium chloride brine, 4 parts of water reducing agent, fly ash and modifier; crushing the red mud, sieving the crushed red mud by a 30-mesh sieve to obtain a red mud raw material, and uniformly mixing the red mud raw material and the chromium slag to obtain a red mud and chromium slag premix; uniformly mixing light-burned magnesium powder with the red mud and chromium slag premix, adding the mixture into magnesium chloride brine, stirring for 2-5 min, adding a modifier, continuously stirring for 3min, and adding a water reducing agent to obtain red mud and chromium slag composite material raw material powder; supplementing water to the red mud and chromium slag composite material raw material powder to enable the mass ratio of the red mud and chromium slag composite material raw material powder to the water to be 100: 30-100: 50, fully stirring to obtain red mud magnesium gel composite material slurry, pouring the red mud magnesium gel composite material slurry into a mold, carrying out vibration molding, curing for 6-24 hours, demolding, and naturally curing to obtain the high-doping-ratio red mud building material.
The magnesium chloride is prepared into an aqueous solution with the mass percentage concentration of 20-30%, a defoaming agent is added, and the mixture is fully stirred until foam of the magnesium chloride solution is eliminated to obtain a clear solution, namely magnesium chloride brine.
The molar ratio of active magnesium oxide to magnesium chloride in the light-burned magnesium powder is 5: 1-9: 1, and the optimal molar ratio of the active magnesium oxide to the magnesium chloride in the light-burned magnesium oxide is 5: 1. The activity of the light-burned magnesium powder is 56.375 percent by adopting a hydration method. Wherein the pH value of the red mud is 12.23.
Example 1: the modifier is a phosphoric acid modifier; 30 parts of phosphoric acid modifier and 60-360 parts of fly ash by mass fraction. Preferably, the mass fractions of the phosphoric acid modifier and the fly ash are 30 parts and 180 parts. Preferably, the phosphoric acid modifier is a phosphoric acid solution with a mass percentage concentration of 25%.
For example 1, performance tests were performed in five groups, and the specific ratios of the five groups are shown in the following table:
the performance tests were performed on the above five groups and the test results are shown in the following table or in figures 1-3:
example 2, further comprising, silicon powder; 20-100 parts of silicon powder by mass.
For example 2, performance tests were performed in five groups, and the specific ratios of the five groups are shown in the following table:
the performance tests were performed on the above five groups and the test results are shown in the following table:
example 3, the modifiers are phosphoric acid, sodium citrate, and oxalic acid; 4.98 parts of phosphoric acid modifier, 15 parts of sodium citrate modifier, 25.12 parts of oxalic acid modifier and 30-150 parts of fly ash in percentage by mass. Preferably, the mass fractions of the components are 4.98 parts of phosphoric acid modifier, 15 parts of sodium citrate modifier, 25.12 parts of oxalic acid modifier and 60 parts of fly ash.
Wherein the phosphoric acid modifier is a phosphoric acid solution with the mass percentage concentration of 25%. The sodium citrate modifier is a sodium citrate solution with the mass percentage concentration of 20-25%. The oxalic acid modifier is oxalic acid solution with the mass percentage concentration of 20-25%.
For example 3, performance tests were performed in five groups, and the specific ratios of the five groups are shown in the following table:
the performance tests were performed on the above five groups and the test results are shown in the following table:
finally, it should be noted that: the above examples are only used to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The high-doping-ratio red mud building material is prepared from the following raw materials in parts by weight: 1200 parts of red mud, 1200 parts of chromium slag, 600 parts of light-burned magnesium powder, 672 parts of magnesium chloride brine and 4 parts of a water reducing agent; it is characterized by also comprising fly ash and a modifier; crushing the red mud, sieving the crushed red mud by a 30-mesh sieve to obtain a red mud raw material, and uniformly mixing the red mud raw material and the chromium slag to obtain a red mud and chromium slag premix; uniformly mixing light-burned magnesium powder with the red mud and chromium slag premix, adding the mixture into magnesium chloride brine, stirring for 2-5 min, adding a modifier, continuously stirring for 3min, and adding a water reducing agent to obtain red mud and chromium slag composite material raw material powder; supplementing water to the red mud and chromium slag composite material raw material powder to enable the mass ratio of the red mud and chromium slag composite material raw material powder to the water to be 100: 30-100: 50, fully stirring to obtain red mud magnesium gel composite material slurry, pouring the red mud magnesium gel composite material slurry into a mold, carrying out vibration molding, carrying out curing for 6-24 hours, carrying out demolding, and carrying out natural curing after demolding to obtain the high-doping-ratio red mud building material;
when the modifier is a phosphoric acid modifier: 30 parts of phosphoric acid modifier and 180 parts of fly ash;
when the modifier is a phosphoric acid modifier, a sodium citrate modifier and an oxalic acid modifier: the modified fly ash modifier comprises, by mass, 4.98 parts of a phosphoric acid modifier, 15 parts of a sodium citrate modifier, 25.12 parts of an oxalic acid modifier and 30-150 parts of fly ash.
2. The high-doping red mud building material of claim 1, wherein when the modifier is a phosphoric acid modifier: also comprises 20-100 parts of silicon powder by weight.
3. The high-doping-ratio red mud building material of claim 1, wherein when the modifier is a phosphoric acid modifier, a sodium citrate modifier and an oxalic acid modifier: the modified fly ash modifier comprises, by mass, 4.98 parts of a phosphoric acid modifier, 15 parts of a sodium citrate modifier, 25.12 parts of an oxalic acid modifier and 60 parts of fly ash.
4. The high-doping-ratio red mud building material as claimed in claim 3, wherein the activity of the light-burned magnesite powder measured by a hydration method is 56.375%.
5. The high-doping-ratio red mud building material as claimed in claim 4, wherein the molar ratio of active magnesium oxide to magnesium chloride in the light-burned magnesium oxide is 5: 1.
6. The high-doping red mud building material of claim 5, wherein the pH value of the red mud is 12.23.
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