CN113831036B - High-free calcium oxide solid waste base gelling material and preparation and application thereof - Google Patents
High-free calcium oxide solid waste base gelling material and preparation and application thereof Download PDFInfo
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Abstract
A high free calcium oxide solid waste base cementing material is prepared by water and high free calcium oxide waste residue, chemical powder grinding agent, exciting agent, and optionally coal gasification residue, wherein the high free calcium oxide waste residue is one or more of fly ash, magnesium residue, and steel slag; the content of free calcium oxide in the fly ash meets the following requirements: free calcium oxide of F-class and C-class fly ashes is respectively more than 1% and 4%; the free calcium oxide in the steel slag exceeds 4 percent; the free calcium oxide in the magnesium slag is more than 4 percent or the magnesium oxide is more than 8 percent. The material can be used as a filling material for coal mine filling mining and is prepared by two-stage excitation, wherein in the step one, a chemical powder grinding agent is completely mixed with water required by preparing a cementing material, and then the mixture is added into high-free calcium oxide waste residue and stirred to prepare slurry; and step two, adding an activator or coal gasification slag and the activator into the slurry, and continuously stirring to finish the preparation of the cementing material. The invention solves the problem of high free calcium oxide stability and realizes the application thereof.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid waste and green coal mining, and particularly relates to a high-free calcium oxide solid waste based cementing material as well as preparation and application thereof.
Background
The filling mining technology is an important component of the green mining technology of coal mines, can combine solid waste utilization with surface subsidence control, has the basic characteristics of high safety, high extraction rate and environmental friendliness, can realize low surface destruction degree, high coal resource extraction rate, solid waste resource utilization and mine area ecological environment protection, becomes one of the fundamental ways for realizing green mining, and is an important measure for relieving the bottleneck restriction of resources, energy, large amount of solid waste, environment and safety and for developing mineral resources in western ecological fragile areas in China.
The cement is the most widely used cementing material in the practical process of filling mining technology, meanwhile, the cement is one of the largest commodities in the world, the huge cement yield and the use amount are accompanied by very obvious environmental cost, and the global carbon dioxide emission amount caused in the cement production process is increased by at least 5 to 8 percent.
The strength requirement of a filling body required in the filling and mining process of a mine is lower, generally about 2-6 MPa, and is greatly different from the common 35MPa, 45MPa or even higher strength concrete in a building, the use of cement for preparing the filling body with low strength is actually a waste, the use of high-cost cement causes the increase of the filling production cost, and the high cost of filling is a main reason for limiting the popularization of the filling and mining technology at present.
In order to reduce the cost, in the filling and mining process, part of common industrial waste residues such as fly ash and steel slag are added to replace part of cement, but the adding amount is limited, and the cost is still high.
In the electric energy mainly using coal, 250-300kg of fly ash is generated when 1 ton of raw coal is combusted, wherein a large amount of fly ash with high content of free calcium oxide can cause concrete expansion and cracking due to poor stability, and the utilization problem is particularly prominent.
The steel slag is the main solid waste of steel enterprises and is formed by quenching after high-temperature smelting. The steel slag contains dicalcium silicate, tricalcium silicate, a small amount of free calcium oxide, free magnesium oxide and the like. Therefore, the steel slag has certain gelling property, but the steel slag has higher content of free calcium oxide and free magnesium oxide, so when the steel slag is applied to building materials, the building cracks due to late hydration, the stability of the building is influenced, and the resource utilization of the steel slag is seriously restricted.
The production of metal magnesium mainly adopts Pidgeon process, and the slag yield is 6.5-8.0 tons per 1 ton of magnesium produced. Because the magnesium slag contains a large amount of free calcium oxide and magnesium oxide, the magnesium slag is easy to expand, has poor stability and low comprehensive utilization rate.
In the prior art, part of fly ash and steel slag can be mixed into cement for use, but the free calcium oxide and free magnesium oxide of the fly ash and the magnesium slag are strictly limited. According to the requirements of national standard fly ash used in cement and concrete (GB/T1596-2017), the mass fractions of free calcium oxide of class F and class C fly ash cannot exceed 1% and 4% respectively. The national standard magnesium slag silicate cement (GB/T23933-2009) requires that the content of magnesium oxide in the steel slag is less than 8%. At present, the main disposal mode of the fly ash, the steel slag and the magnesium slag is still ground stacking or landfill, a large amount of land is occupied, and simultaneously, the resource is greatly wasted.
Chinese patent CN202011088417.X discloses a composite activated low-calcium fly ash cement and a preparation method thereof, wherein the low-calcium fly ash and cement clinker are excited by adopting a composite exciting agent such as strong base and the like to prepare the fly ash cement. The disadvantage is that the fly ash is only used as an admixture, and the main body of the cementing material is cement.
Chinese patent CN201510402506.X discloses a neutral sodium salt alkali-activated low-calcium fly ash cement and a using method thereof, and is characterized in that the cement is composed of low-calcium fly ash, ordinary portland cement and sodium sulfate. The fly ash is used as a blending material of cement.
Chinese patent CN202110108524.2 discloses a fly ash gelled material, a preparation method and application thereof, and adopts a typical alkali excitation method. The activator has high cost and cannot effectively use the high free calcium oxide fly ash.
Chinese patent CN102432206A discloses a chemically-excited magnesium slag-based geopolymer cementing material and a preparation method thereof. The method is characterized in that magnesium slag and slag which can provide inorganic aluminosilicate components are used as raw materials, and the cementing material is prepared under the excitation of a chemical exciting agent, namely sodium silicate.
In order to improve the stability of the fly ash, the steel slag and the magnesium slag, a method of ball milling, water spraying, aging digestion or chemical digestion is often adopted for the high free calcium oxide, but the problems of complex process, high energy consumption and high cost limit the use of the methods.
Chinese patent CN201310490520.0 discloses a digestion method of fly ash free calcium oxide and an application thereof, wherein the main method is to add fly ash into a ball mill and spray water mist into the ball mill. The treatment process is complex, the energy consumption is high, the coal ash is easy to agglomerate, and the further use is not facilitated.
Chinese patent CN201310468024.5 discloses a steel slag stability treatment method, which mainly adopts steel slag powder, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, sulfonated melamine formaldehyde resin and water to prepare a mixed material, and the mixed material is treated for 3 to 8 hours at the temperature of 20 to 50 ℃ after being uniformly mixed. The treatment process is complex, the energy consumption is high, the cost is high, and the treated steel slag is only used as a cement admixture.
Chinese patent CN201310213810.0 discloses a method for improving stability of steel slag and keeping high gelling activity, which adopts a digesting agent and a dispersing agent to treat and modify steel slag powder at 50-60 ℃. The treatment method has the same advantages of complex process, high energy consumption and high cost, and the treated steel slag is only used as a cement admixture.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-free-calcium-oxide solid waste-based cementing material, and preparation and application thereof, so as to effectively solve the problem of high-free-calcium-oxide stability, and completely replace cement in the coal mine filling and mining process, so as to effectively reduce the coal mine filling and mining cost, further promote the popularization and application of the coal mine filling and mining technology, and provide a new way for solid waste disposal in the power generation industry, the coal chemical industry, the magnesium smelting industry and the steel making industry.
In order to achieve the purpose, the invention adopts the technical scheme that:
the high free calcium oxide solid waste base cementing material is prepared from water and the following raw materials in parts by weight:
85-95% of high free calcium oxide waste residue;
1-10% of chemical powder grinding agent;
1-10% of excitant;
or, the water-soluble paint is prepared from water and the following raw materials in parts by weight:
50-80% of high free calcium oxide waste residue;
10 to 40 percent of gasified slag;
2-6% of chemical grinding agent;
3 to 5 percent of excitant;
wherein the high free calcium oxide waste residue is one or more of fly ash, magnesium residue and steel slag;
the content of free calcium oxide in the fly ash meets the following requirements: the mass fractions of free calcium oxide of the F-class fly ash and the C-class fly ash are respectively more than 1% and 4%;
the mass fraction of free calcium oxide in the steel slag exceeds 4 percent;
the mass fraction of free calcium oxide in the magnesium slag is more than 4% or the mass fraction of magnesium oxide is more than 8%.
Preferably, when the high free calcium oxide waste residue is a mixture containing fly ash, the weight percentage of each component in the mixture is as follows:
60% -90% of fly ash and 10% -40% of magnesium slag; or the like, or, alternatively,
60-90% of fly ash and 10-40% of steel slag; or the like, or, alternatively,
50-78% of fly ash, 10-30% of magnesium slag and 10-30% of steel slag;
when the high free calcium oxide waste residue is a mixture without fly ash, the weight percentage of each component in the mixture is as follows:
45-65% of magnesium slag and 35-55% of steel slag.
Preferably, the chemical milling agent is an acidic medium, and the activator is a compound alkali activator.
Preferably, the acidic medium is sulfuric acid, phosphoric acid, hydrochloric acid or H-type cation exchange resin regeneration liquid; the compound alkali activator consists of 2-3 of lime, sodium hydroxide, carbonate and sodium silicate.
The invention also provides a preparation method of the high free calcium oxide solid waste base gelling material, which is prepared by two-stage excitation and comprises the following steps:
step one, completely mixing a chemical powder grinding agent with water required for preparing a cementing material, adding the mixture into high-free calcium oxide waste residue, and stirring to prepare slurry;
and step two, adding an activator or coal gasification slag and the activator into the slurry, and continuously stirring to finish the preparation of the cementing material.
Preferably, the adding amount of the chemical powder grinding agent is added according to the proportion of the measured content of free calcium oxide in the high-free calcium oxide waste residue, and the specific formula is as follows: c = (C)1m1+C2m2+C3m3)/(m1+m2+m3) (ii) a The mol ratio is as follows: 1000C/74: [ H +]1, 0.1-2; wherein C represents the mass percent of free calcium oxide in the solid mixture, C1Represents the mass percentage of free calcium oxide of the fly ash, m1Represents the mass of fly ash, C2Represents the mass percent of free calcium oxide of the magnesium slag, m2Denotes the mass of magnesium slag, C3Represents the mass percent of free calcium oxide of the steel slag, m3The mass of the required water is 70 to 90 percent of the mass of the high free calcium oxide waste residue solid.
Preferably, in the first step:
mixing the chemical powder grinding agent with part of water to form a diluted chemical powder grinding agent, mixing the other part of water with the high-free calcium oxide waste residue to form waste residue slurry, adding the diluted chemical powder grinding agent into the waste residue slurry for 3-5 times, and stirring to prepare slurry; or the like, or, alternatively,
the chemical grinding agent and the prepared cementing material are mixed by water, and then the water is mixed with the high free calcium oxide waste residue and stirred to prepare slurry.
Preferably, in the second step:
when the gas slag is not contained, adding the excitant into the slurry once for mixing and stirring when the excitant is a solid or liquid composite excitant with the same form; when the excitant is a composite excitant with different forms, adding the excitant into the slurry according to different form classifications, mixing and stirring, wherein the sequence is solid firstly and liquid secondly;
when the gas slag is contained, screening and grinding the gas slag, adding the gas slag into the slurry, stirring to form new slurry, and adding the excitant into the new slurry once for mixing and stirring when the excitant is a solid or liquid compound excitant with a certain same form; when the excitant is a composite excitant with different forms, the excitant is added into new slurry according to different form classifications for mixing and stirring, and the sequence is solid firstly and liquid secondly.
The high free calcium oxide solid waste base cementing material can be used as a filling material for coal mine filling mining.
Preferably, the strength of the concrete prepared from the high free calcium oxide solid waste base cementing material and the aggregate is less than 15MPa, wherein the cementing material and the aggregate are calculated according to the mass ratio: 20-50% of high free calcium oxide solid waste base cementing material and 50-80% of aggregate.
Compared with the prior art, the invention has the beneficial effects that:
1. the cementing material is prepared from high-free calcium oxide solid waste, can be used for coal mine filling mining, can completely replace cement, reduces the coal mine filling mining cost, promotes the development of filling mining technology, and provides a new way for solid waste disposal of power plants, steel plants and magnesium plants.
2. The cementing material is prepared by adopting a two-stage excitation method, so that the problem of stability of fly ash containing high free calcium oxide, steel slag and magnesium slag is solved by adopting a chemical milling mode, and the activity of the high free calcium oxide waste slag is excited by adopting a composite exciting agent, and the cementing material has the remarkable advantages of simplicity in operation, good effect, low energy consumption and low cost.
3. The mutual excitation effect between the gasification furnace slag and the high free calcium oxide waste residue is fully utilized, the early strength of the high free calcium oxide solid waste based cementing material is further improved, and a novel gasification furnace slag resource utilization method is provided.
Drawings
FIG. 1 is a sample specimen of a filling body in a well of example 1
FIG. 2 is a macroscopic picture of strength failure of a high free calcium oxide fly ash test piece.
FIG. 3 is a macroscopic view of a specimen of a filling body prepared by mixing the high free calcium oxide-based solid waste cementing material and coal gangue in example 1 of the present invention.
FIG. 4 is a uniaxial compressive strength line diagram of a filling body prepared by mixing the high free calcium oxide-based solid waste cementing material and coal gangue in example 1 of the invention.
Fig. 5 is a flow chart of a preparation method of the solid waste base gelling material with high free calcium oxide in the embodiment 1 of the invention.
Fig. 6 is a flow chart of a preparation method of the high free calcium oxide solid waste based gelling material in the embodiment 11 of the invention.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
The invention firstly provides a high-free calcium oxide solid waste base gelling material, which is prepared from water and the following raw materials in parts by weight in a first scheme:
85-95% of high free calcium oxide waste residue;
1-10% of chemical grinding agent;
1 to 10 percent of excitant.
In a second parallel scheme, the material can also be prepared from water and the following raw materials in parts by weight:
50-80% of high free calcium oxide waste residue;
10 to 40 percent of coal gasification slag;
2-6% of chemical powder grinding agent;
3 to 5 percent of excitant.
In the invention, the high free calcium oxide waste residue is one or a mixture of more of fly ash, magnesium slag and steel slag. And the content of free calcium oxide in the fly ash exceeds the requirement of national standard fly ash used in cement and concrete (GB/T1596-2017), namely the mass fractions of the free calcium oxide in the F-type fly ash and the free calcium oxide in the C-type fly ash exceed 1 percent and 4 percent respectively. The content of free calcium oxide in the steel slag refers to C-type fly ash, namely the mass fraction of the free calcium oxide is more than 4%. The magnesium slag is in accordance with the national standard of magnesium slag portland cement (GB/T23933-2009), namely the mass fraction of free calcium oxide is more than 4% or the mass fraction of magnesium oxide is more than 8%.
Illustratively, when the high free calcium oxide waste residue is a mixture containing fly ash, the weight percentage of each component in the mixture is as follows:
60-90% of fly ash and 10-40% of magnesium slag; or the like, or a combination thereof,
60-90% of fly ash and 10-40% of steel slag; or the like, or, alternatively,
50-78% of fly ash, 10-30% of magnesium slag and 10-30% of steel slag.
When the high free calcium oxide waste residue is a mixture without fly ash, the weight percentage of each component in the mixture is as follows:
45-65% of magnesium slag and 35-55% of steel slag.
Illustratively, the chemical milling agent of the present invention is an acidic medium, and specifically, it may be sulfuric acid, phosphoric acid, hydrochloric acid, or an H-type cation exchange resin regeneration liquid, etc.
Illustratively, the activator of the invention is a compound alkali activator, and specifically can be composed of 2-3 of lime, sodium hydroxide, carbonate and sodium silicate.
The high free calcium oxide solid waste base cementing material is prepared by two-stage excitation, and comprises the following steps:
step one, completely mixing a chemical powder grinding agent with water required by preparing a cementing material, adding the mixture into high-free calcium oxide waste residue, and quickly stirring to prepare slurry. Illustratively, the stirring time may be 1 to 3min.
For example, the chemical milling agent can be mixed with part of water to form a diluted chemical milling agent, the other part of water is mixed with the high-free calcium oxide waste residue to form waste residue slurry, and the diluted chemical milling agent is completely added into the waste residue slurry for 3-5 times and stirred to form slurry; or directly mixing the chemical grinding agent and the prepared cementing material with water, mixing the water with the high-free calcium oxide waste residue, and stirring to prepare slurry.
And step two, adding an activator or coal gasification slag and the activator into the slurry, and continuously stirring to finish the preparation of the cementing material. Illustratively, the stirring time may be 5 to 15min.
For example, when the coal gasification slag is not contained, if the excitant is a solid or liquid composite excitant with the same form, the excitant is added into the slurry at one time for mixing and stirring; if the excitant is a composite excitant with different forms, the excitant is added into the slurry for mixing and stirring according to different form classifications, and the sequence is solid firstly and liquid secondly.
When the gas slag is contained, screening and grinding the gas slag, adding the gas slag into the slurry, stirring to form new slurry, and adding the excitant into the new slurry once for mixing and stirring if the excitant is a solid or liquid compound excitant with a certain same form; if the excitant is a composite excitant with different forms, the excitant is added into new slurry according to different form classifications for mixing and stirring, and the sequence is solid firstly and liquid secondly.
Illustratively, the adding amount of the chemical powder grinding agent is added according to the proportion of the measured content of free calcium oxide in the high-free calcium oxide waste residue, and the specific formula refers to: c = (C)1m1+C2m2+C3m3)/(m1+m2+m3) (ii) a The mol ratio is as follows: 1000C/74: [ H +]1 =0.1 to 2; wherein C represents the mass percent of free calcium oxide in the solid mixture, C1Represents the mass percentage of free calcium oxide of the fly ash, m1Represents the mass of fly ash, C2Represents the mass percent of free calcium oxide of the magnesium slag, m2Denotes the mass of magnesium slag, C3Represents the mass percent of free calcium oxide of the steel slag, m3The mass of the required water is 70 to 90 percent of the mass of the high free calcium oxide waste residue solid.
The obtained high-free calcium oxide solid waste base cementing material can be used in other similar low-strength concrete demand industries, and the typical application industry is coal mine filling mining, for example, the high-free calcium oxide solid waste base cementing material can be used as a filling material for coal mine filling mining.
Illustratively, the strength of concrete prepared from the high-free-calcium-oxide solid waste-based cementing material and aggregates such as gangue and aeolian sand is less than 15MPa, wherein the ratio of the cementing material to the aggregates is as follows by mass: 20-50% of high free calcium oxide solid waste base gelling material and 50-80% of aggregate.
The following are several specific examples of the present invention, wherein examples 1 to 10 are the first high free calcium oxide solid waste based gelling material and the preparation method thereof in the present invention; examples 11 to 15 are the second high free calcium oxide solid waste based gelling material and the preparation method thereof in the present invention.
Example 1
The embodiment comprises the following raw materials in percentage by weight: 93 percent of high free calcium oxide fly ash, 13.2 percent of CaO in the high free calcium oxide fly ash, 4.8 percent of free calcium oxide, 2 percent of chemical milling agent and 5 percent of excitant. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical grinding agent with 30% of water consumption for preparing a cementing material to form a diluted chemical grinding agent, mixing high free calcium oxide fly ash with the rest 70% of water to form waste residue 1, adding the diluted chemical grinding agent into the waste residue slurry for 4 times, and stirring for 3min to prepare waste residue slurry 2; and step two, adding sodium silicate into the waste residue slurry 2, stirring for 1min, adding the waste alkali liquor into the waste residue slurry 2, mixing, and continuously stirring for 5min to complete the preparation of the cementing material, wherein the preparation flow is shown in figure 5. Coal gangue is selected as aggregate, the maximum grain diameter of the coal gangue is 1.5cm, coal mine filling paste with the mass concentration of 80% is prepared for coal mine underground filling, a prepared filling body test piece is shown in figure 3, and the ratio of the cementing material to the aggregate is calculated according to the mass: when the prepared filler is cured for 28 days by 35 percent of the high-free calcium oxide solid waste base cementing material and 65 percent of the aggregate, the uniaxial compressive strength is 4.423MPa; when the prepared filler is cured for 28 days by 40 percent of the high-free calcium oxide solid waste base cementing material and 60 percent of the aggregate, the uniaxial compressive strength is 5.813MPa; when 45% of the high-free calcium oxide solid waste base cementing material and 55% of the aggregate are prepared into a filling body, and the prepared filling body is maintained for 28 days, the uniaxial compressive strength is 6.486MPa; as shown in fig. 4. The proportion of 45% of the high free calcium oxide solid waste base cementing material and 55% of the aggregate is used for filling a certain coal mine in the Yangyang area of Shanxi province, field sampling is shown in figure 1, and the uniaxial compressive strength is 6.8Mpa averagely. The strength of a filler test piece prepared by using the same batch of high free calcium oxide fly ash, 35% of high free calcium oxide, 10% of 42.5 cement and 55% of aggregate by mass is invalid after curing for 14 days, as shown in fig. 2.
Example 2
The embodiment comprises the following raw materials in percentage by weight: 95% of high free calcium oxide fly ash, 9.2% of CaO in the high free calcium oxide fly ash, 2.3% of free calcium oxide, 2% of chemical milling agent and 3% of excitant. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material comprises two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical grinding agent with all water for preparing a cementing material to form a diluted chemical grinding agent, adding the diluted chemical grinding agent into the high-free calcium oxide waste residue in several times, and quickly stirring for 3min to prepare slurry; and step two, adding sodium silicate into the slurry and stirring for 1min, adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Coal gangue is selected as aggregate, coal mine filling paste with the mass concentration of 78% is prepared and used for coal mine underground filling, and the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days by 40 percent of the high-free calcium oxide solid waste base cementing material and 60 percent of the aggregate, the uniaxial compressive strength is 4.856MPa.
Example 3
The embodiment comprises the following raw materials in percentage by weight: 65% of high free calcium oxide fly ash, 26% of magnesium slag, 14.3% of CaO in the high free calcium oxide fly ash, 5.2% of free calcium oxide, 6.3% of free calcium oxide in the magnesium slag, 3% of chemical milling agent and 6% of exciting agent. The chemical grinding agent is hydrochloric acid, and the exciting agent is a sodium hydroxide and sodium silicate composite alkali exciting agent. The preparation method of the high free calcium oxide system solid waste base gelling material comprises two-stage excitation, and specifically comprises the following steps: step one, completely mixing a chemical powder grinding agent with water required for preparing a cementing material, adding the mixture into high-free calcium oxide waste residues in times, and quickly stirring for 3min to prepare slurry; and step two, adding the excitant into the slurry, and continuously stirring for 6min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 80%, and using the coal mine filling paste for coal mine underground filling, wherein the mass ratio of a cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days, the uniaxial compressive strength is 5.267MPa when the high-free calcium oxide solid waste base cementing material is 42 percent and the aggregate is 58 percent.
Example 4
The embodiment comprises the following raw materials in percentage by weight: 70% of high free calcium oxide fly ash, 22% of magnesium slag, 9.3% of CaO in the high free calcium oxide fly ash, 2.2% of free calcium oxide, 5.1% of free calcium oxide in the magnesium slag, 2% of chemical milling agent and 6% of exciting agent. The chemical powder grinding agent is an H-type cation exchange resin regenerated liquid acidic medium, and the exciting agent is a sodium hydroxide and sodium silicate composite alkali exciting agent. The preparation method of the high free calcium oxide system solid waste base cementing material comprises two-stage excitation, and comprises the following steps of firstly, mixing a chemical powder grinding agent with 30% of water consumption for preparing the cementing material to form a diluted chemical powder grinding agent, mixing high free calcium oxide waste residues with the rest 70% of water to form waste residues 1, then putting all the diluted chemical powder grinding agent into waste residue slurry 4 times, and stirring for 3min to prepare waste residue slurry 2; and step two, adding the excitant into the slurry, and continuously stirring for 6min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 80%, and using the coal mine filling paste for coal mine underground filling, wherein the mass ratio of a cementing material to the aggregate is as follows: when 45% of the high free calcium oxide solid waste base cementing material and 55% of the aggregate are prepared into a filling body, and the prepared filling body is maintained for 28 days, the uniaxial compressive strength is 5.483MPa.
Example 5
The embodiment comprises the following raw materials in percentage by weight: 60% of high free calcium oxide fly ash, 33% of steel slag, 16.1% of CaO in the high free calcium oxide fly ash, 5.4% of free calcium oxide, 5.2% of free calcium oxide in the steel slag, 2% of chemical grinding agent and 5% of exciting agent. The chemical grinding agent is H-type cation exchange resin regenerated liquid, and the exciting agent is lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material comprises two-stage excitation, and specifically comprises the following steps: step one, completely mixing a chemical grinding agent and water required for preparing a cementing material, adding the chemical grinding agent into the high-free calcium oxide waste residue in several times, and quickly stirring for 3min to prepare slurry; and step two, firstly, adding lime into the waste slag slurry for 2 min, stirring for 1min, then adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 78%, and using the coal mine filling paste for coal mine underground filling, wherein the cementing material and the aggregate are calculated according to the mass ratio: when the prepared filler is cured for 28 days by using 30 percent of the high-free calcium oxide solid waste base cementing material and 70 percent of the aggregate, the uniaxial compressive strength is 3.365MPa.
Example 6
The embodiment comprises the following raw materials in percentage by weight: 52 percent of high free calcium oxide fly ash, 20 percent of magnesium slag and 20 percent of steel slag, wherein the mass percent of CaO in the high free calcium oxide fly ash is 14.3 percent, the mass percent of free calcium oxide is 5.4 percent, the mass percent of free calcium oxide in the magnesium slag is 6.3 percent, the mass percent of free calcium oxide in the steel slag is 5.2 percent, 2 percent of chemical milling agent and 6 percent of excitant. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water consumption for preparing a cementing material to form a diluted chemical powder grinding agent, mixing high free calcium oxide waste residues with the rest 70% of water to form waste residues 1, adding the diluted chemical powder grinding agent into the waste residue slurry 4 times, and stirring for 3min to prepare waste residue slurry 2; and step two, adding sodium silicate into the waste residue slurry 2, stirring for 1min, adding the waste alkali liquor into the waste residue slurry 2, mixing, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as aggregate, preparing coal mine filling paste with the mass concentration of 78% for coal mine underground filling, wherein the mass ratio of the cementing material to the aggregate is as follows: when the prepared filling body is cured for 28 days by 35 percent of high free calcium oxide solid waste base cementing material and 65 percent of aggregate, the uniaxial compressive strength is 4.561MPa.
Example 7
The embodiment comprises the following raw materials in percentage by weight: 40% of high free calcium oxide fly ash, 30% of magnesium slag and 23% of steel slag, wherein the mass percent of CaO in the high free calcium oxide fly ash is 14.3%, the mass percent of free calcium oxide is 5.4%, the mass percent of free calcium oxide in the magnesium slag is 6.3%, the mass percent of free calcium oxide in the steel slag is 5.2%, 2% of chemical milling agent and 5% of exciting agent. The chemical grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with all water for preparing the cementing material to form a diluted chemical powder grinding agent, adding the diluted chemical powder grinding agent into the high-free calcium oxide waste residue in batches, and quickly stirring for 3min to prepare slurry; and step two, firstly adding lime into the slurry and stirring for 1min, then adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Coal gangue is selected as aggregate, coal mine filling paste with the mass concentration of 81% is prepared and used for coal mine underground filling, and the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is maintained for 28 days by using 38 percent of the high-free calcium oxide solid waste base cementing material and 62 percent of the aggregate, the uniaxial compressive strength is 5.549MPa.
Example 8
The embodiment comprises the following raw materials in percentage by weight: 90% of magnesium slag, 6.3% of free calcium oxide in the magnesium slag, 4% of chemical powder grinding agent and 6% of excitant. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water consumption for preparing a cementing material to form a diluted chemical powder grinding agent, mixing magnesium slag with the rest 70% of water to form waste residue 1, adding the diluted chemical powder grinding agent into waste residue slurry for 4 times, and stirring for 3min to prepare waste residue slurry 2; and step two, adding sodium silicate into the waste residue slurry 2, stirring for 1min, adding the waste alkali liquor into the waste residue slurry 2, mixing, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as aggregate, preparing coal mine filling paste with the mass concentration of 80% for coal mine underground filling, wherein the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days by 45 percent of the high-free calcium oxide solid waste base cementing material and 55 percent of the aggregate, the uniaxial compressive strength is 4.982MPa.
Example 9
The embodiment comprises the following raw materials in percentage by weight: 95% of steel slag, 5.2% of free calcium oxide in the steel slag, 2% of chemical powder grinding agent and 3% of exciting agent. The chemical grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, completely mixing a chemical powder grinding agent with water required for preparing a cementing material, adding the mixture into steel slag in batches, and quickly stirring for 3min to prepare slurry; and step two, firstly adding lime into the waste residue slurry for 2 min, stirring for 1min, then adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 80%, and using the coal mine filling paste for coal mine underground filling, wherein the mass ratio of a cementing material to the aggregate is as follows: when the prepared filling body is maintained for 28 days by 40 percent of high free calcium oxide solid waste base cementing material and 60 percent of aggregate, the uniaxial compressive strength is 6.129MPa.
Example 10
The embodiment comprises the following raw materials in percentage by weight: 40% of magnesium slag, 50% of steel slag, 6.3% of free calcium oxide in the magnesium slag, 5.2% of free calcium oxide in the steel slag, 3% of chemical powder grinding agent and 7% of exciting agent. The chemical grinding agent is H-type cation exchange resin regenerated liquid, and the exciting agent is lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water consumption for preparing a cementing material to form a diluted chemical powder grinding agent, mixing high free calcium oxide waste residue with the rest 70% of water to form waste residue 1, adding the diluted chemical powder grinding agent into waste residue slurry for 4 times, and stirring for 3min to prepare waste residue slurry 2; and step two, firstly adding lime into the waste residue slurry for 2 min, stirring for 1min, then adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. The gangue is selected as an aggregate, coal mine filling paste with the mass concentration of 80% is prepared and used for coal mine underground filling, and the mass ratio of the cementing material to the aggregate is as follows: when the prepared filling body is maintained for 28 days by using 42 percent of high free calcium oxide solid waste base cementing material and 58 percent of aggregate, the uniaxial compressive strength is 4.955MPa.
Example 11
The embodiment comprises the following raw materials in percentage by weight: 68% of high free calcium oxide fly ash, 14.3% of CaO in the high free calcium oxide fly ash, 5.4% of free calcium oxide, 25% of coal gasification slag, 2% of chemical grinding agent and 5% of exciting agent. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water for preparing the cementing material to form a diluted chemical powder grinding agent, mixing the other part of water with high-free calcium oxide waste residues to form waste residue slurry, adding the diluted chemical powder grinding agent into the waste residue slurry for 3-5 times, and stirring to prepare slurry; and step two, screening the gasification furnace slag, grinding the fine furnace slag, adding the fine furnace slag into the slurry, stirring to form slurry 3, adding the sodium silicate into the slurry, stirring for 1min, adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material, wherein the preparation flow is shown in fig. 6. Selecting aeolian sand as aggregate, preparing coal mine filling paste with the mass concentration of 82% for coal mine underground filling, wherein the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days by 45 percent of the high-free calcium oxide solid waste base cementing material and 55 percent of the aggregate, the uniaxial compressive strength is 5.733MPa.
Example 12
The embodiment comprises the following raw materials in percentage by weight: 50% of high free calcium oxide fly ash, 20% of magnesium slag, 14.3% of CaO in the high free calcium oxide fly ash, 5.4% of free calcium oxide, 6.3% of free calcium oxide in the magnesium slag, 25% of gasified slag, 2% of chemical milling agent and 3% of exciting agent. The chemical grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material comprises two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical grinding agent and a prepared cementing material with water, mixing the water with waste residues, and stirring to prepare slurry; and step two, screening the gasification furnace slag, grinding the fine furnace slag, adding the fine furnace slag into the slurry, stirring to form slurry 3, adding lime into the slurry, stirring for 1min, adding waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 78%, and using the coal mine filling paste for coal mine underground filling, wherein the cementing material and the aggregate are calculated according to the mass ratio: when 25% of the high-free calcium oxide solid waste base cementing material and 75% of the aggregate are used for curing the prepared filling body for 28 days, the uniaxial compressive strength is 2.694MPa.
Example 13
The embodiment comprises the following raw materials in percentage by weight: 40% of high free calcium oxide fly ash, 15% of magnesium slag and 15% of steel slag, wherein the mass percent of CaO in the high free calcium oxide fly ash is 14.3%, the mass percent of free calcium oxide is 5.4%, the mass percent of free calcium oxide in the magnesium slag is 6.3%, the mass percent of free calcium oxide in the steel slag is 5.2%, 22% of gasified slag, 2% of chemical grinding agent and 6% of exciting agent. The chemical grinding agent is hydrochloric acid, and the exciting agent is a sodium hydroxide and sodium silicate composite alkali exciting agent. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water for preparing the cementing material to form a diluted chemical powder grinding agent, mixing the other part of water with high-free calcium oxide waste residues to form waste residue slurry, adding the diluted chemical powder grinding agent into the waste residue slurry for 3-5 times, and stirring to prepare slurry; and step two, screening the gasification furnace slag, grinding the fine furnace slag, adding the fine furnace slag into the slurry, stirring to form slurry 3, adding sodium hydroxide and sodium silicate into the slurry simultaneously, and continuously stirring for 5min to complete the preparation of the cementing material. Coal gangue is selected as aggregate, coal mine filling paste with the mass concentration of 80% is prepared and used for coal mine underground filling, and the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days by 50 percent of the high-free calcium oxide solid waste base cementing material and 50 percent of the aggregate, the uniaxial compressive strength is 7.692MPa.
Example 14
The embodiment comprises the following raw materials in percentage by weight: 30% of magnesium slag, 38% of steel slag, 6.3% of free calcium oxide in the magnesium slag, 5.2% of free calcium oxide in the steel slag, 25% of gasified slag, 2% of chemical powder grinding agent and 5% of exciting agent. The chemical powder grinding agent is an acidic medium of an H-type cation exchange resin regenerated liquid, and the exciting agent is a composite alkali exciting agent prepared from sodium silicate and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical powder grinding agent with 30% of water for preparing the cementing material to form a diluted chemical powder grinding agent, mixing the other part of water with high-free calcium oxide waste residues to form waste residue slurry, adding the diluted chemical powder grinding agent into the waste residue slurry for 3-5 times, and stirring to prepare slurry; and step two, screening the gasification furnace slag, grinding the fine furnace slag, adding the fine furnace slag into the slurry, stirring to form slurry 3, adding the sodium silicate into the slurry, stirring for 1min, adding the waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Selecting aeolian sand as an aggregate, preparing coal mine filling paste with the mass concentration of 78%, and using the coal mine filling paste for coal mine underground filling, wherein the cementing material and the aggregate are calculated according to the mass ratio: when the prepared filling body is cured for 28 days by 35 percent of high free calcium oxide solid waste base cementing material and 65 percent of aggregate, the uniaxial compressive strength is 4.872MPa.
Example 15
The embodiment comprises the following raw materials in percentage by weight: 55% of magnesium slag, 6.3% of free calcium oxide in the magnesium slag, 35% of coal gasification slag, 2% of chemical powder grinding agent and 8% of exciting agent. The chemical grinding agent is hydrochloric acid, and the exciting agent is a composite alkali exciting agent prepared from lime and waste alkali liquor. The preparation method of the high free calcium oxide system solid waste base gelling material is two-stage excitation, and specifically comprises the following steps: step one, mixing a chemical grinding agent and a prepared cementing material with water, mixing the water with waste residues, and stirring to prepare slurry; and step two, screening the gasification furnace slag, grinding the fine furnace slag, adding the fine furnace slag into the slurry, stirring to form slurry 3, adding lime into the slurry, stirring for 1min, adding waste alkali liquor into the slurry, and continuously stirring for 5min to complete the preparation of the cementing material. Coal gangue is selected as aggregate, coal mine filling paste with the mass concentration of 80% is prepared and used for coal mine underground filling, and the mass ratio of the cementing material to the aggregate is as follows: when the prepared filler is cured for 28 days by 40 percent of the high-free calcium oxide solid waste base cementing material and 60 percent of the aggregate, the uniaxial compressive strength is 4.117MPa.
Claims (9)
1. The high free calcium oxide solid waste base cementing material is characterized by being prepared from water and the following raw materials in parts by weight:
high free calcium oxide waste residue, 85 to 95 percent;
1 to 10 percent of chemical grinding agent;
1 to 10 percent of excitant;
or, the water-soluble paint is prepared from water and the following raw materials in parts by weight:
50 to 80 percent of high free calcium oxide waste residue;
gasifying slag, 10 to 40 percent;
2 to 6 percent of chemical grinding agent;
3 to 5 percent of excitant;
completely mixing a chemical powder grinding agent with water required for preparing a cementing material, adding the mixture into high-free calcium oxide waste residue, and stirring to prepare slurry; adding an activator or coal gasification slag and the activator into the slurry, and continuously stirring to finish the preparation of the cementing material;
the chemical grinding agent is an acidic medium, the exciting agent is a compound alkali exciting agent, and the compound alkali exciting agent consists of 2-3 of lime, sodium hydroxide, carbonate and sodium silicate;
the high free calcium oxide waste residue is one or a plurality of mixtures of fly ash, magnesium slag and steel slag;
the content of free calcium oxide in the fly ash meets the following requirements: the mass fractions of free calcium oxide of the F-class fly ash and the C-class fly ash are respectively more than 1% and 4%;
the mass fraction of free calcium oxide in the steel slag exceeds 4 percent;
the mass fraction of free calcium oxide in the magnesium slag is more than 4% or the mass fraction of magnesium oxide is more than 8%.
2. The high free calcium oxide solid waste-based cementing material as claimed in claim 1, wherein when the high free calcium oxide waste residue is a mixture containing fly ash, the weight percentage of each component in the mixture is as follows:
60% -90% of fly ash and 10% -40% of magnesium slag; or the like, or, alternatively,
60-90% of fly ash and 10-40% of steel slag; or the like, or, alternatively,
50-78% of fly ash, 10-30% of magnesium slag and 10-30% of steel slag;
when the high free calcium oxide waste residue is a mixture without fly ash, the weight percentage of each component in the mixture is as follows:
45-65% of magnesium slag and 35-55% of steel slag.
3. The high free calcium oxide solid waste based gelling material of claim 1, wherein the acidic medium is sulfuric acid, phosphoric acid, hydrochloric acid or H type cation exchange resin regeneration liquid.
4. The method for preparing the high-free calcium oxide solid waste based gelling material as claimed in claim 1, characterized in that the high-free calcium oxide solid waste based gelling material is prepared by two-stage excitation, as follows:
step one, completely mixing a chemical powder grinding agent with water required for preparing a cementing material, adding the mixture into high-free calcium oxide waste residue, and stirring to prepare slurry;
and step two, adding an activator or coal gasification slag and the activator into the slurry, and continuously stirring to finish the preparation of the cementing material.
5. The preparation method according to claim 4, wherein the chemical powder grinding agent is added according to the proportion of the content of free calcium oxide in the high-free-calcium-oxide waste residue to be measured, specificallyThe formula is as follows: c = (C)1m1+C2m2+C3m3)/(m1+m2+m3) (ii) a The mol ratio is as follows: 1000C/74, [ H + ] =0.1 to 2; wherein C represents the mass percent of free calcium oxide in the solid mixture, C1Represents the mass percent of free calcium oxide of the fly ash, m1Represents the mass of fly ash, C2Represents the mass percent of free calcium oxide of the magnesium slag, m2Denotes the mass of magnesium slag, C3Represents the mass percent of free calcium oxide of the steel slag, m3The mass of the required water is 70-90% of the mass of the high free calcium oxide waste residue solid.
6. The method according to claim 4, wherein in the first step:
mixing the chemical powder grinding agent with part of water to form a diluted chemical powder grinding agent, mixing the other part of water with the high-free calcium oxide waste residue to form waste residue slurry, adding the diluted chemical powder grinding agent into the waste residue slurry for 3-5 times, and stirring to prepare slurry; or the like, or, alternatively,
the chemical grinding agent and the prepared cementing material are mixed by water, and then the water is mixed with the high free calcium oxide waste residue and stirred to prepare slurry.
7. The method according to claim 4, wherein in the second step:
when the gas slag does not exist, adding the excitant into the slurry once to mix and stir when the excitant is a solid or liquid composite excitant with the same form; when the excitant is a composite excitant with different forms, adding the excitant into the slurry according to different form classifications, mixing and stirring, wherein the sequence is solid firstly and liquid secondly;
when the gas slag is contained, screening and grinding the gas slag, adding the gas slag into the slurry, stirring to form new slurry, and adding the excitant into the new slurry once for mixing and stirring when the excitant is a solid or liquid composite excitant with a certain same form; when the excitant is a composite excitant with different forms, the excitant is added into new slurry according to different form classifications for mixing and stirring, and the sequence is solid firstly and liquid secondly.
8. Use of the high free calcium oxide solid waste based cementitious material of claim 1 as a fill material for coal mine fill mining.
9. The application of the high-free-calcium-oxide solid waste-based cementing material and the aggregate as claimed in claim 8, wherein the strength of concrete prepared from the high-free-calcium-oxide solid waste-based cementing material and the aggregate is less than 15MPa, and the ratio of the cementing material to the aggregate is as follows by mass: 20-50% of high-free calcium oxide solid waste base gelling material and 50-80% of aggregate.
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