CN116813226A - Fly ash-bacteria complex biological curing agent and preparation method and application thereof - Google Patents

Fly ash-bacteria complex biological curing agent and preparation method and application thereof Download PDF

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CN116813226A
CN116813226A CN202311073287.6A CN202311073287A CN116813226A CN 116813226 A CN116813226 A CN 116813226A CN 202311073287 A CN202311073287 A CN 202311073287A CN 116813226 A CN116813226 A CN 116813226A
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fly ash
bacteria complex
bacteria
curing agent
preparing
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CN116813226B (en
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温树杰
黄翔
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Jiangxi University of Science and Technology
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Abstract

The invention relates to solidification of soil and sand materials, in particular to a biological solidifying agent of a fly ash-bacteria complex, a preparation method and application thereof, comprising two parts of a fly ash-bacteria complex and a cementing agent; the fly ash-bacteria complex is formed by mixing neutral fly ash particles with bacillus pasteurizus bacteria liquid for adsorption and drying, and the cementing agent is formed by mixing calcium chloride and urea with supernatant fluid in the fly ash improvement process and then recrystallizing. When in use, the mass ratio is 1: and 1, taking the fly ash-bacteria complex and the cementing agent, mixing into a curing object, compacting and curing after mixing uniformly. The method has the advantages of low cost, good effect, convenient process and no secondary pollution.

Description

Fly ash-bacteria complex biological curing agent and preparation method and application thereof
Technical Field
The invention relates to solidification of soil and sand materials, in particular to a fly ash-bacteria complex biological solidifying agent, a preparation method and application thereof.
Background
At present, the annual production of industrial solid waste in China has reachedApproximately 10 hundred million tons, the accumulated stock quantity exceeds 67 hundred million tons, and the occupied land reaches 65412 ten thousand meters 2 Wherein the discharge amount of the fly ash exceeds 6.5 hundred million tons and accounts for approximately 10 percent of the accumulated storage amount, how to utilize and dispose the fly ash is an important problem. The coal ash in China has a plurality of comprehensive utilization ways and is mainly used for cement and concrete production, engineering filling, structure backfilling and land reclamation; a great deal of research is also carried out in the fields of extracting useful metal substances and minerals from the fly ash, preparing corrosion-resistant additive materials, polymer materials, molecular sieves and other high-added-value utilization fields. However, the utilization of fly ash is still mainly based on building materials, and the high-value recycling technology has high cost and complex process and is not suitable for industrial production.
On the other hand, in recent years, the development of sustainable development of transportation infrastructure by using biological materials instead of physical and chemical materials has become a leading-edge hot spot for global transportation infrastructure technology research. The following problems are often faced in the current application process for biological materials: the biological material has high cost, low adhesiveness and complex production process, so that the application and popularization range is smaller.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a microbial curing agent taking fly ash as a carrier and a preparation method thereof. The method has the advantages of low cost, good effect, convenient process and no secondary pollution.
The invention is realized in such a way that the biological curing agent of the fly ash-bacteria complex comprises two parts of the fly ash-bacteria complex and the cementing agent; the fly ash-bacteria complex is formed by mixing neutral fly ash particles with bacillus pasteurizus bacteria liquid for adsorption and drying, and the cementing agent is formed by mixing calcium chloride and urea with supernatant fluid in the fly ash improvement process and then recrystallizing.
The preparation method of the biological curing agent for the fly ash-bacteria complex comprises the steps of preparing the fly ash-bacteria complex and preparing a cementing agent, wherein the preparation method of the fly ash-bacteria complex comprises the following steps:
(1) Adding fly ash into an ammonium chloride solution, stirring for reaction, filtering and drying to obtain neutral fly ash particles;
(2) Inoculating the bacillus pasteurization seed solution into a liquid culture medium, and performing shake culture at constant temperature to obtain bacillus pasteurization seed solution;
(3) Loading neutral fly ash particles into a stirrer, adding bacillus liquid, stirring and adsorbing, and freeze-drying to obtain a fly ash-bacteria complex;
the preparation of the cementing agent comprises the following steps:
(4) Collecting filtrate in the process of producing neutral fly ash particles, and precipitating in a precipitation tank to obtain supernatant;
(5) Adding calcium chloride and urea into the supernatant, stirring uniformly, regulating pH to be neutral, and recrystallizing to obtain the cementing agent.
The mass ratio of the fly ash to the ammonium chloride is 0.5-0.7, the concentration of the ammonium chloride is 0.5mol/L, the stirring speed is 300r/min, the stirring time is 20min, the drying temperature is 105 ℃, and the drying time is 24h.
The preparation method of the fly ash-bacteria complex biological curing agent comprises the step (4) that the pore diameter of a filtering screen is 5000 meshes.
The preparation method of the fly ash-bacteria complex biological curing agent comprises the step of preparing the bacillus barbituric seed liquid with the concentration of 5x10 9 cfu/mL, wherein the concentration of the bacillus pasteurization bacterial liquid is 6-8 x10 7 cfu/mL。
According to the preparation method of the fly ash-bacteria complex biological curing agent, the liquid culture medium is 1000mL of deionized water, 20g of urea, 5g of peptone, 3g of beef extract, 10mg of manganese sulfate and pH=7.2-7.4.
In the step (2), the inoculation rate of the bacillus pasteurizer bacterial liquid is 1%, the constant-temperature shake culture temperature is 37 ℃, the shake rate is 140r/min, and the culture time is 24 hours.
The preparation method of the fly ash-bacteria complex biological curing agent comprises the steps that the mass ratio of neutral fly ash particles to bacillus pasteurization bacteria liquid is 0.60-0.75; the temperature in the stirrer is 25-40 ℃, the stirring speed is 300r/min, and the stirring time is 40min.
In the step (3), the freeze-drying temperature is-10 to-40 ℃ and the absolute pressure is 4-7 pa.
The preparation method of the biological curing agent for the fly ash-bacteria complex comprises the following steps of (1) preparing a supernatant with pH=7, wherein the cementing liquid is the supernatant, and the mass ratio of calcium chloride to urea is 1000:220:30.
the application of the biological curing agent of the fly ash-bacteria complex in the curing of soil and sand materials is that the soil and sand materials are called as a curing object together and comprise:
step one, adjusting the water content of a cured object to be less than 15%;
step two, according to the mass ratio of 1:1, taking and blending a fly ash-bacteria complex and a cementing agent into a cured object, wherein the use amount of the fly ash-bacteria complex is 20% -25% of the cured object;
step three, compacting and curing after mixing uniformly; the curing temperature is controlled to be 30-35 ℃, and the curing time is not less than 7d;
the percentages are mass percentages.
The application of the biological curing agent for the fly ash-bacteria complex in the curing of soil and sand materials comprises the steps that firstly, the water content of a curing object is adjusted, when the water content is above 15%, quicklime is doped for reducing water, and the curing agent for the fly ash-bacteria complex can be added after the temperature is reduced to room temperature; when the quicklime is used as the water reducing agent, the dosage of the cementing agent is reduced according to the content of calcium ions contained in the doping amount of the quicklime, and meanwhile, the dosage of urea is reduced in a same ratio.
The application of the fly ash-bacteria complex biological curing agent in the curing of soil and sand materials further comprises the following steps: when the pH of the cured object is more than 10, an appropriate amount of an acidic material including, but not limited to, one or more of wollastonite, diatomaceous earth, bentonite and kaolin should be added to adjust the pH to 10 or less.
Compared with the traditional method, the method for preparing the fly ash-bacteria complex by adsorbing bacteria with neutral fly ash particles can effectively reduce the production cost of bacterial carrier materials, reduce the loss of microorganisms in soil solidification and improve the uniformity of the distribution of biological materials in the solidified soil; when the coal ash-bacteria complex and the cementing agent are adopted to strengthen the soil body, the coal ash-bacteria complex is used as the center to enrich free calcium ions, so that the cementing efficiency is remarkably improved, and the solidification effect is improved; the fly ash-bacteria complex takes neutral fly ash particles as bacterial carrier objects, provides a new direction for the resource utilization of the fly ash, greatly reduces the energy consumption in the fly ash utilization, is more green and environment-friendly as a soil body curing agent, and accords with the sustainable development concept.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic illustration of bacterial adsorption of neutral fly ash particles;
FIG. 2 is a graph showing the formation rate of calcium carbonate by the cement reaction of fly ash and bacteria.
Detailed Description
The invention relates to a biological curing agent of a fly ash-bacteria complex, a preparation method and application thereof, comprising two parts of a fly ash-bacteria complex and a cementing agent; the fly ash-bacteria complex is formed by mixing neutral fly ash particles with bacillus pasteurizus bacteria liquid for adsorption and drying, and the cementing agent is formed by mixing calcium chloride and urea with supernatant fluid in the fly ash improvement process and then recrystallizing.
The invention will be further described with reference to the following specific examples,
example 1
(1) Adding the fly ash into 0.5mol/L ammonium chloride solution, wherein the mass ratio of the fly ash to the ammonium chloride solution is 0.5-0.7, the stirring speed is 300r/min, the stirring time is 20min, filtering and collecting the fly ash, adding the fly ash into a washing tank, washing the fly ash with clear water, and the volume ratio of the fly ash to water is 1:5, filtering and drying, wherein the drying temperature is 105 ℃ and the drying time is 24 hours, so as to obtain neutral fly ash particles;
(2) Will beAt a concentration of 5x10 9 Inoculating cfu/mL of bacillus barbituric seed liquid into a liquid culture medium, wherein the inoculation rate is 1%, the culture medium comprises 1000mL of deionized water, 20g of urea, 5g of peptone, 3g of beef extract, 10mg of manganese sulfate, pH=7.2-7.4, and carrying out constant-temperature shake culture for 24 hours to obtain the bacillus barbituric seed liquid with the concentration of 6-8 x10 7 cfu/mL of a bacillus pasteurization bacterial solution;
(3) And (3) loading neutral fly ash particles into a stirrer, adding bacillus pasteurization liquid, wherein the mass ratio of the neutral fly ash particles to the bacillus pasteurization liquid is 0.6, the temperature in the stirrer is 25 ℃, the stirring speed is 300r/min, the stirring is 40min, the filtration and the constant-temperature drying are carried out for 24 hours, the freeze-drying temperature is-10 to-40 ℃, and the absolute pressure is 4-7 pa, so that the fly ash-bacteria complex is obtained. FIG. 1 shows the adsorption of neutral fly ash particles to Bacillus pasteurisation, as can be seen when the adsorption reached saturation at a stirring time of 30min, at which the bacterial concentration of the fly ash-bacteria complex was 9.97x10 7 cfu/g;
(4) Placing the collected filtrate into a sedimentation tank for sedimentation for 24 hours, taking supernatant, adding calcium chloride and urea into the supernatant, wherein the mass ratio of the supernatant to the calcium chloride to the urea is 1000 respectively: 110: 30. 1000:220:30 and 1000:330:30, uniformly stirring, adding 1mol/L sodium hydroxide and 1mol/L hydrochloric acid to adjust the PH to be 7.0, and recrystallizing to obtain 1mol/L cementing agent, 2mol/L cementing agent and 3mol/L cementing agent;
(5) The fly ash-bacteria complex is respectively mixed with 1mol/L cementing agent, 2mol/L cementing agent and 3mol/L cementing agent, the mass ratio of the fly ash-bacteria complex to the 1mol/L cementing agent, the 2mol/L cementing agent and the 3mol/L cementing agent is 0.1, the mixture is stirred uniformly, and the mixture is placed in a reaction chamber at 30 ℃ to fully react for 7d, and the yield of calcium carbonate is analyzed.
Example 2
The difference from example 1 is that the mass ratio of the fly ash-bacteria complex in step (5) to 1mol/L binder, 2mol/L binder and 3mol/L binder is 0.2.
Example 3
The difference from example 1 is that the mass ratio of the fly ash-bacteria complex in step (5) to 1mol/L binder, 2mol/L binder and 3mol/L binder is 0.3.
Example 4
The difference from example 1 is that the mass ratio of the fly ash-bacteria complex in step (5) to 1mol/L binder, 2mol/L binder and 3mol/L binder is 0.4.
Example 5
The difference from example 1 is that the mass ratio of the fly ash-bacteria complex in step (5) to 1mol/L binder, 2mol/L binder and 3mol/L binder is 0.5.
FIG. 2 shows the results of the calcium carbonate yields of examples 1-5, showing that the yield of the fly ash-bacterial composite mixed with 2mol/L cement and 3mol/L cement is greater than that of the fly ash-bacterial composite mixed with 1mol/L cement, and that the calcium carbonate yields are substantially identical. The calcium carbonate yield was maximized when the mass ratio of fly ash-bacterial complex to cement was 0.4, at which point the calcium carbonate yield was 11.81% (see example 4).
Example 6
(1) Adding 2mol/L cementing agent into the red sandstone hole slag, wherein the mass ratio of the cementing agent to the red sandstone hole slag is 0.15, and uniformly stirring to obtain a mixture;
(2) Adding the mixture into a cylindrical mold with an inner diameter of 39mm and a barrel height of 80mm, placing the cylindrical mold in a curing chamber at 30 ℃, curing and molding for 7d, and analyzing the compressive strength.
Example 7
(1) Adding the fly ash-bacteria complex and the red sandstone hole slag into a stirrer, and uniformly mixing the fly ash-bacteria complex and the red sandstone hole slag with the mass ratio of 0.05 to obtain a fly ash-bacteria complex hole slag mixture;
(2) Adding 2mol/L cementing agent into the coal ash-bacterial complex cavity slag mixture, wherein the mass ratio of the cementing agent to the coal ash-bacterial complex cavity slag mixture is 0.15, and uniformly stirring to obtain a mixture;
(3) Adding the mixture into a cylindrical mold with an inner diameter of 39mm and a barrel height of 80mm, placing the cylindrical mold in a curing chamber at 30 ℃, curing and molding for 7d, and analyzing the compressive strength.
Example 8
The difference from example 7 is that the mass ratio of fly ash-bacteria complex to red sand cave slag in step (1) is 0.10.
Example 9
The difference from example 7 is that the mass ratio of fly ash-bacteria complex to red sand cave slag in step (1) is 0.15.
Example 10:
the difference from example 7 is that the mass ratio of fly ash-bacteria complex to red sand cave slag in step (1) is 0.2.
Example 11:
the difference from example 7 is that the mass ratio of fly ash-bacteria complex to red sand cave slag in step (1) is 0.25.
Example 12:
the difference from example 7 is that the mass ratio of fly ash-bacteria complex to red sand cave slag in step (1) is 0.3.
Table 1 shows the results of the compressive strength, it was found that when the concentration of the cementing liquid was 2mol/L, the compressive strength of the test piece after 7d of curing was increased and then decreased with the increase of the mixing amount of the fly ash-bacteria complex, and when the mixing amount of the fly ash-bacteria complex was 25%, the compressive strength was maximized, and at this time, the compressive strength was 2.385MPa (example 11), and the strength was increased by 2.215MPa as compared with the case of not mixing the fly ash-bacteria complex. After that, the concentration of the cementing liquid is further increased, and the compressive strength begins to be reduced to some extent, because the content of the fly ash is too high, so that the overall compressive strength is reduced.
TABLE 1
Examples Curing time Cementing liquid Amount of complex (%) Compressive strength (MPa)
6 7d 2mol/L 0 0.170
7 7d 2mol/L 5 0.561
8 7d 2mol/L 10 1.320
9 7d 2mol/L 15 1.864
10 7d 2mol/L 20 2.353
11 7d 2mol/L 25 2.385
12 7d 2mol/L 30 2.278
The application of the biological curing agent for the fly ash-bacteria complex in the curing of soil and sand materials comprises the steps of adding quicklime to reduce water when the water content of a curing object is above 15%, and adding the curing agent for the fly ash-bacteria complex after the temperature is reduced to room temperature; when the quicklime is used as the water reducing agent, the dosage of the cementing agent is reduced according to the content of calcium ions contained in the doping amount of the quicklime, and meanwhile, the dosage of urea is reduced in a same ratio.
The application of the fly ash-bacteria complex biological curing agent in the curing of soil and sand materials further comprises the following steps: when the pH of the cured object is more than 10, an appropriate amount of an acidic material including, but not limited to, one or more of wollastonite, diatomaceous earth, bentonite and kaolin should be added to adjust the pH to 10 or less.
The fly ash exists in an aluminum-rich glass body, is an aggregate of various mineral monomer particles with high dispersity, has the characteristics of small particles, large specific surface area, high porosity, high activity, strong adsorption capacity and the like, and has higher adsorption efficiency by taking neutral fly ash particles as a bacterial carrier material. In the solidification process, the fly ash-bacteria complex is distributed more uniformly in the soil body, and the solidified soil body has higher compressive strength and shear strength.

Claims (13)

1. The biological curing agent for the fly ash-bacteria complex is characterized by comprising two parts of a fly ash-bacteria complex and a cementing agent; the fly ash-bacteria complex is formed by mixing neutral fly ash particles with bacillus pasteurizus bacteria liquid for adsorption and drying, and the cementing agent is formed by mixing calcium chloride and urea with supernatant fluid in the fly ash improvement process and then recrystallizing.
2. The method for preparing the biological curing agent for the fly ash-bacteria complex according to claim 1, which comprises the steps of preparing the fly ash-bacteria complex and preparing a cementing agent, wherein the preparation of the fly ash-bacteria complex comprises the following steps:
(1) Adding fly ash into an ammonium chloride solution, stirring for reaction, filtering and drying to obtain neutral fly ash particles;
(2) Inoculating the bacillus pasteurization seed solution into a liquid culture medium, and performing shake culture at constant temperature to obtain bacillus pasteurization seed solution;
(3) Loading neutral fly ash particles into a stirrer, adding bacillus liquid, stirring and adsorbing, and freeze-drying to obtain a fly ash-bacteria complex;
the preparation of the cementing agent comprises the following steps:
(4) Collecting filtrate in the process of producing neutral fly ash particles, and precipitating in a precipitation tank to obtain supernatant;
(5) Adding calcium chloride and urea into the supernatant, stirring uniformly, regulating pH to be neutral, and recrystallizing to obtain the cementing agent.
3. The method for preparing the biological curing agent for the fly ash-bacteria complex according to claim 2, wherein the mass ratio of the fly ash to the ammonium chloride is 0.5-0.7, the concentration of the ammonium chloride is 0.5mol/L, the stirring speed is 300r/min, the stirring time is 20min, the drying temperature is 105 ℃, and the drying time is 24h.
4. The method for preparing a biological curing agent for a fly ash-bacteria complex according to claim 2, wherein the pore size of the filtering screen used in the step (4) is 5000 mesh.
5. The method for preparing a biological curing agent of a fly ash-bacteria complex according to claim 2, which comprises the following steps ofCharacterized in that the concentration of the bacillus pasteurizer seed solution is 5x10 9 cfu/mL, wherein the concentration of the bacillus pasteurization bacterial liquid is 6-8 x10 7 cfu/mL。
6. The method for preparing the biological curing agent for the fly ash-bacteria complex according to claim 2, wherein the liquid culture medium is 1000mL of deionized water, 20g of urea, 5g of peptone, 3g of beef extract, 10mg of manganese sulfate and pH=7.2-7.4.
7. The method for preparing the biological curing agent of the fly ash-bacteria complex according to claim 2, wherein in the step (2), the inoculation rate of the bacillus pasteurizer bacterial solution is 1%, the constant-temperature shake culture temperature is 37 ℃, the shake rate is 140r/min, and the culture time is 24h.
8. The method for preparing the fly ash-bacteria complex biological curing agent according to claim 2, wherein the mass ratio of the neutral fly ash particles to the bacillus pasteurization solution is 0.60-0.75; the temperature in the stirrer is 25-40 ℃, the stirring speed is 300r/min, and the stirring time is 40min.
9. The method for preparing a biological curing agent for a fly ash-bacteria complex according to claim 2, wherein in the step (3), the freeze-drying temperature is-10 to-40 ℃ and the absolute pressure is 4-7 Pa.
10. The method for preparing the biological curing agent of the fly ash-bacteria complex according to claim 2, wherein the pH=7 of the supernatant, and the mass ratio of the supernatant, calcium chloride and urea in the cementing liquid is 1000:220:30.
11. the application of the biological curing agent for the fly ash-bacteria complex in the curing of soil and sand materials according to claim 1, wherein the soil and sand materials are collectively called as a curing object and comprise:
step one, adjusting the water content of a cured object to be less than 15%;
step two, according to the mass ratio of 1:1, taking and blending a fly ash-bacteria complex and a cementing agent into a cured object, wherein the use amount of the fly ash-bacteria complex is 20% -25% of the cured object;
step three, compacting and curing after mixing uniformly; the curing temperature is controlled to be 30-35 ℃, and the curing time is not less than 7d;
the percentages are mass percentages.
12. The application of the biological curing agent for the fly ash-bacteria complex in curing soil and sand materials according to claim 11, wherein the first step of adjusting the water content of the cured object comprises the steps of adding quicklime to reduce water when the water content is above 15%, and adding the curing agent for the fly ash-bacteria complex after the temperature is reduced to room temperature; when the quicklime is used as the water reducing agent, the dosage of the cementing agent is reduced according to the content of calcium ions contained in the doping amount of the quicklime, and meanwhile, the dosage of urea is reduced in a same ratio.
13. The use of a fly ash-bacteria complex biological curing agent according to claim 1 in soil mass and sand curing, further comprising: when the pH of the cured object is more than 10, an acidic material including, but not limited to, one or more of wollastonite, diatomaceous earth, bentonite and kaolin should be added to adjust the pH to 10 or less.
CN202311073287.6A 2023-08-24 2023-08-24 Fly ash-bacteria complex biological curing agent and preparation method and application thereof Active CN116813226B (en)

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