CN112877234B - Paenibacillus mucilaginosus, microorganism-excited circulating fluidized bed fly ash cementing material, method and application - Google Patents
Paenibacillus mucilaginosus, microorganism-excited circulating fluidized bed fly ash cementing material, method and application Download PDFInfo
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Abstract
The invention provides paenibacillus mucilaginosus and application thereof, a microorganism-excited circulating fluidized bed fly ash cementing material and a preparation method and application thereof, and belongs to the technical field of cementing materials. The paenibacillus mucilaginosus LT1906 provided by the invention has the preservation number of CGMCC No.21337, can dissolve silicate and aluminosilicate minerals in the fly ash of the circulating fluidized bed and increase the active SiO2The dissolution of the circulating fluidized bed fly ash is used for exciting the circulating fluidized bed fly ash cementing material, improving the problems of large water demand, low early strength and the like of the circulating fluidized bed fly ash, and improving the recycling comprehensive utilization of the circulating fluidized bed fly ash in the building material field.
Description
Technical Field
The invention belongs to the technical field of cementing materials, and particularly relates to paenibacillus mucilaginosus, a culture method and application thereof, a microorganism-excited circulating fluidized bed fly ash cementing material, and a preparation method and application thereof.
Background
Circulating Fluidized Bed (CFB) fly ash is SO used by thermal power plant for controlling combustion of low-grade coal2Discharging, and adding limestone into the furnace to desulfurize to generate sulfur-fixing fly ash. The CFB fly ash has potential pozzolanic activity and self-hardening property, and can be used as an auxiliary cementing material for cement and concrete. However, the CFB fly ash has a loose and porous surface, a high calcium and sulfur content and a high ignition loss, and is used as an auxiliary cementing material for cement and concrete, which has a large water demand, a low early strength and a high later expansion rate, and severely restricts the comprehensive recycling of the CFB fly ash in the field of building materials, so that the development of a CFB fly ash activity excitation technology capable of effectively improving the problems of the large water demand, the low early strength and the like of the CFB fly ash as the cementing material is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides paenibacillus mucilaginosus, a culture method and application thereof, a microorganism-excited circulating fluidized bed fly ash cementing material, a preparation method and application thereof. The paenibacillus mucilaginosus provided by the invention is used for activating CFB fly ash, effectively solves the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material, and improves the comprehensive resource utilization of CFB fly ash in the field of building materials.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906, and the preservation number is CGMCC No. 21337.
The invention provides a method for culturing Paenibacillus mucilaginosus LT1906, which comprises the following steps: inoculating Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 to a seed culture medium for seed culture to obtain a Paenibacillus mucilaginosus seed solution; inoculating the obtained Paenibacillus mucilaginosus seed liquid to a fermentation culture medium to obtain a Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid;
the seed culture medium comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/LK2HPO4，0.1～0.2g/LMgSO4·7H2O，0.002～0.005g/L FeCl3， 0.2～0.5g/L CaCO3And 0.2 to 0.5g/L (NH)4)2SO4The pH value of the seed culture medium is 7.0-7.5; the temperature of the seed culture is 30-35 ℃, the time of the seed culture is 24-48 h, and the rotation speed of the seed culture is 160-200 rpm;
the fermentation medium comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/L K2HPO4，0.1～0.2g/L MgSO4·7H2O，0.002～0.005g/L FeCl3And 0.2 to 0.5g/L of CaCO3The pH value of the fermentation medium is 7.0-7.5, the inoculation amount of the fermentation culture is 5% -10%, the temperature is 30-32 ℃, the rotation speed of the fermentation culture is 160-200 rpm, and the time is 24-60 h.
The invention provides application of Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 in the technical scheme in exciting fly ash gelation of a circulating fluidized bed.
The invention provides a fly ash cementing material of a microorganism-excited circulating fluidized bed, which comprises the following raw materials: circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus LT1906 and vinegar residue leachate in the technical scheme. Preferably, the mass ratio of the circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 and the vinegar residue leachate in the technical scheme is 100: (9-27): (18-36).
Preferably, the circulating fluidized bed fly ash is a solid waste generated by power generation of a circulating fluidized bed boiler, and the circulating fluidized bed fly ash comprises the following components in percentage by mass: SiO 22≥35％，f-CaO≤4％，SO3Less than or equal to 3 percent, and the specific surface area of 330-400 m2And 80 mu m of screen residue is 15 to 20 percent per kg.
Preferably, the bacterial concentration of the Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid is 106～107The bacterial suspension has a viscosity of 2-15 mPas per mL.
Preferably, the preparation method of the vinegar residue leachate comprises the following steps: mixing water and fresh vinegar residue according to the mass ratio (800-1000): 1, standing for 24-36 hours at 4-10 ℃, and filtering to remove solid vinegar residue to obtain vinegar residue leachate.
The invention provides a preparation method of a microorganism-excited circulating fluidized bed fly ash cementing material in the technical scheme, which comprises the following steps: and (3) mixing the circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus LT1906 and the vinegar residue leachate to obtain the microorganism-excited circulating fluidized bed fly ash cementing material.
The invention provides the application of the microbial-excited circulating fluidized bed fly ash cementing material in the technical scheme or the microbial-excited circulating fluidized bed fly ash cementing material obtained by the preparation method in the technical scheme in the building material field.
Has the advantages that:
the Paenibacillus mucilaginosus LT1906 provided by the invention has Latin article of Paenibacillus mucinosus and a preservation number of CGMCC No. 21337. The paenibacillus mucilaginosus LT1906 provided by the invention can dissolve silicate and aluminosilicate minerals in CFB fly ash and increase active SiO2The content of the calcium silicate hydrate gel (C-S-H) is beneficial to accelerating the generation of the calcium silicate hydrate gel (C-S-H), thereby improving the gel strength; the paenibacillus mucilaginosus can also damage II-CaSO on the surface of CFB fly ash4The crystal form reduces the hydration product dihydrate gypsum and relieves the later expansion problem; the paenibacillus mucilaginosus can also secrete a large amount of extracellular mucopolysaccharide, is combined with free water which cannot effectively react through hydrogen bonds, and has the effects of reducing water and delaying coagulation, so that the water demand of CFB fly ash is reduced, and the rheological property of slurry is improved. The paenibacillus mucilaginosus LT1906 provided by the invention can be used for exciting the modification of CFB fly ash, improving the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material, and improving the resource comprehensive utilization of CFB fly ash in the field of building materials.
Biological preservation Instructions
Paenibacillus mucilaginosus LT1906, Latin article is Paenibacillus mucoginosus, and is preserved in China general microbiological culture Collection center of the Committee for culture Collection of microorganisms with the preservation number: CGMCC No.21337, preservation date of 2020, 12 months and 09 days, and preservation address No. 3 of West Lu No. 1 of Beijing, Chaoyang district, Chaozhou.
Drawings
FIG. 1 is a tree phylogenetic from Paenibacillus mucilaginosus LT1906 of the present invention;
FIG. 2 is an SEM photograph of the cement of example 1 used to stabilize hydration products of silt at different ages in example 4, wherein A is the age of 3d, B is the age of 7d, and C is the age of 28 d;
figure 3 is an XRD pattern of each treatment group of example 7.
Detailed Description
The invention provides Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906, and the preservation number is CGMCC No. 21337. The invention provides a colloidal spore-like rodThe bacterial colony of the bacterium (Paenibacillus mucinosus) LT1906 is characterized by being like a glass bead, colorless, transparent, moist, glossy, smooth in bacterial colony, neat in edge, sticky and elastic in colloid, and can be pulled into a filament when being picked up. The 16S rDNA sequence of the Paenibacillus mucilaginosus is compared with the 16S rDNA sequence published in GenBank by using BLAST software, the similarity with 15 strains of bacillus (bacillus) and Paenibacillus (Paenibacillus) is more than 99 percent, and a phylogenetic tree is shown in figure 1. The paenibacillus mucilaginosus LT1906 provided by the invention can dissolve silicate and aluminosilicate minerals in CFB fly ash and increase active SiO2The content of (A) is favorable for accelerating the generation of C-S-H gel and improving the gel strength; the paenibacillus mucilaginosus can also damage II-CaSO on the surface of CFB fly ash4Crystal form, CaSO4Increasing solubility, insoluble CaSO4The reduction leads the hydration product dihydrate gypsum to be reduced, and can relieve the later expansion problem; moreover, the paenibacillus mucilaginosus can secrete a large amount of extracellular mucopolysaccharide, can be combined with free water which cannot effectively react through hydrogen bonds, and has the effects of reducing water and delaying coagulation, so that the water demand of CFB fly ash is reduced, the rheological property of slurry is improved, and the workability and the subsequent processability are improved. Therefore, the paenibacillus mucilaginosus LT1906 provided by the invention can be used for modifying CFB fly ash, so that the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material are solved, and the resource comprehensive utilization of CFB fly ash in the field of building materials is improved.
The invention provides a method for culturing Paenibacillus mucilaginosus LT1906, which comprises the following steps: inoculating Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 to a seed culture medium for seed culture to obtain a Paenibacillus mucilaginosus seed solution; inoculating the obtained Paenibacillus mucilaginosus seed liquid to a fermentation culture medium to obtain the Paenibacillus mucilaginosus LT1906 bacterial liquid. In the present invention, the seed culture medium preferably comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/L K2HPO4，0.1～0.2g/LMgSO4·7H2O，0.002～0.005g/L FeCl3，0.2～0.5g/L CaCO3And 0.2 to 0.5g/L (NH)4)2SO4(ii) a Further preferred are components comprising the following mass concentrations: 5g/L sucrose, 0.1g/LK2HPO4，0.1g/L MgSO4·7H2O，0.002g/LFeCl3， 0.2g/L CaCO3And 0.2g/L (NH)4)2SO4. In the invention, the pH of the seed culture medium is preferably 7.0-7.5, and more preferably 7.2. The culture medium formula provided by the invention provides an optimal nutritional condition for mass propagation of the strain, so as to promote the strain to rapidly propagate to obtain a bacterial liquid. In the invention, the temperature of the seed culture is preferably 30-35 ℃, and more preferably 30 ℃; the time for seed culture is preferably 24-48 h, and further preferably 36 h; the rotation speed of the seed culture is preferably 160-200 rpm, and more preferably 180 rpm. Under the specific seed culture condition, the invention ensures that the culture time of the strain reaching the maximum concentration is shortest, and greatly shortens the culture time of the strain. After the paenibacillus mucilaginosus seed liquid is obtained, the obtained paenibacillus mucilaginosus seed liquid is inoculated to a fermentation culture medium according to the inoculation amount of 5-10%, and is further preferably inoculated to 10% for fermentation culture, and the specific inoculation amount can balance the flora size and the sugar production capacity. In the invention, the fermentation medium comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/L K2HPO4， 0.1～0.2g/LMgSO4·7H2O，0.002～0.005g/L FeCl3And 0.2 to 0.5g/L of CaCO3(ii) a More preferably 5g/L sucrose, 0.1g/L K2HPO4，0.1g/L MgSO4·7H2O， 0.002g/LFeCl3And 0.2g/L CaCO3. In the present invention, the pH of the fermentation medium is preferably 7.0 to 7.5, and more preferably 7.2. The fermentation medium can promote the strain to produce sugar, and is the optimal nutrient condition for the strain to produce sugar. In the invention, the temperature of the fermentation culture is preferably 30-32 ℃, and more preferably 30 ℃; the fermentation culture time is preferably 24-60 h, and more preferably 36 h; the rotation speed of the fermentation culture is preferably180 to 200rpm, more preferably 180 rpm. The specific fermentation culture conditions of the invention can ensure that the culture time of the strain reaching the maximum sugar production concentration is shortest and the fermentation culture time is shortened.
The invention provides the application of Paenibacillus mucilaginosus LT1906 in the technical scheme in exciting circulating fluidized bed fly ash, which can improve the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material and improve the comprehensive resource utilization of the CFB fly ash in the field of building materials (such as pipeline and roadbed engineering backfill operation and coal mine goaf backfill treatment).
The invention provides a fly ash cementing material of a microorganism-excited circulating fluidized bed, which comprises the following raw materials: circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus LT1906 and vinegar residue leachate in the technical scheme. In the invention, the specific surface area of the fly ash cementing material of the microorganism-excited circulating fluidized bed is 600-720 m2/kg, more preferably 645 to 680m2Per kg; the activity index of the fly ash cementing material of the microbial excitation circulating fluidized bed is more than or equal to 60 percent, and the preferable activity index is 65 percent. After being excited by microorganisms, the fly ash cementing material of the microorganism-excited circulating fluidized bed provided by the invention has the advantages that the specific surface area and the activity index are obviously improved, the higher the specific surface area is, the larger the surface energy is, the higher the hydration reaction activity is, the more easily hydration reaction is generated to generate a large amount of hydration products, so that the density of hardened slurry is improved, and the strength activity index is also higher.
In the present invention, the mass ratio of the circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus (Paenibacillus mucinarginosus) LT1906 and the vinegar residue leachate in the above technical scheme is preferably 100: (9-27): (18-36), more preferably 100: (9-18): (27 to 36), more preferably 100: 9: 36; the invention further limits the dosage relation of the bacterial liquid, the vinegar residue leaching liquid and the fly ash to ensure that Ca is contained2+And the dissolution proportion of Si is optimal, so that the optimal reaction concentration is provided for the hydration reaction.
In the present invention, the recycle streamThe fluidized bed fly ash is solid waste generated by power generation of a circulating fluidized bed boiler, and the circulating fluidized bed fly ash preferably comprises the following components in percentage by mass: SiO 22≥35％，f-CaO≤4％，SO3Less than or equal to 3 percent, and the specific surface area is 330-400 m2Per kg, 80 mu m screen residue 15-20%; more preferably: SiO 2241.5％，f-CaO 3％， SO 32% of specific surface area 400m2Kg, 80 μm screen residue 15%.
In the invention, the bacterial concentration of the Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid is preferably 106～107one/mL, more preferably 2X 106Per mL; the viscosity of the bacterial liquid is preferably 2 to 15 mPas, and more preferably 6 mPas. In the present invention, the bacterial liquid preferably includes Paenibacillus mucilaginosus (Paenibacillus mucinagonosus) LT1906 bacterial liquid obtained by the culture method described in the above technical scheme. According to the invention, the specific concentration and viscosity of the bacterial liquid are selected to ensure the content of capsules in the bacterial liquid, and the capsules mainly contain extracellular polymers which are necessary conditions for bacteria to adhere to the surface of minerals to form a complex, so that the degradation of fly ash is promoted, and the dissolution of active ingredients such as active silicon is improved.
In the present invention, the preparation method of the vinegar residue leachate preferably comprises the following steps: mixing water and fresh vinegar residue according to the mass ratio (800-1000): 1, standing for 24-36 hours at 4-10 ℃, filtering to remove solid vinegar residue, and obtaining vinegar residue leachate. In the invention, the mass ratio of the water to the fresh vinegar residue is (800-1000): 1, more preferably 1000: 1, so that the acetic acid can be fully dissolved out; in the invention, the standing temperature is 4-10 ℃, and the further optimization is 8 ℃; the standing time is 24-26 h, and more preferably 24 h. In the invention, the total acid content in the obtained vinegar residue leaching solution is preferably more than or equal to 6 percent, and more preferably 8.9 percent; the content of acetic acid is not less than 5%, and more preferably 6.5%. The vinasse leaching solution can improve Ca2+The dissolution rate of the water-soluble calcium salt is increased, and more hydration reactant Ca is provided2+With colloidal budThe bacillus has the combined action, so that the generation of C-S-H gel is accelerated, and the early self-gelling strength is improved; meanwhile, the vinasse leaching solution fully utilizes vinasse wastes, realizes recycling of the vinasse wastes, not only reduces the production cost, but also can reduce the pollution of the vinasse wastes to the environment.
The microbial-excited circulating fluidized bed fly ash cementing material provided by the invention overcomes the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material, fully excites the potential pozzolanic activity and self-gelling property of the CFB fly ash, and improves the recycling comprehensive utilization of the CFB fly ash in the field of building materials.
The invention provides a preparation method of a microorganism-excited circulating fluidized bed fly ash cementing material in the technical scheme, which comprises the following steps: and (3) mixing the circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus LT1906 and the vinegar residue leachate to obtain the microorganism-excited circulating fluidized bed fly ash cementing material. The preparation method of the fly ash cementing material of the microbial-activated circulating fluidized bed provided by the invention has the advantages of simple process, low energy consumption and no secondary pollution, and the prepared fly ash cementing material of the circulating fluidized bed solves the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material.
The invention provides the application of the microbial-excited circulating fluidized bed fly ash cementing material in the technical scheme or the application of the microbial-excited circulating fluidized bed fly ash cementing material obtained by the preparation method in the technical scheme in the field of building materials. In the present invention, the field of building materials is preferably low strength cementitious filling materials. In the invention, the low-strength gelled filling material is preferably applied to pipeline and roadbed engineering backfill operation and coal mine goaf backfill treatment.
In order to further illustrate the present invention, the following examples are provided to describe in detail a Paenibacillus mucilaginosus and a cultivation method and application thereof, a microorganism-excited circulating fluidized bed fly ash cementing material and a preparation method and application thereof, which should not be construed as limiting the scope of the present invention.
Example 1
Fly ash cementing material for microorganism-excited circulating fluidized bed
1. Obtaining a Paenibacillus mucilaginosus (Paenibacillus muciniginosus) LT1906 bacterial liquid
(1) Inoculating a single colony of the paenibacillus mucilaginosus to a seed culture medium for seed culture, wherein the paenibacillus mucilaginosus is the paenibacillus mucilaginosus (Paenii bacillus mucilaginosus) LT1906, and the preservation number is CGMCC No. 21337; the seed medium consisted of the following concentrations of components: 5g/L sucrose, 0.1g/L K2HPO4，0.1g/ L MgSO4·7H2O，0.002g/L FeCl3，0.2g/L CaCO3And 0.2g/L (NH)4)2SO4And the pH value of the seed culture medium is 7.2, and the seed culture medium is shake-cultured for 36 hours at the temperature of 30 ℃ to obtain the paenibacillus mucilaginosus seed solution.
(2) Transferring the obtained paenibacillus mucilaginosus seed liquid to a fermentation culture medium with the inoculation amount of 10%, wherein the fermentation culture medium comprises the following components in concentration: 5g/L sucrose, 0.1g/L K2HPO4，0.1g/L MgSO4·7H2O，0.002g/L FeCl3And 0.2g/L CaCO3The pH value of the fermentation medium is 7.2, and the fermentation medium is shake-cultured for 36h at the temperature of 30 ℃ until the thallus concentration is 2 multiplied by 106The strain per mL and the viscosity of the strain are 6 mPas, and a paenibacillus mucilaginosus LT1906 bacterial solution is obtained.
2. Mixing water and fresh vinegar residue according to a mass ratio of 1000: 1, uniformly mixing, standing for 24 hours at the temperature of 8 ℃, and filtering to remove solid vinegar residues to obtain a vinegar residue leachate, wherein the total acid content of the vinegar residue leachate is 8.9 percent, and the acetic acid content is 6.5 percent.
3. Mixing circulating fluidized bed fly ash, Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid and vinegar residue leachate according to the mass ratio of 100: 9: 36, wherein SiO in the fly ash of the circulating fluidized bed is uniformly mixed241.5% of f-CaO, 3% of SO32% of the total amount of the dispersion, and a specific surface area of 400% m2Per kg, 80 μm screen residue 15%. After mixing, the preparation is obtainedThe microorganism excites the fly ash cementing material of the circulating fluidized bed.
Example 2
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: the mass ratio of the circulating fluidized bed fly ash to the Paenibacillus mucilaginosus LT1906 bacterial liquid to the vinegar residue leachate is 100: 18: 27.
example 3
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: the seed culture time is 48h, the fermentation culture time is 24h, and the thallus concentration is 5 x 106The viscosity of the obtained product is 12 mPas.
Example 4
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: the mass ratio of the circulating fluidized bed fly ash to the Paenibacillus mucilaginosus LT1906 bacterial liquid to the vinegar residue leachate is 100: 9: 20.
example 5
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: water and fresh vinegar residue according to the mass ratio of 800: 1, uniformly mixing, standing at 8 ℃ for 36 hours, and filtering to remove solid vinegar residue to obtain vinegar residue leachate, wherein the total acid content of the vinegar residue leachate is 8.2%, and the acetic acid content is 5.65%.
Comparative example 1
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: paenibacillus mucilaginosus LT1906 is replaced by Bacillus mucilaginosus AS1.232 (available from Shanghai township limited Biotech).
Comparative example 2
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: treating the circulating fluidized bed fly ash by only using a Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid, wherein the mass ratio of the circulating fluidized bed fly ash to the Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid is 100: 9.
comparative example 3
The preparation method of the fly ash cementing material of the vinegar residue leaching solution circulating fluidized bed is the same as that of the fly ash cementing material in example 1, and is characterized in that: treating the fly ash of the circulating fluidized bed only by using vinegar residue leachate, wherein the mass ratio of the fly ash of the circulating fluidized bed to the vinegar residue leachate is 100: 36.
comparative example 4
The preparation method of the fly ash cementing material of the microorganism-excited circulating fluidized bed is the same as that of the example 1, and is characterized in that: replacing the vinegar residue leachate with an acetic acid aqueous solution with the volume percentage concentration of 5%.
Comparative example 5
The preparation method of the fly ash cementing material of the circulating fluidized bed is the same as that of the example 1, and is different from the following points: and replacing water with the paenibacillus mucilaginosus LT1906 bacterial liquid and the vinegar residue leaching liquid.
Comparative example 6
The preparation method of the alkali-activated fly ash cementing material for the circulating fluidized bed is the same as that in example 1, and is characterized in that: and replacing the paenibacillus mucilaginosus LT1906 bacterial liquid and the vinegar residue leachate with NaOH aqueous solution to ensure that the final concentration of NaOH is 2M.
Example 6
The cement mortar performance of different cementing materials obtained in examples 1-5 and comparative examples 1-4, untreated circulating fluidized bed fly ash and I-III grade fly ash are compared, water requirements, 28d activity indexes and specific surface areas of different cementing materials are inspected, and detection results are shown in table 1.
Wherein, the fluidity of contrast mortar (250 g of cement, 750g of standard sand and 125mL of water addition) and test mortar (175 g of cement, X g of different cementing materials obtained in the above examples and comparative examples or 75g of untreated circulating fluidized bed fly ash/I-III class fly ash and 750g of standard sand) is measured according to GB/T2419, and the water requirement of the fly ash is determined according to the ratio of the water addition when the fluidity of the test mortar reaches 130 mm-140 mm to the water addition 125mL of the contrast mortar. The amounts of the different gelling materials obtained in the above examples and comparative examples in the test mortar were calculated as follows, X being 75g (9+36+100)/100 in examples 1, 3 and 5, 75g (18+27+100)/100 in example 2 and 75g (9+20+100)/100 in example 4; for the water addition amount of the test sand, the total water addition amount is (the mass of the bacterial liquid-the dry weight of the bacteria-the mass of the components of the culture medium) + (the mass of the vinegar residue leaching solution-the mass of the total acid) + the actual water addition amount in the water demand test.
Activity index the compression strength of a control mortar (450 g cement, 1350g standard sand, 225ml water) and a test mortar (315 g cement, X g different cements obtained in the above examples and comparative examples or untreated circulating fluidized bed fly ash/grade I-III fly ash 135g standard sand 1350g water) 28d were determined according to the test method of GB/T17671-1999, and the activity index of the test mortar was determined as the ratio of the compression strength of the two. For the different binders obtained in the above examples and comparative examples in the test mortar, X135 g (9+36+100)/100 in examples 1, 3 and 5, X135 g (18+27+100)/100 in example 2 and X135 g (9+20+100)/100 in example 4; for the different gelled materials obtained in the above examples and comparative examples in the test mortar, the actual water addition amount in the activity index test was 225mL × 1g/mL- (bacterial liquid amount-bacterial dry weight-medium component amount) - (vinegar residue leachate amount-total acid amount).
TABLE 1 results of performance test of cement mortar by different cementing materials
From the results in table 1, it can be seen that the cementing materials of the examples of the present invention have slightly different specific surface areas, water demand ratios and 28d activity indexes compared with those of class i-iii fly ash, but are significantly superior to those of the comparative examples and untreated circulating fluidized bed fly ash, and show good application effects, after the circulating fluidized bed fly ash is modified by paenibacillus mucilaginosus LT1906 according to the method of the present invention, the particle morphology and pore structure are significantly improved, and the adverse effects of water demand and workability are eliminated to a certain extent.
The different gelled materials obtained in examples 1-5 and comparative examples 1-4, untreated circulating fluidized bed fly ash and class I-III fly ash were used for stabilizing silt, wherein 200g of silt, 145g of untreated circulating fluidized bed fly ash/class I-III fly ash or Xg of the different gelled materials obtained in the above examples and comparative examples, and 10g of water were mixed uniformly, filled into a 40 x 40mm mold, molded by vibration, and subjected to standard maintenance, and the conditions of stabilizing the strength of the silt in each of treatment groups 3d, 7d and 28d were examined. For the amounts of different gelling materials obtained in the above examples and comparative examples, X145 g (9+36+100)/100 for examples 1, 3 and 5, X145 g (18+27+100)/100 for example 2, and X145 g (9+20+100)/100 for example 4; for the different gelled materials obtained in the above examples and comparative examples, the actual water addition amount was 10g- (bacteria liquid amount-bacteria dry weight-medium component amount) - (vinegar residue leachate amount-total acid amount). The detection results are shown in Table 2; SEM pictures of the cement of example 1 used to stabilize different age hydrates of silt are shown in FIG. 2.
TABLE 2 Strength results after stabilization of silt soil by different treatment groups
From the results in table 2, it can be seen that the compressive strength of the silt soil of the cement material of the embodiment of the present invention after early stabilization is significantly increased, and the compressive strength of the silt soil is continuously increased with the extension of the hydration period. On one hand, active silicon-aluminum components dissolved out by the bacterial liquid are gradually increased, and on the other hand, the bacterial liquid acts on the fly ash to gradually increase the specific surface area, so that the hydration reaction activity is enhanced, more hydration products are generated, and the structure is more compact.
FIG. 2 is an SEM photograph of the cement of example 1 used to stabilize different ages of hydrated products of silt, where A is age 3d, B is age 7d, and C is age 28 d. As is clear from the results shown in FIG. 2, at the age of 3d, acicular ettringite and flocculent C-S-H were formed, and a large gap was formed between the hydrated products; when the mixture is aged 7 days, a large amount of ettringite and C-S-H are generated along with the progress of hydration reaction, and the connection among hydration products is relatively tight; when the calcium carbonate is aged for 28 days, the needle-shaped ettringite and the flocculent C-S-H are gelled and connected more densely, and are mutually cemented to form a three-dimensional network structure, which shows that the hydration degree and the crystallization degree of a hydration product are higher and higher along with the extension of the age, the crystal particles are obviously increased, and the strength of a filling body is correspondingly enhanced.
Example 7
XRD scanning (Haoyuan DX-2700BH multifunctional diffractometer) is carried out on the microorganism excited circulating fluidized bed fly ash cementing material obtained in example 1 and the circulating fluidized bed fly ash obtained in comparative example 5 and untreated circulating fluidized bed fly ash, the influence of different treatments on the crystal structure of the circulating fluidized bed fly ash material is analyzed, and the detection result is shown in figure 3.
FIG. 3 is an XRD spectrum of each treatment group, wherein the circulating fluidized bed fly ash after bacterial liquid treatment is the microbial-activated circulating fluidized bed fly ash binding material obtained in example 1, and the circulating fluidized bed fly ash after water treatment is the circulating fluidized bed fly ash binding material obtained in comparative example 5. From the results of fig. 3, it can be seen that the position of the diffraction peak of the fly ash material of the circulating fluidized bed treated by the bacillus mucilaginosus bacterial liquid of the invention is not changed, which indicates that no crystal phase change is caused; but reduces the quartz (SiO)2) And anhydrite (II-CaSO)4) The intensity of diffraction peaks and the degeneracy and broadening of partial diffraction peaks show that the ordered structures of quartz and anhydrite crystals in partial circulating fluidized bed fly ash are destroyed after the bacillus mucilaginosus is modified, the lattice defects are increased, the reaction capacity is released, and the reaction activity is improved.
Example 8
The influence of the treatment methods of example 1, comparative example 5 and comparative example 6 on the dissolution rule of Si and Al in the circulating fluidized bed fly ash was examined, wherein the detection method of Si and Al is ICP-MS (Agilent 8900 inductively coupled plasma chromatograph). The results are shown in tables 3 and 4.
TABLE 3 influence of the treatment groups on Si elution (unit: mg/L)
| Time | Water (W) | 2MNaOH | Example 1 |
| 0.5d | 32.31 | 305.43 | 59.04 |
| 1d | 56.28 | 613.23 | 112.35 |
| 2d | 59.21 | 628.55 | 747.86 |
| 3d | 61.33 | 635.18 | 944.61 |
As can be seen from table 3, the maximum Si elution amount of the fly ash of the circulating fluidized bed in the bacillus mucilaginosus bacterial liquid of example 1 is greater than 2M NaOH; under the strong alkaline environment of 2M NaOH, Si reaches the highest dissolution amount at 1d and then basically remains unchanged; in the Bacillus mucilaginosus bacterial liquid environment of example 1, the elution amount of Si gradually increased and reached the maximum at 3 d.
TABLE 4 influence of the treatment groups on Al elution (unit: mg/L)
As can be seen from Table 4, the amount of Al eluted from the circulating fluidized bed fly ash in the Bacillus mucilaginosus bacterial liquid of example 1 was slightly higher than that in water, and was much lower than that in 2M NaOH.
In conclusion, after the circulating fluidized bed fly ash is activated by the bacillus mucilaginosus bacterial liquid, the surface structure and the internal crystal structure of the particles are eroded, broken bonds are increased, and SiO is generated2Is easier to dissolve out, and improves the total dissolution amount, thereby improving the reaction activity.
The results of the above embodiments show that when Paenibacillus mucilaginosus (Paenibacillus muciniginosus) LT1906 provided by the invention is used for modifying CFB fly ash, the problems of large water demand, low early strength and the like of CFB fly ash as a cementing material are effectively improved, the preparation process of the prepared microorganism-excited circulating fluidized bed fly ash cementing material is simple, the energy consumption is low, no secondary pollution is generated, and the resource comprehensive utilization of CFB fly ash in the field of building materials is improved.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 is characterized by having a preservation number of CGMCC No. 21337.
2. The method for culturing Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 according to claim 1, which comprises the following steps: inoculating Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 to a seed culture medium for seed culture to obtain a Paenibacillus mucilaginosus seed solution; inoculating the obtained Paenibacillus mucilaginosus seed liquid to a fermentation culture medium to obtain a Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid;
the seed culture medium comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/LK2HPO4，0.1～0.2g/LMgSO4·7H2O，0.002～0.005g/L FeCl3，0.2～0.5g/L CaCO3And 0.2 to 0.5g/L (NH)4)2SO4The pH value of the seed culture medium is 7.0-7.5; the temperature of the seed culture is 30-35 ℃, the time of the seed culture is 24-48 h, and the rotation speed of the seed culture is 160-200 rpm;
the fermentation medium comprises the following components in mass concentration: 5-10 g/L sucrose, 0.1-0.2 g/L K2HPO4，0.1～0.2g/L MgSO4·7H2O，0.002～0.005g/L FeCl3And 0.2 to 0.5g/L of CaCO3The pH value of the fermentation medium is 7.0-7.5, the inoculation amount of the fermentation culture is 5% -10%, the temperature is 30-32 ℃, the rotation speed of the fermentation culture is 160-200 rpm, and the time is 24-60 hours.
3. Use of Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 as defined in claim 1 for exciting circulating fluidized bed fly ash.
4. A fly ash cementing material of a microorganism-excited circulating fluidized bed is characterized by comprising the following raw materials: circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus LT1906 and vinegar residue leachate of the Paenibacillus mucilaginosus LT 1.
5. The microbial-activated circulating fluidized bed fly ash cementing material according to claim 4, wherein the mass ratio of the circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus (Paenibacillus muciniaginosus) LT1906 of claim 1 and the vinegar residue leachate is 100: (9-27): (18-36).
6. The microbial-activated fly ash cementing material for the circulating fluidized bed according to claim 4, wherein the fly ash for the circulating fluidized bed is a solid waste generated by burning coal in a circulating fluidized bed boiler, and comprises the following components in percentage by mass: SiO 22≥35％，f-CaO≤4％，SO3Less than or equal to 3 percent, and the specific surface area of 330-400 m2And 80 mu m of screen residue is 15 to 20 percent per kg.
7. The microbial-excited circulating fluidized bed fly ash cementing material according to claim 4, wherein the bacterial concentration in the Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 bacterial liquid is 106～107The bacterial suspension has a viscosity of 2-15 mPas per mL.
8. The microbial-activated fly ash cementitious material for a circulating fluidized bed according to claim 4, wherein the preparation method of the vinegar residue leachate comprises the following steps: mixing water and fresh vinegar residue according to the mass ratio (800-1000): 1, standing for 24-36 hours at 4-10 ℃, and filtering to remove solid vinegar residue to obtain vinegar residue leachate.
9. The preparation method of the fly ash cementing material of the microbial-excited circulating fluidized bed according to any one of claims 4 to 8, which is characterized by comprising the following steps: mixing circulating fluidized bed fly ash, the bacterial liquid of Paenibacillus mucilaginosus (Paenibacillus mucilaginosus) LT1906 and vinegar residue leachate to obtain the microorganism-excited circulating fluidized bed fly ash cementing material.
10. The microbial-activated fly ash cementing material of a circulating fluidized bed according to any one of claims 4 to 8 or the microbial-activated fly ash cementing material of a circulating fluidized bed obtained by the preparation method according to claim 9 is applied to the field of building materials.
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Application publication date: 20210601 Assignee: Jiexiu Dehui Energy Co.,Ltd. Assignor: Taiyuan University of Technology Contract record no.: X2022140000008 Denomination of invention: A kind of colloidal bacillus, microbial activated circulating fluidized bed fly ash cementitious material and its method and Application Granted publication date: 20211015 License type: Common License Record date: 20220714 |