CN110510986B - Modified paste filling material based on magnesium oxychloride gelling system and preparation method thereof - Google Patents
Modified paste filling material based on magnesium oxychloride gelling system and preparation method thereof Download PDFInfo
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- CN110510986B CN110510986B CN201910879441.6A CN201910879441A CN110510986B CN 110510986 B CN110510986 B CN 110510986B CN 201910879441 A CN201910879441 A CN 201910879441A CN 110510986 B CN110510986 B CN 110510986B
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
Abstract
The invention relates to a modified paste filling material based on a magnesium oxychloride gel system, belonging to the technical field of building materials. The components are as follows: 25-30% of brine, 20-35% of tail salt, 25-40% of magnesium oxide, 1-5% of rice hull ash, 1-5% of kaolin gangue fluidized bed ash, 0.5-1% of SHMP complex catalyst, 1-4% of rubber powder, 0.5-2% of M-blending agent and 1-5% of whisker. The invention solves the problems of poor performances of strength shrinkage, moisture absorption and halogen regain and the like in the prior art of a magnesium oxychloride gelling system.
Description
Technical Field
The invention relates to a modified paste filling material based on a magnesium oxychloride gel system, belonging to the technical field of building materials.
Background
Because of the shortage of sylvite resources, the external dependency of potash fertilizers in China is still kept about 50%, and about 600-700 million tons of potash fertilizers need to be imported every year. For the exploitation of underground soluble solid sylvite ore, the condition of shortage of sylvite ore resources in China is relieved to a great extent, and the external dependence of potash fertilizer in China is reduced. But secondary geological disasters such as surface subsidence and the like are easily caused for a goaf formed by underground mining; a large amount of sodium chloride tail salt and magnesium chloride tail liquid are by-produced in the production of the potash fertilizer, and serious environmental pollution is caused if the potassium fertilizer is discarded on the ground. This problem has not been solved well, hindering large-scale exploitation of sylvite ores.
In order to reduce the adverse effect of the sylvite mining on the surrounding geology and environment and realize the comprehensive utilization of the whole tailings, people in the engineering propose to utilize a magnesium oxychloride gelling system to fill the underground goaf according to the main component characteristics of the tail salt and the tail liquid generated in the sylvite mining process, so that the sodium chloride tail salt and the magnesium chloride tail liquid which are byproducts in the potash fertilizer production process can be greatly consumed, and the environmental protection requirement of the surrounding environment of the goaf can be effectively ensured. However, in practical application, the filling body has the disadvantages of strength shrinkage, moisture absorption and halogen regain, and the like.
Aiming at the performance defects of the magnesium oxychloride gelling system, people also carry out more deep exploration and propose some modification measures. The research finds that: the instability of the magnesium oxychloride gelling system has the following reasons: (1) the hydration product of the magnesium oxychloride cement cannot exist stably, and is easy to hydrolyze or generate crystal phase transformation when the surrounding liquid environment changes; (2) because a large amount of chloride ions exist in a gelling system, the chloride ions have strong adsorption capacity on water molecules, so that the liquid environment is changed, and the internal brine is dissolved out (namely, the brine is returned), so that the crystalline phase is hydrolyzed, and the strength is reduced; (3) the skeleton structure in the gel system is formed by mutually staggering 518-phase rod-shaped structures and 318-phase rod-shaped structures, and once a crystal phase is decomposed, the skeleton structure of the whole system is damaged, so that the volume shrinkage is caused, and the strength is reduced.
At present, in the method for improving the performance of the magnesium oxychloride gelling system, compared with other additives, the phosphoric acid or soluble phosphate has better effect of improving the water resistance of the gelling system. But the setting speed of the magnesium oxychloride cement is slowed down, so that the early strength of the magnesium oxychloride cement is reduced, and the engineering application is influenced.
Disclosure of Invention
The invention provides a modified paste filling material based on a magnesium oxychloride gel system aiming at the defects of the existing system, and solves the problems of poor performances of strength shrinkage, moisture absorption and halogen regain and the like in the prior art of the magnesium oxychloride gel system.
The technical scheme of the invention is as follows:
a modified paste filling material based on a magnesium oxychloride gelling system comprises the following components in percentage by weight: the modified magnesium oxide brine comprises magnesium oxide, brine, tail salt and a modified material, wherein the modified material consists of a siliceous material, an organic matter and whiskers. The siliceous material component comprises kaolin gangue fluidized bed ash and rice hull ash, and the organic matter component comprises redispersible rubber powder, a SHMP complex catalyst and an M-blending agent.
The invention solves the inherent defects of poor water resistance, strength shrinkage, easy moisture absorption and halogen return of the magnesium oxychloride gelling system, and provides technical guarantee for the industrial application of the magnesium oxychloride gelling system.
As a further technical scheme, the paint comprises the following components in percentage by weight:
25-30% of brine, 20-35% of tail salt, 25-40% of magnesium oxide, 1-5% of rice hull ash, 1-5% of kaolin gangue fluidized bed ash, 0.5-1% of SHMP complex catalyst, 1-4% of redispersible rubber powder, 0.5-2% of M-blending agent and 1-5% of whisker.
As a further technical scheme, the concentration of the magnesium chloride in the brine is 20-32%.
As a further technical scheme, the tail salt is formed into a certain particle size distribution after mechanical grinding, and is composed of three salt ores with different particle sizes of coarse salt, medium salt and fine salt, wherein the mass ratio of the coarse salt, the medium salt and the fine salt in the modified paste filler is (5% -20%): (5-15%): (5% -15%), the particle size of the coarse salt is 2.36-4.75 mm, the particle size of the medium salt is 1.18-2.36 mm, and the particle size of the fine salt is 0.6-1.18 mm.
As a further technical scheme, the activity of the magnesium oxide is 65-70%.
As a further technical scheme, the redispersible latex powder is VAE solid rubber powder which is prepared from a copolymer of ethylene and vinyl acetate and polyvinyl alcohol serving as a protective colloid.
As a further technical scheme, the rice hull ash is high-activity rice hull ash which is obtained by taking rice hulls as combustion residues and calcining at low temperature.
As a further technical scheme, the kaolin gangue fluidized bed ash is generated by calcining a silica-alumina mineral at 600-900 ℃, mechanical grinding is needed to improve the activity of the silica-alumina mineral, the ash is put into a ball mill for grinding, the rotating speed is 220-240 r/min, and the grinding time is 30-50 min.
As a further technical scheme, the SHMP complex catalyst is sodium hexametaphosphate solid powder.
As a further technical scheme, the M-blending agent is water-soluble organic compound solid powder.
As a further technical scheme, the whisker is calcium carbonate whisker.
A preparation method of a modified paste filling material based on a magnesium oxychloride gelling system comprises the following steps:
s1, weighing each component according to the formula of any one of the modified paste fillers based on the magnesium oxychloride gel system for later use;
s2, mixing the magnesium oxide, the crystal whisker and the brine, and uniformly stirring for 5-15 min to obtain uniform slurry;
s3, uniformly mixing the rice hull ash, kaolin gangue fluidized bed ash and a SHMP complex catalyst;
s4, adding the uniform mixture obtained in the step S3 into the slurry obtained in the step S2, and stirring for 10-15 min;
s5, adding the redispersible rubber powder and the M-blending agent into the mixture obtained in the step S4 at the same time, and stirring for 5-10 min;
s6, adding tail salt with a certain gradation into the slurry prepared in the step S5, and stirring for 10-30 min to obtain the modified paste filler based on the magnesium oxychloride gel system, wherein the gradation of the tail salt is as follows: the mass ratio of the coarse salt, the medium salt and the fine salt in the modified paste filler is 5-20%: 5% -15%: 5 to 15 percent.
As a further technical solution, between the step S2 and the step S3, a step S30 is further included: and (3) grinding the kaolin gangue fluidized bed ash in a ball mill with the rotating speed of 220-240 r/min for 30-50 min to obtain the activated kaolin gangue fluidized bed ash.
The principle and the beneficial effects of the invention are as follows:
1. in the invention, in order to increase the stability of the hydration product in a gelling system, a siliceous material component is introduced into the modified material. During the formulation of the magnesium oxychloride material, MgO is generally in excess. The proper increase of MgO can raise the pH value of the slurry and raise the reaction rate to ensure MgCl2The excessive magnesium oxide in the system affects the volume stability of the MOC and also causes blooming. Active siliceous material rice husk ash and kaolin gangue fluidized bed ash slag are introduced into the system, and active SiO contained in the active siliceous material2Can be hydrated with excessive magnesium oxide to form insoluble salt MgSiO3：
3MgO+4Si02+8H20→3MgO·4SiO2·H2O
Amorphous SiO in Low temperature Rice Hull Ash (L-RHA)2The content can reach more than 90 percent, and all the components areNanoscale active SiO2Gel particles with large specific surface area (50-100 m)2/g), so that the low-temperature rice hull ash has high pozzolanic activity. Nanoscale active SiO in L-RHA2The particles can not only eliminate the influence of the redundant magnesium oxide, but also ensure that Si is still dissolved in the 5-1-8 crystal phase cavity and simultaneously change the 5-1-8 crystal phase and Mg (OH)2The matching of the two components makes the structure matching of the reaction products more reasonable, the microstructure more compact and the effect is more obvious when the time is longer.
Kaolin gangue fluidized bed ash slag is widely existed in pit mouth power stations in various places. The kaolin coal gangue widely exists in northern coal producing areas in China, and the fluidized bed combustion technology is an effective process for treating low-calorific-value fuel. The coal gangue CFB ash discharged by a power plant is large in quantity and low in price, and is usually generated by calcining a silica-alumina mineral in a medium-temperature region (600-900 ℃), so that the coal gangue CFB ash has high potential pozzolanic activity.
Although active SiO in the siliceous material2Can react with MgO at normal temperature, but the reaction speed is slow. To accelerate the reaction, hexametaphosphate (SHMP) was introduced. Catalyst energy with Ca2+、Mg2+Form complex, reduce the energy barrier of chemical reaction, reduce the activation energy required by chemical reaction, and obviously promote Mg (OH)2Dissolving Mg in the solution2+And OH-The concentration is increased at the same time, so that free SiO3]2-The concentration is increased. The concentration of the reactant is increased, so that the alkali-activated reaction is accelerated, and the improvement of MgO-SiO is facilitated2–H2The reaction speed of the O system is increased, namely the generation speed of M-S-H is increased.
2. The magnesium oxychloride cement stone is a porous polycrystalline stacking structure. The matrix strength is reduced, the volume stability is unstable, the fundamental reason is that the internal crystal structure is hydrolyzed and damaged, so that the fibrous framework is dissolved, and along with the dissolution of hydrolysis products, the space occupied by the crystal structure in the matrix is changed into a loose pore structure. The skeleton structure is destroyed, resulting in a decrease in strength, and under the action of external pressure, appearance volume shrinkage also occurs.
The crystal whisker not only has a needle-bar structure similar to a slurry matrix skeleton, but also has a grain material size reaching the micron level, and can realize the filling effect to a greater extent, so that the filler can form a three-dimensional network skeleton structure similar to a reaction product crystal in the matrix; the chemical stability of the whisker enables the whisker to still play a skeleton role after the 518 crystal phase is decomposed and destroyed, thereby improving the stability of the microstructure. The whisker belongs to inorganic salts, has better physical and chemical 'cohesiveness' with an MOC matrix according to a similar compatibility theory, can better inhibit the generation of microcracks on a microscale and improves the compactness and the stability of a matrix structure.
3. In the present invention, the content of chloride ion in the solution is controlled by using M-blending agent. The M-modulator is a water-soluble organic compound having a cyclic molecular structure capable of containing anions and forming a complex with small anions. The magnesium oxychloride gel system is easy to absorb moisture and return to halogen, and is related to chloride ions in the solution to a great extent. Chloride ion is easy to react with H due to its electron-rich structure2O forms quasi-hydrogen bonds for affinity, a large amount of moisture in the air enters a gelling system to break liquid balance, so that crystals are hydrolyzed, magnesium chloride is dissolved out, and the phenomenon of halogen return is caused. Because the mixing amount of the M-blending agent is small and the speed of the organic complexing reaction is slow, the modifier can not influence the early crystallization hardening reaction and has better fixation effect on chloride ions in the solution in the solid after the matrix is hardened.
4. The microstructure of the magnesium oxychloride cement stone has porosity, so that the internal pore structure of the magnesium oxychloride cement stone is beneficial to the entry of external moisture and the destruction of the chemical balance in internal liquid, thereby causing the hydrolysis of a crystal phase, and simultaneously providing a channel for the dissolution of a hydrolysis product magnesium chloride to form a vicious circle and cause the destruction of the structure. Therefore, the invention improves the porous matrix from different angles and improves the compactness of the matrix. On the physical level, the introduction of organic matters is mainly started. The redispersible rubber powder can be uniformly dispersed in the cementing material, and can be changed into emulsion when meeting water, and the emulsion enters a pore structure to play a certain role in blocking; secondly, the film-shaped structure formed in the emulsion can block the contact of the crystal structure and water, and prevent the crystal structure from being hydrated and decomposed.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the technical solutions.
Chemical admixtures used in the following examples: the redispersible rubber powder is VAE rubber powder which is prepared from copolymer of ethylene and vinyl acetate and polyvinyl alcohol as protective colloid; the rice hull ash is a waste residue generated by a certain rice hull generator set; the kaolin gangue fluidized bed ash comes from a gangue power plant; CaCO3The crystal whisker is produced by domestic enterprises, has the length of 20-30 mu m and the diameter of 0.5-2 mu m; m-blending agents are pure chemical agents produced by a certain company.
Example 1
A modified paste filling material based on a magnesium oxychloride gelling system comprises the following components in percentage by weight:
28% of brine, 30% of tail salt, 32% of magnesium oxide, 3% of rice hull ash, 2% of kaolin gangue fluidized bed ash, 0.5% of SHMP complex catalyst, 2% of redispersible rubber powder, 0.5% of M-blending agent and 2% of whisker.
The preparation method comprises the following steps:
s1, weighing each component according to the formula of the modified paste filler based on the magnesium oxychloride gel system for later use;
s2, uniformly stirring the magnesium oxide, the crystal whisker and the brine (the concentration of the magnesium chloride is 28.0%) for 8min to obtain uniform slurry;
s30, grinding the kaolin gangue fluidized bed ash in a ball mill with the rotating speed of 220r/min for 45min to obtain activated kaolin gangue fluidized bed ash.
S3, uniformly mixing the rice hull ash, kaolin gangue fluidized bed ash and a SHMP complex catalyst together, and stirring for 5 min;
s4, adding the uniform mixture obtained in the step S3 into the slurry obtained in the step S2, and stirring for 10 min;
s5, adding the redispersible rubber powder and the M-blending agent into the mixture obtained in the step S4 at the same time, and stirring for 5 min;
s6, grading as follows: the mass ratio of the crude salt to the medium salt to the fine salt is 15%: 8%: and adding 7% of tail salt into the prepared slurry, and stirring for 15min to obtain the modified paste filler based on the magnesium oxychloride gelling system.
The properties of the modified paste filler based on the magnesium oxychloride gelling system obtained in this example are shown in table 1.
Table 1 results of tests on the properties of modified paste fillers based on a magnesium oxychloride gelling system obtained in example 1
Example 2
A modified paste filling material based on a magnesium oxychloride gelling system comprises the following components in percentage by weight:
25% of brine, 22% of tail salt, 40% of magnesium oxide, 1% of rice hull ash, 1% of kaolin gangue fluidized bed ash, 0.8% of SHMP complex catalyst, 4% of redispersible rubber powder, 1.2% of M-blending agent and 5% of whisker.
The preparation method comprises the following steps:
s1, weighing each component according to the formula of the modified paste filler based on the magnesium oxychloride gel system for later use;
s2, uniformly stirring the magnesium oxide, the crystal whisker and the brine (the concentration of the magnesium chloride is 32.0%) for 10min to obtain uniform slurry;
s30, grinding the kaolin gangue fluidized bed ash in a ball mill with the rotating speed of 230r/min for 40min to obtain activated kaolin gangue fluidized bed ash.
S3, uniformly mixing the rice hull ash, kaolin gangue fluidized bed ash and a SHMP complex catalyst together, and stirring for 8 min;
s4, adding the uniform mixture obtained in the step S3 into the slurry obtained in the step S2, and stirring for 12 min;
s5, adding the redispersible rubber powder and the M-blending agent into the mixture obtained in the step S4 at the same time, and stirring for 7 min;
s6, grading as follows: the mass ratio of the crude salt to the medium salt to the fine salt is 10%: 7%: 5 percent of tail salt is added into the prepared slurry and stirred for 20min, thus obtaining the modified paste filling material based on the magnesium oxychloride gel system.
The performance test of the quick-hardening early-strength composite repair mortar obtained in the example is shown in table 2.
Table 2 test results of the properties of the quick hardening early strength type composite repair mortar obtained in example 2
Example 3
A modified paste filling material based on a magnesium oxychloride gelling system comprises the following components in percentage by weight:
30% of brine, 20% of tail salt, 35% of magnesium oxide, 5% of rice hull ash, 5% of kaolin gangue fluidized bed ash, 1% of SHMP complex catalyst, 1% of redispersible rubber powder, 2% of M-blending agent and 1% of whisker.
The preparation method comprises the following steps:
s1, weighing each component according to the formula of the modified paste filler based on the magnesium oxychloride gel system for later use;
s2, uniformly stirring the magnesium oxide, the crystal whisker and the brine (the concentration of the magnesium chloride is 20%) for 10min to obtain uniform slurry;
s30, grinding the kaolin gangue fluidized bed ash in a ball mill with the rotation speed of 240r/min for 40min to obtain activated kaolin gangue fluidized bed ash.
S3, uniformly mixing the rice hull ash, kaolin gangue fluidized bed ash and a SHMP complex catalyst together, and stirring for 10 min;
s4, adding the uniform mixture obtained in the step S3 into the slurry obtained in the step S2, and stirring for 15 min;
s5, adding the redispersible rubber powder and the M-blending agent into the mixture obtained in the step S4 at the same time, and stirring for 10 min;
s6, grading as follows: the mass ratio of the crude salt to the medium salt to the fine salt is 10%: 5%: and adding 5% of tail salt into the prepared slurry, and stirring for 25min to obtain the modified paste filler based on the magnesium oxychloride gelling system.
The performance test of the quick-hardening early-strength composite repair mortar obtained in the example is shown in Table 3.
Table 3 test results of the properties of the quick hardening early strength type composite repair mortar obtained in example 3
Example 4
A modified paste filling material based on a magnesium oxychloride gelling system comprises the following components in percentage by weight:
25% of brine, 35% of tail salt, 25% of magnesium oxide, 5% of rice hull ash, 5% of kaolin gangue fluidized bed ash, 1% of SHMP complex catalyst, 1% of redispersible rubber powder, 2% of M-blending agent and 1% of whisker.
The procedure was as in example 3.
Claims (10)
1. A modified paste filling material based on a magnesium oxychloride gelling system is characterized by comprising the following components in percentage by weight: 25-30% of brine, 20-35% of tail salt, 25-40% of magnesium oxide, 1-5% of rice hull ash, 1-5% of kaolin gangue fluidized bed ash, 0.5-1% of SHMP complex catalyst, 1-4% of redispersible rubber powder, 0.5-2% of M-blending agent and 1-5% of whisker, wherein the M-blending agent is water-soluble organic compound solid powder.
2. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 1, wherein the tail salt is composed of three salt ores of different grain sizes of coarse salt, medium salt and fine salt, and the mass ratio of the coarse salt, the medium salt and the fine salt in the modified paste filler is (5% -20%): (5-15%): (5% -15%), the particle size of the coarse salt is 2.36-4.75 mm, the particle size of the medium salt is 1.18-2.36 mm, and the particle size of the fine salt is 0.6-1.18 mm.
3. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 1 or 2, wherein the rice hull ash is a high-activity rice hull ash after low-temperature calcination; the kaolin gangue fluidized bed ash is produced by calcining a silica-alumina mineral at 600-900 ℃.
4. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 1 or 2, wherein the SHMP complex catalyst is solid powder of sodium hexametaphosphate; the whisker is calcium carbonate whisker; the redispersible latex powder is VAE rubber powder which is prepared from copolymer of ethylene and vinyl acetate and polyvinyl alcohol as protective colloid.
5. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 3, wherein the SHMP complex catalyst is sodium hexametaphosphate solid powder; the whisker is calcium carbonate whisker; the redispersible latex powder is VAE rubber powder which is prepared from copolymer of ethylene and vinyl acetate and polyvinyl alcohol as protective colloid.
6. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 1, 2 or 5, wherein the concentration of magnesium chloride in the brine is 20-32%; the activity of the magnesium oxide is 65-70%.
7. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 3, wherein the concentration of magnesium chloride in the brine is 20-32%; the activity of the magnesium oxide is 65-70%.
8. The modified paste filler based on a magnesium oxychloride gelling system as claimed in claim 4, wherein the concentration of magnesium chloride in the brine is 20-32%; the activity of the magnesium oxide is 65-70%.
9. A preparation method of a modified paste filling material based on a magnesium oxychloride gelling system is characterized by comprising the following steps:
s1, weighing each component for later use according to the formula of the modified paste filler based on the magnesium oxychloride gelling system as claimed in any one of claims 1 to 8;
s2, mixing the magnesium oxide, the crystal whisker and the brine, and uniformly stirring for 5-15 min to obtain uniform slurry;
s3, uniformly mixing the rice hull ash, kaolin gangue fluidized bed ash and a SHMP complex catalyst;
s4, adding the uniform mixture obtained in the step S3 into the slurry obtained in the step S2, and stirring for 10-15 min;
s5, adding the redispersible rubber powder and the M-blending agent into the mixture obtained in the step S4 at the same time, and stirring for 5-10 min;
s6, adding the tail salt into the slurry prepared in the step S5, and stirring for 10-30 min to obtain the modified paste filler based on the magnesium oxychloride gelling system, wherein the tail salt is graded as follows: the mass ratio of the coarse salt, the medium salt and the fine salt in the modified paste filler is (5-20%): (5-15%): (5% to 15%).
10. The preparation method of claim 9, wherein the kaolin gangue fluidized bed ash is subjected to grinding in a ball mill with a rotation speed of 220-240 r/min for 30-50 min before being mixed with the rice hull ash and the SHMP complex catalyst, so as to obtain the activated kaolin gangue fluidized bed ash.
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| CN106800384A (en) * | 2017-03-17 | 2017-06-06 | 信阳师范学院 | A kind of composite modified method for improving magnesium oxychloride cementing material performance |
| CN107586092A (en) * | 2017-08-28 | 2018-01-16 | 中农国际钾盐开发有限公司 | It is a kind of can be with sylvite ore casting resin of long distance pumping and preparation method thereof |
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