Preparation method of bio-based fly ash admixture
Technical Field
The invention belongs to the technical field of concrete solid waste admixture, and particularly relates to a preparation method of a bio-based fly ash admixture.
Background
The concrete is an artificial stone material prepared from cement, sand stone, water, necessary additives and admixtures according to a certain proportion through uniformly stirring, closely compacting, curing and hardening. The high-strength concrete has high compressive strength, good durability and wide strength grade range, is widely applied to civil engineering, and is the most common building material in daily life. The cement is a main component playing a role in gelation in concrete, is a powdery hydraulic inorganic cementing material, and brings great pollution to the environment in the production process. According to statistics, 1kg of concrete is averageBall warming potential was approximately 981 kg CO2Equivalent, by 2018, the total amount of the global concrete reaches 483 hundred million tons, and CO is discharged accumulatively2The amount has reached 4.0X 1015 kg CO2Equivalent weight is currently recognized as the major cause of global warming.
China is the first major mining country in the world, and abundant coal mine resources provide sufficient power for people and simultaneously generate high-pollution active waste called fly ash. The fly ash is a material with a structure similar to that of natural mineral and is prepared from crystalline SiO2As a main component, there are a large amount of CaO, Al, etc. on the surface and inside2O3And Fe2O3And the gray tiny amorphous solid vitreous micro-beads with the particle size of the active ingredients being between 1 and 100 mu m. Statistically, 1 ton of fly ash is produced per 2 tons of coal consumed. By the end of 2018, the annual output of the fly ash in China reaches 7.00 hundred million tons, and the output is the first in the world. However, the solid waste powder is accumulated or buried in nature for a long time, and the accumulated coal ash can foul rivers, occupy cultivated lands and produce dust pollution, thereby causing serious ecological environment problems. In order to solve the problem of solid waste, people utilize the volcanic ash activity of the fly ash to replace part of cement to be used as admixture in concrete, so that the fly ash is changed into valuable, the working performance of the concrete can be improved, the cement can be saved, and remarkable economic benefit is obtained. However, since these powders themselves have a stable crystal structure during the use of fly ash, their activity is difficult to be excited without treatment. The surface of the material is modified by physical or chemical methods to meet the use requirements.
The ball milling method is the simplest physical method for changing the form of the fly ash, can directly change the particle size of the fly ash and increase the specific surface area of the fly ash particles, thereby improving the hydration reaction efficiency of cement. In 2017, Jiangbo and the like prove that the best effect is obtained when the fly ash is subjected to ball milling for 15 min and is used for replacing 10% of cement. Also, by adding an inorganic base or an alkaline salt to the fly ash, SiO on the surface thereof is dissolved2Is the most commonly used chemical modification method. Fr 1989any et al first confirmed that sodium hydroxide can directly change the glass bead form of the fly ash, and improve the hydration reaction rate of the fly ash. With the research, in 2019, the organic chemical modification method is adopted by ruqiangming and the like, and the triethanolamine is proved to change the activity of the fly ash to a certain extent. However, these modification methods have problems of difficulty in activating the activity of the powder, easy agglomeration, high cost, and high pollution.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a bio-based fly ash admixture, which utilizes the bio-modified fly ash as the admixture to change the fly ash into valuable and increase the later-period compressive strength of cement mortar.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a bio-based fly ash admixture comprises the following steps:
firstly, culturing silicate bacteria to obtain activated silicate bacteria liquid;
step two, preparing a modified culture solution, wherein the modified culture solution comprises the following components: 2-5 g/L of sucrose and MgSO4 0.5 g/L,FeCl3 0~0.005 g/L,Na2HPO40.5-2 g/L, pH 7.0-9.0, and autoclaving;
thirdly, mixing the activated silicate bacteria liquid with the modified culture solution according to the volume ratio of (0.5-2): (8-9.5);
fourthly, modifying the surface of the fly ash particles by silicate bacteria: adding untreated fly ash into a mixed solution of an activated silicate bacteria liquid and a modified culture solution, stirring, standing for 1 h, removing a supernatant, and rinsing a precipitate to obtain biological-based fly ash;
and fifthly, drying the bio-based fly ash to constant weight to obtain the bio-based fly ash admixture.
Further, the silicate bacteria are cultured in the first step, after the frozen silicate bacteria are unfrozen at normal temperature, 1.0 mL of the melted silicate bacteria liquid is taken to be transferred to 10 mL of the activation culture liquid, after the shaking culture is carried out for 24-48 h, 1.0 mL of the bacteria liquid is taken to be transferred to 100 mL of the activation culture liquid, and the shaking culture is continued for 20-30 h, so that the activated silicate bacteria liquid is obtained; wherein the frozen silicate bacteria are bacillus mucilaginosus stored in an ultra-low temperature refrigerator at minus 80 ℃, the shaking culture temperature is 30 ℃, and the shaking culture rotating speed is 150-180 rpm.
Further, the composition of the activation culture solution is as follows: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO42 g/L, 1 g/L of glass powder, 7.0-7.5 of pH, and carrying out autoclaving at 121 ℃ for 15 min.
Further, the pH value of the modified culture solution in the second step is 7.0-7.5; autoclaving at 121 deg.C for 15 min.
Further, the mass ratio of the fly ash to the mixed liquid in the fourth step is (0.5-1): 2; the stirring temperature is 20-35 ℃; the stirring speed is 100 rpm-200 rpm, the stirring time is 1 d-5 d, and the rinsing times are 0-3.
Further, the stirring temperature is 25-30 ℃; the stirring speed is 150 rpm-180 rpm; the stirring time is 3 d to 5 d; the rinsing times are 1-2 times.
Further, in the fifth step, the bio-based fly ash is dried in a constant temperature drying oven at a low temperature to a constant weight to obtain the bio-based fly ash admixture, wherein the temperature of the constant temperature drying oven is 50-60 ℃.
Further, the fly ash is II-grade fly ash, and the specific surface area of the fly ash is 900 m2/kg~1000 m2Per kg, the residue percentage of 45 mu m sieve is 10-25%.
Further, the silicate bacteria are Bacillus mucilaginosus.
Further, the bacterial concentration of the activated silicate bacteria liquid is 1 multiplied by 107~1×109 cfu/mL。
The metabolites of silicate bacteria are exopolysaccharides and organic acids secreted by Bacillus mucilaginosus.
The bacillus mucilaginosus strain is prepared by the following steps of (1) the bacillus mucilaginosus strain is prepared by the following steps: bacillus mucilaginosus, guangdong collection of microorganisms, accession number GDMCC 1.15.
The preparation principle of the invention is as follows: silicate bacteria can secrete extracellular viscous macromolecular substances such as polysaccharide, micromolecular organic acid and other metabolites, and the metabolites have acidolysis, complexation, redox, flocculation dispersion and other effects on the silicon-containing minerals, so that the lattice structure of the minerals is destroyed, and the silicon elements in the minerals are released. The fly ash is similar to a natural mineral structure and is made of SiO2As a main component, Al is present on the surface and inside2O3CaO and Fe2O3Etc. of active ingredients. Therefore, silicate bacteria can perform a corrosion action on siliceous components on the surface of the fly ash, so that insoluble silicon is changed into soluble silicon, silicon elements on the surface of the powder are partially removed, the surface structure of the fly ash is changed, the specific surface area of the powder is increased, and the chemical activity of the surface of the fly ash can be further improved.
The invention has the beneficial effects that:
compared with the prior art, the preparation method of the bio-based fly ash admixture provided by the invention has the following advantages: (1) the fly ash modified by the biological method is used as an admixture, so that the fly ash can be changed into valuable, the preparation condition is mild, the operation is simple and easy, the cost is relatively low, complex and expensive equipment is not needed, no secondary pollution is caused, and the like. (2) The method has low requirement on the grade of the used fly ash, can effectively stimulate the chemical activity of the surface of the fly ash under the condition of no need of pretreatment, and the prepared bio-based fly ash can quickly increase the later-stage compressive strength of cement mortar, and has a strength activity index far superior to that of common fly ash under the same mixing amount; (3) the bio-based fly ash prepared by the method is not easy to agglomerate and has good dispersibility, because a layer of biomacromolecule metabolite is attached to the surface of the powder, the bio-based fly ash has good dispersing effect and is beneficial to improving the working performance of concrete; (4) compared with the common fly ash, the biomacromolecule metabolite on the surface of the bio-based fly ash can reduce the water demand of the cement mortar, and further can reduce the dosage of the water reducing agent in concrete. Therefore, the quality of the common fly ash admixture can be improved through modifying the surface of the fly ash by the microorganism, the green and environment-friendly ecological performance of the admixture preparation is enhanced, the admixture is a supplement of the existing admixture, and the application prospect in the field of concrete production is good.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Unfreezing frozen bacillus mucilaginosus at normal temperature, taking 1.0 mL of the thawed bacillus mucilaginosus liquid to transfer into 10 mL of activated culture solution, carrying out shake culture for 48 h, taking 1.0 mL of the liquid to transfer into 100 mL of the activated culture solution, and continuing to carry out shake culture for 24 h. Adding the activated bacillus mucilaginosus bacterial liquid into 800 mL of modified culture solution containing 400g of fly ash by 10 percent of inoculation amount, stirring at 180 rpm at 30 ℃ for 1 d, standing for 1 h, removing supernatant, rinsing bottom sediment for 1 time, and drying in a constant-temperature drying oven at 50 ℃ until the weight is constant, thus obtaining the bio-based fly ash admixture.
The composition of the activation culture solution is as follows: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO42 g/L, 1 g/L of glass powder, 7.0-7.5 of pH, and carrying out autoclaving at 121 ℃ for 15 min.
The modified culture solution comprises the following components: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO4 2 g/L, pH 7.0-7.5, and autoclaving at 121 ℃ for 15 min.
Example 2
Unfreezing frozen bacillus mucilaginosus at normal temperature, taking 1.0 mL of the thawed bacillus mucilaginosus liquid to transfer into 10 mL of activated culture solution, carrying out shake culture for 48 h, taking 1.0 mL of the liquid to transfer into 100 mL of the activated culture solution, and continuing to carry out shake culture for 24 h. Adding the activated bacillus mucilaginosus bacterial liquid into 800 mL of modified culture solution containing 400g of fly ash by 10 percent of inoculation amount, stirring at 180 rpm at 30 ℃ for 3 d, standing for 1 h, removing supernatant, and drying bottom sediment in a constant-temperature drying oven at 50 ℃ until the weight is constant to obtain the biological-based fly ash admixture.
The composition of the activation culture solution is as follows: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO42 g/L, 1 g/L of glass powder, pH 7.0-7.2, and autoclaving at 121 ℃ for 15 min.
The modified culture solution comprises the following components: sucrose 2 g/L, MgSO4 0.5 g/L,Na2HPO40.5 g/L, pH 7.0-7.5, and autoclaving at 121 ℃ for 15 min.
Example 3
Unfreezing frozen bacillus mucilaginosus at normal temperature, taking 1.0 mL of the thawed bacillus mucilaginosus liquid to transfer into 10 mL of activated culture solution, carrying out shake culture for 48 h, taking 1.0 mL of the liquid to transfer into 100 mL of the activated culture solution, and continuing to carry out shake culture for 24 h. Adding the activated bacillus mucilaginosus into 800 mL of modified culture solution containing 400g of fly ash by 10 percent of inoculation amount, stirring at 180 rpm at 30 ℃ for 3 d, standing for 1 h, removing supernatant, rinsing bottom sediment for 1 time, and drying in a constant-temperature drying oven at 50 ℃ until the weight is constant, thus obtaining the bio-based fly ash admixture.
The composition of the activation culture solution is as follows: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO42 g/L, 1 g/L of glass powder, 7.0-7.5 of pH, and carrying out autoclaving at 121 ℃ for 15 min.
The modified culture solution comprises the following components: sucrose 2 g/L, MgSO4 0.5 g/L,Na2HPO40.5 g/L, pH 7.0-7.5, and autoclaving at 121 ℃ for 15 min.
Example 4
Unfreezing frozen bacillus mucilaginosus at normal temperature, taking 1.0 mL of the thawed bacillus mucilaginosus liquid to transfer into 10 mL of activated culture solution, carrying out shake culture for 48 h, taking 1.0 mL of the liquid to transfer into 100 mL of the activated culture solution, and continuing to carry out shake culture for 24 h. Adding the activated bacillus mucilaginosus into 800 mL of modified culture solution containing 400g of fly ash by 10 percent of inoculation amount, stirring at 180 rpm at 30 ℃ for 5d, standing for 1 h, removing supernatant, rinsing bottom sediment for 1 time, and drying in a constant-temperature drying oven at 50 ℃ until the weight is constant, thus obtaining the bio-based fly ash admixture.
The composition of the activation culture solution is as follows: sucrose 5 g/L, MgSO4 0.5 g/L,FeCl3 0.005 g/L,Na2HPO42 g/L, 1 g/L of glass powder, 7.0-7.5 of pH, and carrying out autoclaving at 121 ℃ for 15 min.
The modified culture solution comprises the following components: sucrose 2 g/L, MgSO4 0.5 g/L,Na2HPO40.5 g/L, pH 7.0-7.5, and autoclaving at 121 ℃ for 15 min.
Comparative example
Fly ash used in examples 1-4.
And (3) forming a mortar test piece by adopting the mortar mixing proportion in GB/T1596-2017 fly ash for cement and concrete, ensuring the mixing amount to be consistent between the comparative example and the example, and curing the formed mortar under the standard condition. Table 1 shows the comparison of the performance of the bio-based fly ash admixtures of examples 1-4 with the fly ash of the comparative example.
TABLE 1 comparison of performance of bio-based fly ash admixture and fly ash prepared in this example
The results in table 1 show that after bacillus mucilaginosus is used for eroding the surface of the fly ash, the specific surface area of the powder is obviously increased along with the prolonging of the action time of the bacteria, which indicates that the surface structure of the powder is changed and the improvement of the chemical reaction activity of the surface of the fly ash is promoted. After the biological-based fly ash admixture is used for manufacturing the cement mortar test piece, the activity indexes of the biological-based fly ash and the common fly ash are basically the same when the biological-based fly ash admixture is maintained for 7 d, which shows that the biological-based fly ash and the common fly ash have almost no difference in the influence on the early compressive strength of the cement mortar test piece. However, when the curing lasts for 28 days, the strength activity index of the bio-based fly ash is obviously improved compared with that of the common fly ash, and particularly, the strength activity index of the bio-based fly ash obtained by the longer time of the bacterial erosion fly ash is improved more quickly. It is noted that the phenomenon of strength activity index reduction appears after ordinary fly ash is maintained for 28 days, which reflects that the compressive strength of the cement mortar test piece in the later period is slowly increased due to low activity and poor quality of the used fly ash. In general, the early compressive strength of the cement mortar is not obviously improved by the bio-based fly ash, but the later compressive strength is increased quickly. The method shows that after the corrosion action of the bacillus mucilaginosus, part of siliceous components on the surface of the fly ash are removed, the specific surface area of the powder is increased, the pore structure of the surface is changed, and the chemical reaction activity of the surface of the fly ash can be effectively improved. Compared with the common fly ash, macromolecular metabolites such as extracellular polysaccharide and the like coated on the surface of the bio-based fly ash play roles of a dispersing agent and a water reducing agent to a certain extent, so that the using amount of the water reducing agent in concrete can be reduced, and the working performance of the concrete can be improved. Therefore, the bio-based fly ash prepared by the method is used as an admixture in the field of concrete production, and has a good application prospect.
The above examples are merely representative of a few embodiments of the present invention, and although the description is specific and detailed, the present invention should not be construed as limited the scope of the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.