CN109320192A - A kind of modified filler of microorganism and preparation method - Google Patents

A kind of modified filler of microorganism and preparation method Download PDF

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Publication number
CN109320192A
CN109320192A CN201811314164.6A CN201811314164A CN109320192A CN 109320192 A CN109320192 A CN 109320192A CN 201811314164 A CN201811314164 A CN 201811314164A CN 109320192 A CN109320192 A CN 109320192A
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microorganism
culture
modified filler
solution
preparation
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张吉雄
李猛
郭仕婕
宋卫剑
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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Publication of CN109320192A publication Critical patent/CN109320192A/en
Priority to PCT/CN2019/092466 priority patent/WO2020093704A1/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00Compositions for artificial stone, not containing binders
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21FSAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F15/00Methods or devices for placing filling-up materials in underground workings
    • E21F15/005Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Mining & Mineral Resources (AREA)
  • Zoology (AREA)
  • Biotechnology (AREA)
  • Wood Science & Technology (AREA)
  • Genetics & Genomics (AREA)
  • Ceramic Engineering (AREA)
  • Biochemistry (AREA)
  • Virology (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Microbiology (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • General Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

The invention discloses a kind of modified fillers of microorganism and preparation method, the filler to be mainly made of Coal Gangue Structure material and cementing material.Wherein Coal Gangue Structure material is made of gangue and flyash according to the weight ratio of 40~45:1;Cementing material is made of selected bacillus culture solution, urea/calcium chloride mixed liquor the volume ratio of 1:9~12.The weight ratio of the Coal Gangue Structure material and cementing material is 5.6~7.2:1.Filler of the present invention, its microorganism induction mineralising reaction is mild, and remains to play a role after microorganism is dead, improves the intensity of filler, be conducive to the safe and efficient of filling mining, there is excellent environment friendly, durability and have good promotion prospect and application value.

Description

A kind of modified filler of microorganism and preparation method
Technical field
The invention belongs to coal mine filling production technique fields, and in particular to a kind of microorganism for underground filling is modified to fill Filling chock material and preparation method.
Background technique
In China, " under three " press coal amount huge, with the development of the social economy, these coal resources need to exploit.It is comprehensive The utilization of mechanization solid filling coal-mining technique greatly improves the recovery ratio for pressing coal " under three ", improves coal resources Utilization rate reduces subsidence, is a kind of environmental-friendly greenization recovery method, and have extensive engineer application, obtains Good society, economy and environmental benefit.But there are gap before traditional filler aggregate, gangue surface does not have Microbial reaction occurs, the supporting role of gangue could not be made full use of, best support effect is not achieved.And traditional Cement in cemented filling material can cause undesirable influence to underground water.And microorganism can by itself vital movement, Mineralization occurs between the surrounding medium of surrounding, and constantly accumulates, ultimately forms hard rock --- calcite, it will be loose Scattered gangue consolidation becomes the entirety with some strength.By the effect of microorganism, environment will not be caused to damage, simultaneously The strength and stability of filler can be improved.
Therefore, it is necessary to invent a kind of modified filler of microorganism, raising makes full use of gangue, to improve filling The intensity of material, while achieving the purpose that environmental-friendly.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides a kind of modified filling material of microorganism Material and preparation method, give full play to the interaction of microorganism and gangue, ensure that the intensity of the filler.
Technical solution: to achieve the above object, the technical solution adopted by the present invention are as follows:
The modified filler of a kind of microorganism applied to underground filling, by Coal Gangue Structure material and cementing material group At, in which:
Coal Gangue Structure material is made of gangue and flyash according to the weight ratio of 40~45:1;
Cementing material is made of bacillus culture solution, urea-calcium chloride mixed liquor according to the volume ratio of 1:9~12;
The weight ratio of the Coal Gangue Structure material and cementing material is 5.6~7.2:1.
Further, the Coal Gangue Structure material, gangue partial size is in 10mm or less.
Further, the preparation of the bacillus culture solution includes actication of culture process, seed culture process, fermentation Three steps of process, three steps are related to activation medium, seed culture medium, fermentation medium, dosage be respectively 20ml, 1L、1L。
Further, activation medium is LB solid slope culture medium, the activation for bacillus;
Seed culture medium is fluid nutrient medium, and the ingredient for including in every 1L has: 0.15g NH4Cl、0.02g KH2PO4、 0.2g KCl、0.15g MgCl2·6H2O、0.01g MnSO4·2H2O, 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO3And 5.8g Na2CO3, remainder is water, natural pH, for promoting the generation and enrichment of gemma;
Ingredient includes LB culture medium and 0.1g MnSO in the every 1L of fermentation medium4·2H2O is as inducer.
Further, the urea-calcium chloride mixed solution is urea and CaCl2The solution of composition is mixed, every 200ml is mixed Close includes 15g urea, 9g CaCl in solution2, remainder is water.
The preparation method of the modified filler of above-mentioned microorganism, comprising the following steps:
(1) activation of Bacillus: the bacillus single bacterium on inclined-plane is taken to fall within the fresh inclined-plane LB, 35 DEG C of constant temperature trainings Support 48h;
(2) culture of seed liquor: on the inclined-plane, picking single colonie is inoculated into liquid seed culture medium, revolving speed 200rpm, 35 DEG C of overnight incubations;
(3) preparation of fermentation liquid: being inoculated with by 7% and measure seed culture fluid shaking flask culture in fermentation culture, 150rpm, Bacterium solution is made in 35 DEG C of culture 72h;
(4) preparation of structural material: 10mm gangue below and flyash are chosen, is placed on test specimen model;
(5) perfusion of bacterium solution: using peristaltic pump to be pumped into cultured bacterium solution into test specimen model with the rate of 3ml/min, Infusion time is 3-5min;
(6) after step (5) completes 1h, urea-perfusion of mixed solution: is injected into test specimen model with 9ml/min rate Calcium chloride mixed solution, wherein being pumped into the time just to fill model as standard;
(7) after step (6) reacts 5h, fresh bacterium solution the circumfusion of bacterium solution: is pumped into test specimen model again;To abundant Continue to inject bacterium solution after reaction until it cannot reinject, wherein being pumped into the time just to fill model as standard;
(8) the modified filler sample of final cementing formation microorganism.
Further, moulded dimension used in step (4) is 7cm × 7cm × 7cm.
The utility model has the advantages that a kind of microorganism provided by the invention is modified filler and preparation method, compared with prior art, Have the advantage that the present invention takes full advantage of that microorganism growth response rate is controllable, microbial performance early period can optimize, ring The advantages that border pollution small, relative low price, the spontaneous microbial mineralization principle of nature is applied to the preparation of filler Process.And microorganism can be occurred mineralization with gangue surface, loose gangue is consolidated by the vital movement of itself Form for the entirety with some strength.The filler is conducive to the safe and efficient of filling mining, and it is solid to improve gangue etc. The utilization rate of body waste.By the effect of microorganism, the energy-saving and environmental protection and ecological performance of filler are promoted, are beneficial Innovation, has a good application prospect.
Detailed description of the invention
Fig. 1 microorganism is modified filler preparation method process flow chart;
Fig. 2 microorganism is modified filler preparation method process schematic representation;
Fig. 3 microorganism is modified filler section microscopical structure schematic diagram.
In figure: 1-screening gangue;2-choose strain;3-inoculation inclined-planes;4-optimum culture conditions;The training of 5-seeds Nutrient solution;6-fermentation cultures;7-mixed solutions;8-bacterium solutions;9-gangues enter mould;10-perfusion bacterium solutions;11-perfusions are mixed Close liquid;12-microorganisms are modified filler test specimen;13-gangues;14-mineralization product calcium carbonate;15-flyash.
Specific embodiment
The present invention is a kind of microorganism modified material applied to underground filling, and the filler is mainly by gangue Structural material and cementing material composition.Wherein Coal Gangue Structure material is by gangue and flyash according to the weight ratio of 40~45:1 Composition;Cementing material is made of selected bacillus culture solution, urea-calcium chloride mixed liquor the volume ratio of 1:9~12.Institute The weight ratio for stating Coal Gangue Structure material and cementing material is 5.6~7.2:1.Filler of the present invention, microorganism lure It is mild to lead mineralising reaction, and remains to play a role after microorganism is dead, improves the intensity of filler, is conducive to filling and opens That adopts is safe and efficient, has excellent environment friendly, durability and has good promotion prospect and application value.
The present invention will be further explained with reference to the accompanying drawings and examples.
Embodiment
The present invention is that a kind of modified filler of microorganism and preparation method are described as follows as shown in Figure 1, 2:
The modified filler of microorganism for underground filling, is mainly made of Coal Gangue Structure material and cementing material. Wherein Coal Gangue Structure material is made of gangue and flyash according to the weight ratio of 40~45:1;Cementing material is by selected bud Spore bacillus culture solution, urea/calcium chloride mixed liquor are made of the volume ratio of 1:9~12;The Coal Gangue Structure material and cementing The weight ratio of material is 5.6~7.2:1.
Used Coal Gangue Structure material, gangue partial size is in 10mm or less.Used cementing material includes bud The culture solution and urea-CaCl of spore bacillus2Aqueous solution.The preparation of the bacillus culture solution includes actication of culture mistake Three journey, seed culture process, fermentation process steps, three steps are related to activation medium, seed culture medium, fermented and cultured Base, dosage are respectively 20ml, 1L, 1L.
Activation medium is LB solid slope culture medium, for the activation of bacillus, volume 20ml.Seed culture medium For fluid nutrient medium, the ingredient for including in every 1L has: 0.15g NH4Cl、0.02g KH2PO4、0.2g KCl、0.15g MgCl2·6H2O、0.01g MnSO4·2H2O, 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO3And 5.8g Na2CO3, remainder is water, natural pH, for promoting the generation and enrichment of gemma.The ingredient for including in the every 1L of fermentation medium has LB Culture medium and 0.1g MnSO4·2H2O is as inducer.
The ingredient for including in the every 200ml of mixed solution has urea 15g, CaCl29g, remainder are water.Effect is to provide Ca2 +, cause microbial mineralization.
The preparation method of the modified filler of microorganism is as shown in Figure 2, wherein 1- screens gangue;2- chooses strain;3- It is inoculated with inclined-plane;4- optimum culture condition;5- seed culture fluid;6- fermentation culture;7- mixed solution;8- bacterium solution;9- gangue Enter mould;Bacterium solution is perfused in 10-;Mixed liquor is perfused in 11-;12- microorganism is modified filler test specimen.Specifically includes the following steps:
(1) activation of Bacillus: the bacillus single bacterium on inclined-plane is taken to fall within the fresh inclined-plane LB, 35 DEG C of constant temperature trainings Support 48h;
(2) culture of seed liquor: on the inclined-plane, picking single colonie is inoculated into liquid seed culture medium, revolving speed 200rpm, 35 DEG C of overnight incubations;
(3) preparation of fermentation liquid: being inoculated with by 7% and measure seed culture fluid shaking flask culture in fermentation culture, 150rpm, Bacterium solution is made in 35 DEG C of culture 72h;
(4) preparation of structural material: choosing 10mm gangue below and flyash is placed on test specimen model;
(5) perfusion of bacterium solution: using peristaltic pump to be pumped into cultured bacterium solution into test specimen model with the rate of 3ml/min, 3-5min is perfused;
(6) perfusion of mixed solution.After step (5) completes 1h, urea-is injected into test specimen model with 9ml/min rate Calcium chloride mixed solution;The time is wherein pumped into just to fill model as standard.
(7) circumfusion of bacterium solution: after step (6) reacts 5h, fresh bacterium solution is pumped into test specimen model again, to abundant Continue to inject bacterium solution after reaction until it cannot reinject;The time is wherein pumped into just to fill model as standard.
(8) the modified filler sample of microorganism is formed after final cementing 8 times.
Moulded dimension used above is 7cm × 7cm × 7cm.
As shown in figure 3, resulting product is prepared for the present invention, since microorganism is attached to 15 table of gangue 13 and flyash Face, therefore mineralization product calcium carbonate 14 is also generated in same position.Bacillus nutrients in bacterium solution to be pumped into after about 7 days Matter is depleted, and bacillus can die off, while leaving mineralization product calcium carbonate.By the circumfusion of bacterium solution, mine Changing product can be combined together, and gangue and flyash are adhered into an entirety.The resistance to compression of traditional coal waste filling material is light Degree is 2.0MPa or so, and the modified filler of the novel microbial as made from the innovative approach, compression strength obviously mention Height reaches 2.5MPa.Entire reaction carries out at room temperature, and 50 DEG C or less can occur the reaction, and are not accompanied by and significantly put Hot endothermic process.This innovative approach filling effect more preferably, improves the safety coefficient of shaft production, used the cost of material is low It is honest and clean, it reacts pollution-free, is effectively utilized the solid waste such as gangue, achieved the purpose that protect environment, there is good push away Wide prospect and application value.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (7)

1. a kind of modified filler of microorganism applied to underground filling, it is characterised in that: by Coal Gangue Structure material and glue Tie material composition, in which:
Coal Gangue Structure material is made of gangue and flyash according to the weight ratio of 40~45:1;
Cementing material is made of bacillus culture solution, urea-calcium chloride mixed liquor according to the volume ratio of 1:9~12;
The weight ratio of the Coal Gangue Structure material and cementing material is 5.6~7.2:1.
2. the modified filler of microorganism according to claim 1, it is characterised in that: the Coal Gangue Structure material, Its gangue partial size is in 10mm or less.
3. the modified filler of microorganism according to claim 1, it is characterised in that: the bacillus culture solution Preparation include actication of culture process, three seed culture process, fermentation process steps, three steps be related to activation medium, Seed culture medium, fermentation medium, dosage are respectively 20ml, 1L, 1L.
4. the modified filler of microorganism according to claim 3, it is characterised in that:
Activation medium is LB solid slope culture medium, the activation for bacillus;
Seed culture medium is fluid nutrient medium, and the ingredient for including in every 1L has: 0.15g NH4Cl、0.02g KH2PO4、0.2g KCl、0.15g MgCl2·6H2O、0.01g MnSO4·2H2O, 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO3And 5.8g Na2CO3, remainder is water, natural pH, for promoting the generation and enrichment of gemma;
Ingredient includes LB culture medium and 0.1g MnSO in the every 1L of fermentation medium4·2H2O is as inducer.
5. the modified filler of microorganism according to claim 1, it is characterised in that: the urea-calcium chloride mixing is molten Liquid is urea and CaCl2The solution of composition is mixed, includes 15g urea, 9g CaCl in every 200ml mixed solution2, remainder is water.
6. the preparation method of the modified filler of any microorganism according to claim 1~5, it is characterised in that: including Following steps:
(1) activation of Bacillus: the bacillus single bacterium on inclined-plane is taken to fall within the fresh inclined-plane LB, 35 DEG C of constant temperature incubations 48h;
(2) culture of seed liquor: on the inclined-plane, picking single colonie is inoculated into liquid seed culture medium, revolving speed 200rpm, and 35 DEG C Overnight incubation;
(3) preparation of fermentation liquid: being inoculated with by 7% and measure seed culture fluid shaking flask culture in fermentation culture, 150rpm, and 35 DEG C 72h is cultivated, bacterium solution is made;
(4) preparation of structural material: 10mm gangue below and flyash are chosen, is placed on test specimen model;
(5) perfusion of bacterium solution: using peristaltic pump to be pumped into cultured bacterium solution into test specimen model with the rate of 3ml/min, perfusion Time is 3-5min;
(6) after step (5) completes 1h, urea-chlorination the perfusion of mixed solution: is injected into test specimen model with 9ml/min rate Calcium mixed solution, wherein being pumped into the time just to fill model as standard;
(7) after step (6) reacts 5h, fresh bacterium solution the circumfusion of bacterium solution: is pumped into test specimen model again;To sufficiently react After continue inject bacterium solution until it cannot reinject, wherein being pumped into the time just to fill model as standard;
(8) the modified filler sample of final cementing formation microorganism.
7. the preparation method of the modified filler of microorganism according to claim 6, it is characterised in that: step (4) is used Moulded dimension be 7cm × 7cm × 7cm.
CN201811314164.6A 2018-11-06 2018-11-06 A kind of modified filler of microorganism and preparation method Pending CN109320192A (en)

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CN110513111A (en) * 2019-08-14 2019-11-29 中国矿业大学(北京) A kind of cementing lane formula filling coal mining method of separation of solid and liquid filling type microorganism
WO2020093704A1 (en) * 2018-11-06 2020-05-14 中国矿业大学 Microbial modification filling material and preparation method
CN111153650A (en) * 2020-01-08 2020-05-15 太原理工大学 MICP technology-based mining plugging material
CN111377627A (en) * 2020-02-18 2020-07-07 温州大学 Method for reinforcing residual soil by novel microbial inorganic cementing material and spraying equipment thereof
CN111912684A (en) * 2020-08-10 2020-11-10 中国矿业大学 Preparation system of mine microbial mineralization filling material
CN111978026A (en) * 2020-09-04 2020-11-24 中国矿业大学(北京) Mineralized and sealed CO2Mining microbial cementing filling material and preparation method thereof
CN113185170A (en) * 2021-03-31 2021-07-30 西安交通大学 Method for modifying coal gangue aggregate based on microbial induction technology
CN114751685A (en) * 2022-05-11 2022-07-15 辽宁工程技术大学 MICP principle-based ecological solid carbon filling material and preparation method thereof
CN115093167A (en) * 2022-06-21 2022-09-23 宁夏大学 Method for preparing roadbed by utilizing solid waste in microorganism mineralization and cementation industry

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WO2020093704A1 (en) * 2018-11-06 2020-05-14 中国矿业大学 Microbial modification filling material and preparation method
CN110513111A (en) * 2019-08-14 2019-11-29 中国矿业大学(北京) A kind of cementing lane formula filling coal mining method of separation of solid and liquid filling type microorganism
CN111153650A (en) * 2020-01-08 2020-05-15 太原理工大学 MICP technology-based mining plugging material
CN111377627A (en) * 2020-02-18 2020-07-07 温州大学 Method for reinforcing residual soil by novel microbial inorganic cementing material and spraying equipment thereof
CN111912684A (en) * 2020-08-10 2020-11-10 中国矿业大学 Preparation system of mine microbial mineralization filling material
CN111978026A (en) * 2020-09-04 2020-11-24 中国矿业大学(北京) Mineralized and sealed CO2Mining microbial cementing filling material and preparation method thereof
CN111978026B (en) * 2020-09-04 2021-08-27 中国矿业大学(北京) Mineralized and sealed CO2Mining microbial cementing filling material and preparation method thereof
CN113185170A (en) * 2021-03-31 2021-07-30 西安交通大学 Method for modifying coal gangue aggregate based on microbial induction technology
CN113185170B (en) * 2021-03-31 2023-04-25 西安交通大学 Method for modifying gangue aggregate based on microbial induction technology
CN114751685A (en) * 2022-05-11 2022-07-15 辽宁工程技术大学 MICP principle-based ecological solid carbon filling material and preparation method thereof
CN115093167A (en) * 2022-06-21 2022-09-23 宁夏大学 Method for preparing roadbed by utilizing solid waste in microorganism mineralization and cementation industry

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