WO2020093704A1 - Microbial modification filling material and preparation method - Google Patents

Microbial modification filling material and preparation method Download PDF

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WO2020093704A1
WO2020093704A1 PCT/CN2019/092466 CN2019092466W WO2020093704A1 WO 2020093704 A1 WO2020093704 A1 WO 2020093704A1 CN 2019092466 W CN2019092466 W CN 2019092466W WO 2020093704 A1 WO2020093704 A1 WO 2020093704A1
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coal gangue
filling material
medium
microbial
solution
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PCT/CN2019/092466
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Chinese (zh)
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张吉雄
李猛
郭仕婕
宋卫剑
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中国矿业大学
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, 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
    • C12N1/20—Bacteria; Culture media therefor
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F15/00—Methods or devices for placing filling-up materials in underground workings
    • E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • the invention belongs to the technical field of coal mine filling and mining, and in particular relates to a microbial modified filling material for underground filling and a preparation method.
  • Microorganisms through their own life activities, can undergo mineralization with the surrounding environmental media and continue to accumulate, eventually forming a hard rock-calcite, consolidating loose coal gangue into a whole with a certain strength. Through the action of microorganisms, it will not cause damage to the environment, and at the same time can improve the strength and stability of the filling material.
  • the present invention provides a microbial modified filling material and preparation method, which fully exerts the interaction of microorganisms and coal gangue and ensures the strength of the filling material.
  • a microbial modified filling material used for underground filling is composed of coal gangue structure material and cementing material, among which:
  • Coal gangue structural material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1;
  • the cementing material is composed of Bacillus culture solution and urea-calcium chloride mixture according to the volume ratio of 1: 9 ⁇ 12;
  • the weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
  • the particle size of the gangue is below 10 mm.
  • the preparation of the Bacillus culture solution includes three steps: a bacterial species activation process, a seed culture process, and a fermentation process.
  • the three steps involve an activation medium, a seed medium, and a fermentation medium, and the dosage is 20 ml, respectively. , 1L, 1L.
  • the activation medium is an LB solid slant medium used for the activation of Bacillus
  • the seed medium is a liquid medium, and the components contained in each 1L are: 0.15g NH 4 Cl, 0.02g KH 2 PO 4 , 0.2g KCl, 0.15g MgCl 2 ⁇ 6H 2 O, 0.01g MnSO 4 ⁇ 2H 2 O , 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO 3 and 5.8g Na 2 CO 3 , the rest is water, natural pH, used to promote the formation and enrichment of spores;
  • the components of the fermentation medium per liter include LB medium and 0.1 g MnSO 4 ⁇ 2H 2 O as inducers.
  • the mixed urea-calcium chloride solution is a solution composed of urea and CaCl 2 , and each 200 ml of the mixed solution includes 15 g of urea and 9 g of CaCl 2 , and the rest is water.
  • the preparation method of the above microbial modified filling material includes the following steps:
  • Perfusion of bacterial solution a peristaltic pump is used to pump the cultured bacterial solution into the specimen model at a rate of 3ml / min, and the perfusion time is 3-5min;
  • step (5) Perfusion of mixed solution: After step (5) is completed for 1 h, the urea-calcium chloride mixed solution is injected into the specimen model at a rate of 9 ml / min, where the pumping time is based on just filling the model;
  • Circulating perfusion of bacterial solution After reacting for 5 hours in step (6), re-pump fresh bacterial solution into the specimen model; after full reaction, continue to inject bacterial solution until it can no longer be injected.
  • Full model is standard;
  • the size of the model used in step (4) is 7 cm ⁇ 7 cm ⁇ 7 cm.
  • a microbial modified filling material and preparation method provided by the present invention have the following advantages: the present invention fully utilizes the microbial growth reaction rate can be adjusted, the early stage microbial performance can be optimized, and the environmental pollution is small , The relatively low price and other advantages, the principle of spontaneous microbial mineralization in nature is applied to the preparation process of filling materials. And the microbes can mineralize with the surface of coal gangue through their own life activities, and consolidate the loose coal gangue into a whole with a certain strength.
  • the filling material is conducive to the safe and efficient filling and mining, and improves the utilization rate of solid waste such as coal gangue. Through the action of microorganisms, improving the energy-saving, environmental protection and ecological performance of filling materials is a beneficial innovation and has good application prospects.
  • Figure 1 Process flow chart of preparation method of microbial modified filling material
  • Figure 2 Schematic diagram of the preparation method of microbial modified filling material
  • Figure 3 Schematic diagram of the microstructure of the cross-section of the microbial modified filling material.
  • the invention is a microbial modified material used for downhole filling.
  • the filling material is mainly composed of coal gangue structure material and cement material.
  • the coal gangue structure material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1;
  • the cementing material is composed of the selected Bacillus culture solution and the urea-calcium chloride mixed solution is a volume ratio of 1: 9 to 12 .
  • the weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
  • the filling material of the present invention has a mild mineralization reaction induced by microorganisms, and can still play a role after the death of microorganisms, which improves the strength of the filling material, is beneficial to the safety and efficiency of filling and mining, and has excellent environmental friendliness, durability and Has a good promotion prospects and application significance.
  • the present invention is a microbial modified filling material and preparation method, as shown in Figures 1 and 2 and explained as follows:
  • the microbial modified filling material used for downhole filling is mainly composed of coal gangue structure material and cementing material.
  • the coal gangue structure material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1;
  • the cementing material is composed of the selected Bacillus culture solution and the urea / calcium chloride mixed solution is a volume ratio of 1: 9 to 12 ;
  • the weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
  • the gangue structure material used has a gangue particle size of 10 mm or less.
  • the cementing material used includes a culture solution of Bacillus and an aqueous solution of urea-CaCl 2 .
  • the preparation of the Bacillus culture solution includes three steps: a bacterial species activation process, a seed culture process, and a fermentation process. 1L.
  • the activation medium is an LB solid slant medium used for the activation of Bacillus, with a volume of 20 ml.
  • the seed medium is a liquid medium, and the components contained in each 1L are: 0.15g NH 4 Cl, 0.02g KH 2 PO 4 , 0.2g KCl, 0.15g MgCl 2 ⁇ 6H 2 O, 0.01g MnSO 4 ⁇ 2H 2 O , 0.2g yeast extract, 4.28 g trisodium citrate, 3.5g NaHCO 3, and 5.8g Na 2 CO 3, the remainder being water, the pH naturally, for promoting spore formation and enrichment.
  • the components contained in the fermentation medium per 1 L include LB medium and 0.1 g MnSO 4 ⁇ 2H 2 O as inducers.
  • Each 200ml of the mixed solution contains 15g of urea, 9g of CaCl 2 and the rest is water. The role is to provide Ca 2+ and trigger microbial mineralization.
  • Fig. 2 The preparation method of the microbial modified filling material is shown in Fig. 2, in which, 1- screening coal gangue; 2- selecting strains; 3- inoculation slope; 4- optimizing culture conditions; 5- seed culture liquid; 6- fermentation culture liquid ; 7- mixed solution; 8- bacterial liquid; 9- coal gangue into the mold; 10- perfusion bacterial liquid; 11- perfusion mixed liquid; 12- microbial modified filling material test piece. It includes the following steps:
  • Perfusion of bacterial solution a peristaltic pump is used to pump the cultured bacterial solution into the specimen model at a rate of 3ml / min, and perfusion is carried out for 3-5min;
  • step (6) Perfusion of mixed solution. After step (5) is completed for 1 h, the urea-calcium chloride mixed solution is injected into the specimen model at a rate of 9 ml / min; where the pumping time is based on just filling the model.
  • Circulating perfusion of bacterial solution After reacting for 5 hours in step (6), re-pump fresh bacterial solution into the specimen model, and continue to inject the bacterial solution after the full reaction until it can no longer be injected; where the pumping time is just to fill Full model is standard.
  • the size of the model used above is 7cm ⁇ 7cm ⁇ 7cm.
  • the mineralized product calcium carbonate 14 is also generated at the same position. After about 7 days, the Bacillus nutrients in the bacterial liquid to be pumped are exhausted, and the Bacillus will die one after another, while the mineralized product calcium carbonate is left. After the circulation of the bacterial liquid, the mineralized products will be combined together, and the coal gangue and fly ash will be adhered into a whole.
  • the compressive lightness of traditional coal gangue filling materials is about 2.0 MPa, and the compressive strength of the new microbial modified filling materials produced by this innovative method is significantly increased to 2.5 MPa.
  • the whole reaction is carried out at room temperature, and the reaction can occur below 50 ° C without obvious exothermic and endothermic processes.
  • This innovative method has better filling effect, improves the safety factor of mine production, the materials used are low in cost, the reaction is non-polluting, and the solid wastes such as coal gangue are effectively used to achieve the purpose of protecting the environment and has good promotion prospects and Value.

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Abstract

Disclosed are a microbial modification filling material and a preparation method, wherein the filling material is mainly composed of a coal gangue structural material and a cementitious material. The coal gangue structural material is mainly composed of coal gangue and fly ash in a weight ratio of 40-45 : 1; and the cementitious material is composed of a selected Bacillus culture solution and a urea/calcium chloride mixed liquid at a volume ratio of 1 : 9-12. The weight ratio of coal gangue structural material to cementitious material is 5.6-7.2 : 1. The filling material has a mild mineralized reaction induced by microorganisms, and can still play a role after microbial death, which improves filling material strength, facilitates safe and efficient filling and mining, is highly environmentally friendly and durable and has a good promotion prospect and application value.

Description

一种微生物改性充填材料及制备方法Microbial modified filling material and preparation method 技术领域Technical field
本发明属于煤矿充填开采技术领域，具体涉及一种用于井下充填的微生物改性充填材料及制备方法。The invention belongs to the technical field of coal mine filling and mining, and in particular relates to a microbial modified filling material for underground filling and a preparation method.
背景技术Background technique
在我国，“三下”压煤量巨大，随着社会经济的发展，这些煤炭资源亟需开采。综合机械化固体充填采煤技术的运用，极大地提高了“三下”压煤的采出率，提高了煤炭资源的利用率，降低了地表沉陷，是一种环境友好的绿色化开采方法，并有广泛的工程应用，取得了良好的社会、经济和环境效益。但是传统的充填材料骨料之前存在空隙，煤矸石表面没有发生微生物反应，没能充分利用煤矸石的支撑作用，达不到最好的支撑效果。并且在传统的胶结充填材料中的水泥会对地下水造成不良的影响。而微生物可以通过自身的生命活动，与周围的环境介质之间发生矿化作用，并不断积累，最终形成坚硬的岩石——方解石，将松散的煤矸石固结成为带有一定强度的整体。通过微生物的作用，不会对环境造成损伤，同时可提高充填材料的强度和稳定性。In China, the amount of coal under "three strikes" is huge. With the development of social economy, these coal resources need to be mined urgently. The application of comprehensive mechanized solid filling coal mining technology has greatly improved the "three under" coal recovery rate, increased the utilization rate of coal resources, and reduced surface subsidence. It is an environmentally friendly green mining method, and It has a wide range of engineering applications and has achieved good social, economic and environmental benefits. However, there is a gap before the traditional filling material aggregate, no microbial reaction occurs on the surface of the coal gangue, the supporting effect of the coal gangue is not fully utilized, and the best supporting effect cannot be achieved. And the cement in the traditional cemented filling material will have an adverse effect on groundwater. Microorganisms, through their own life activities, can undergo mineralization with the surrounding environmental media and continue to accumulate, eventually forming a hard rock-calcite, consolidating loose coal gangue into a whole with a certain strength. Through the action of microorganisms, it will not cause damage to the environment, and at the same time can improve the strength and stability of the filling material.
因此，需要发明一种微生物改性充填材料，提高对煤矸石的充分利用，来改善充填材料的强度，同时达到环境友好的目的。Therefore, there is a need to invent a microbial modified filling material to improve the full utilization of coal gangue to improve the strength of the filling material and achieve the purpose of environmental friendliness.
发明内容Summary of the invention
发明目的：为了克服现有技术中存在的不足，本发明提供一种微生物改性充填材料及制备方法，充分发挥微生物与煤矸石的相互作用，保证了该充填材料的强度。Object of the invention: In order to overcome the shortcomings in the prior art, the present invention provides a microbial modified filling material and preparation method, which fully exerts the interaction of microorganisms and coal gangue and ensures the strength of the filling material.
技术方案：为实现上述目的，本发明采用的技术方案为：Technical solution: To achieve the above purpose, the technical solution adopted by the present invention is:
一种应用于井下充填的微生物改性充填材料，由煤矸石结构材料和胶结材料组成，其中：A microbial modified filling material used for underground filling is composed of coal gangue structure material and cementing material, among which:
煤矸石结构材料由煤矸石和粉煤灰按照40～45:1的重量比组成；Coal gangue structural material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1;
胶结材料由芽孢杆菌培养液、尿素-氯化钙混合液按照1:9～12的体积比组成；The cementing material is composed of Bacillus culture solution and urea-calcium chloride mixture according to the volume ratio of 1: 9 ～ 12;
所述煤矸石结构材料和胶结材料的重量比为5.6～7.2:1。The weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
进一步的，所述的煤矸石结构材料，其煤矸石粒径在10mm以下。Further, in the gangue structure material, the particle size of the gangue is below 10 mm.
进一步的，所述的芽孢杆菌培养液的制备包括菌种活化过程、种子培养过程、发酵过程三个步骤，该三个步骤涉及活化培养基、种子培养基、发酵培养基，其用量分别为 20ml、1L、1L。Further, the preparation of the Bacillus culture solution includes three steps: a bacterial species activation process, a seed culture process, and a fermentation process. The three steps involve an activation medium, a seed medium, and a fermentation medium, and the dosage is 20 ml, respectively. , 1L, 1L.
进一步的，活化培养基是LB固体斜面培养基，用于芽孢杆菌的活化；Further, the activation medium is an LB solid slant medium used for the activation of Bacillus;
种子培养基为液体培养基，每1L中包含的成分有：0.15g NH 4Cl、0.02g KH 2PO 4、0.2g KCl、0.15g MgCl 2·6H 2O、0.01g MnSO 4·2H 2O、0.2g酵母提取物、4.28g柠檬酸三钠、3.5g NaHCO 3及5.8g Na 2CO 3，余下为水，自然pH，用于促进芽孢的生成和富集； The seed medium is a liquid medium, and the components contained in each 1L are: 0.15g NH 4 Cl, 0.02g KH 2 PO 4 , 0.2g KCl, 0.15g MgCl 2 · 6H 2 O, 0.01g MnSO 4 · 2H 2 O , 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO 3 and 5.8g Na 2 CO 3 , the rest is water, natural pH, used to promote the formation and enrichment of spores;
发酵培养基每1L中成分包括LB培养基和0.1g MnSO 4·2H 2O作为诱导物。 The components of the fermentation medium per liter include LB medium and 0.1 g MnSO 4 · 2H 2 O as inducers.
进一步的，所述尿素-氯化钙混合溶液为尿素和CaCl 2混合组成的溶液，每200ml混合溶液中包括15g尿素、9g CaCl 2，余下为水。 Further, the mixed urea-calcium chloride solution is a solution composed of urea and CaCl 2 , and each 200 ml of the mixed solution includes 15 g of urea and 9 g of CaCl 2 , and the rest is water.
上述的微生物改性充填材料的制备方法，包括以下步骤：The preparation method of the above microbial modified filling material includes the following steps:
(1)芽孢杆菌菌种的活化：取斜面上的芽孢杆菌单菌落于新鲜LB斜面，35℃恒温培养48h；(1) Activation of Bacillus species: take the single Bacillus colonies on the inclined surface on a fresh LB inclined surface and incubate at a constant temperature of 35 ℃ for 48h;
(2)种子液的培养：在该斜面挑取单菌落接种进液体种子培养基中，转速200rpm，35℃培养过夜；(2) Cultivation of seed liquid: pick a single colony on the slant to inoculate into liquid seed medium, rotate at 200 rpm, and culture at 35 ° C overnight;
(3)发酵液的制备：按7％接种量取种子培养液于发酵培养液中摇瓶培养，150rpm，35℃培养72h，制得菌液；(3) Preparation of fermentation broth: take seed culture broth in the fermentation broth at 7% inoculation volume, shake the flask in the fermentation broth, incubate at 150 rpm, 35 ° C for 72h, and prepare the bacterial broth;
(4)结构材料的准备：选取10mm以下的煤矸石和粉煤灰，放置在试件模型上；(4) Preparation of structural materials: select coal gangue and fly ash under 10mm and place them on the specimen model;
(5)菌液的灌注：采用蠕动泵以3ml/min的速率向试件模型中泵入培养好的菌液，灌注时间为3-5min；(5) Perfusion of bacterial solution: a peristaltic pump is used to pump the cultured bacterial solution into the specimen model at a rate of 3ml / min, and the perfusion time is 3-5min;
(6)混合溶液的灌注：步骤(5)完成1h后，以9ml/min速率向试件模型中注入尿素-氯化钙混合溶液，其中泵入时间以刚好灌满模型为标准；(6) Perfusion of mixed solution: After step (5) is completed for 1 h, the urea-calcium chloride mixed solution is injected into the specimen model at a rate of 9 ml / min, where the pumping time is based on just filling the model;
(7)菌液的循环灌注：步骤(6)反应5h后，重新向试件模型中泵入新鲜菌液；待充分反应后继续注入菌液至不能再注入为止，其中泵入时间以刚好灌满模型为标准；(7) Circulating perfusion of bacterial solution: After reacting for 5 hours in step (6), re-pump fresh bacterial solution into the specimen model; after full reaction, continue to inject bacterial solution until it can no longer be injected. Full model is standard;
(8)最终胶结形成微生物改性充填材料试样。(8) The final cementation forms a sample of microbial modified filling material.
进一步的，步骤(4)所用的模型尺寸为7cm×7cm×7cm。Further, the size of the model used in step (4) is 7 cm × 7 cm × 7 cm.
有益效果：本发明提供的一种微生物改性充填材料及制备方法，与现有技术相比，具有以下优势：本发明充分利用了微生物生长反应速率可调控、前期微生物性能可优化、环境污染小、价格相对低廉等优点，将自然界自发的微生物矿化原理应用于充填材料的制备过程。且微生物可以通过自身的生命活动，与煤矸石表面发生矿化作用，将松散的煤矸石固结成为带有一定强度的整体。该充填材料有利于充填开采的安全高效，提高了 煤矸石等固体废弃物的利用率。通过微生物的作用，提升充填材料的节能、环保和生态性能，是有益的创新，具有良好的应用前景。Beneficial effect: Compared with the prior art, a microbial modified filling material and preparation method provided by the present invention have the following advantages: the present invention fully utilizes the microbial growth reaction rate can be adjusted, the early stage microbial performance can be optimized, and the environmental pollution is small , The relatively low price and other advantages, the principle of spontaneous microbial mineralization in nature is applied to the preparation process of filling materials. And the microbes can mineralize with the surface of coal gangue through their own life activities, and consolidate the loose coal gangue into a whole with a certain strength. The filling material is conducive to the safe and efficient filling and mining, and improves the utilization rate of solid waste such as coal gangue. Through the action of microorganisms, improving the energy-saving, environmental protection and ecological performance of filling materials is a beneficial innovation and has good application prospects.
附图说明BRIEF DESCRIPTION
图1微生物改性充填材料制备方法工艺流程图；Figure 1 Process flow chart of preparation method of microbial modified filling material;
图2微生物改性充填材料制备方法工艺示意图；Figure 2 Schematic diagram of the preparation method of microbial modified filling material;
图3微生物改性充填材料截面细观结构示意图。Figure 3 Schematic diagram of the microstructure of the cross-section of the microbial modified filling material.
图中：1—筛选煤矸石；2—选取菌种；3—接种斜面；4—优化培养条件；5—种子培养液；6—发酵培养液；7—混合溶液；8—菌液；9—煤矸石入模；10—灌注菌液；11—灌注混合液；12—微生物改性充填材料试件；13—煤矸石；14—矿化产物碳酸钙；15—粉煤灰。In the picture: 1—screen coal gangue; 2—select strains; 3- inoculate slope; 4—optimize culture conditions; 5-—seed culture; 6—fermentation culture; 7—mixed solution; 8—bacteria; 9— Coal gangue into the mold; 10-infusion of bacterial liquid; 11-infusion mixture; 12-microbial modified filling material specimen; 13-gangue; 14-mineralized product calcium carbonate; 15- fly ash.
具体实施方式detailed description
本发明为一种应用于井下充填的微生物改性材料，所述的充填材料主要由煤矸石结构材料和胶结材料组成。其中煤矸石结构材料由煤矸石和粉煤灰按照40～45:1的重量比组成；胶结材料由所选用芽孢杆菌培养液、尿素-氯化钙混合液由1:9～12的体积比组成。所述煤矸石结构材料和胶结材料的重量比为5.6～7.2:1。本发明所述充填材料，其微生物诱导矿化反应温和，且在微生物死亡后仍能发挥作用，提高了充填材料的强度，有利于充填开采的安全高效，具有优异的环境友好性、耐久性和有良好的推广前景及应用意义。The invention is a microbial modified material used for downhole filling. The filling material is mainly composed of coal gangue structure material and cement material. The coal gangue structure material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1; the cementing material is composed of the selected Bacillus culture solution and the urea-calcium chloride mixed solution is a volume ratio of 1: 9 to 12 . The weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1. The filling material of the present invention has a mild mineralization reaction induced by microorganisms, and can still play a role after the death of microorganisms, which improves the strength of the filling material, is beneficial to the safety and efficiency of filling and mining, and has excellent environmental friendliness, durability and Has a good promotion prospects and application significance.
下面结合附图和实施例对本发明作更进一步的说明。The present invention will be further described below with reference to the drawings and embodiments.
实施例Examples
本发明是一种微生物改性充填材料及制备方法，如图1、2所示，说明如下：The present invention is a microbial modified filling material and preparation method, as shown in Figures 1 and 2 and explained as follows:
用于井下充填的微生物改性充填材料，主要由煤矸石结构材料和胶结材料组成。其中煤矸石结构材料由煤矸石和粉煤灰按照40～45:1的重量比组成；胶结材料由所选用芽孢杆菌培养液、尿素/氯化钙混合液由1:9～12的体积比组成；所述煤矸石结构材料和胶结材料的重量比为5.6～7.2:1。The microbial modified filling material used for downhole filling is mainly composed of coal gangue structure material and cementing material. The coal gangue structure material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1; the cementing material is composed of the selected Bacillus culture solution and the urea / calcium chloride mixed solution is a volume ratio of 1: 9 to 12 ; The weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
所使用的煤矸石结构材料，其煤矸石粒径在10mm以下。所使用的胶结材料包括芽孢杆菌的培养液和尿素-CaCl 2的水溶液。所述的芽孢杆菌培养液的制备包括菌种活化过程、种子培养过程、发酵过程三个步骤，该三个步骤涉及活化培养基、种子培养基、发酵培养基，其用量分别为20ml、1L、1L。 The gangue structure material used has a gangue particle size of 10 mm or less. The cementing material used includes a culture solution of Bacillus and an aqueous solution of urea-CaCl 2 . The preparation of the Bacillus culture solution includes three steps: a bacterial species activation process, a seed culture process, and a fermentation process. 1L.
活化培养基是LB固体斜面培养基，用于芽孢杆菌的活化，体积为20ml。种子培养 基为液体培养基，每1L中包含的成分有：0.15g NH 4Cl、0.02g KH 2PO 4、0.2g KCl、0.15g MgCl 2·6H 2O、0.01g MnSO 4·2H 2O、0.2g酵母提取物、4.28g柠檬酸三钠、3.5g NaHCO 3和5.8g Na 2CO 3，余下为水，自然pH，用于促进芽孢的生成和富集。发酵培养基每1L中包含的成分有LB培养基和0.1g MnSO 4·2H 2O作为诱导物。 The activation medium is an LB solid slant medium used for the activation of Bacillus, with a volume of 20 ml. The seed medium is a liquid medium, and the components contained in each 1L are: 0.15g NH 4 Cl, 0.02g KH 2 PO 4 , 0.2g KCl, 0.15g MgCl 2 · 6H 2 O, 0.01g MnSO 4 · 2H 2 O , 0.2g yeast extract, 4.28 g trisodium citrate, 3.5g NaHCO 3, and 5.8g Na 2 CO 3, the remainder being water, the pH naturally, for promoting spore formation and enrichment. The components contained in the fermentation medium per 1 L include LB medium and 0.1 g MnSO 4 · 2H 2 O as inducers.
混合溶液每200ml中包含的成分有尿素15g，CaCl 29g，余下为水。作用在于提供Ca 2+，引发微生物矿化。 Each 200ml of the mixed solution contains 15g of urea, 9g of CaCl 2 and the rest is water. The role is to provide Ca 2+ and trigger microbial mineralization.
微生物改性充填材料的制备方法如图2所示，其中，1-筛选煤矸石；2-选取菌种；3-接种斜面；4-优化培养条件；5-种子培养液；6-发酵培养液；7-混合溶液；8-菌液；9-煤矸石入模；10-灌注菌液；11-灌注混合液；12-微生物改性充填材料试件。具体包括以下步骤：The preparation method of the microbial modified filling material is shown in Fig. 2, in which, 1- screening coal gangue; 2- selecting strains; 3- inoculation slope; 4- optimizing culture conditions; 5- seed culture liquid; 6- fermentation culture liquid ; 7- mixed solution; 8- bacterial liquid; 9- coal gangue into the mold; 10- perfusion bacterial liquid; 11- perfusion mixed liquid; 12- microbial modified filling material test piece. It includes the following steps:
(1)芽孢杆菌菌种的活化：取斜面上的芽孢杆菌单菌落于新鲜LB斜面，35℃恒温培养48h；(1) Activation of Bacillus species: take the single Bacillus colonies on the inclined surface on a fresh LB inclined surface and incubate at a constant temperature of 35 ℃ for 48h;
(2)种子液的培养：在该斜面挑取单菌落接种进液体种子培养基中，转速200rpm，35℃培养过夜；(2) Cultivation of seed liquid: pick a single colony on the slant to inoculate into liquid seed medium, rotate at 200 rpm, and culture at 35 ° C overnight;
(3)发酵液的制备：按7％接种量取种子培养液于发酵培养液中摇瓶培养，150rpm，35℃培养72h，制得菌液；(3) Preparation of fermentation broth: take seed culture broth in the fermentation broth at 7% inoculation volume, shake the flask in the fermentation broth, incubate at 150 rpm, 35 ° C for 72h, and prepare the bacterial broth;
(4)结构材料的准备：选取10mm以下的煤矸石和粉煤灰放置在试件模型上；(4) Preparation of structural materials: coal gangue and fly ash under 10mm are selected and placed on the specimen model;
(5)菌液的灌注：采用蠕动泵以3ml/min的速率向试件模型中泵入培养好的菌液，灌注3-5min；(5) Perfusion of bacterial solution: a peristaltic pump is used to pump the cultured bacterial solution into the specimen model at a rate of 3ml / min, and perfusion is carried out for 3-5min;
(6)混合溶液的灌注。步骤(5)完成1h后，以9ml/min速率向试件模型中注入尿素-氯化钙混合溶液；其中泵入时间以刚好灌满模型为标准。(6) Perfusion of mixed solution. After step (5) is completed for 1 h, the urea-calcium chloride mixed solution is injected into the specimen model at a rate of 9 ml / min; where the pumping time is based on just filling the model.
(7)菌液的循环灌注：步骤(6)反应5h后，重新向试件模型中泵入新鲜菌液，待充分反应后继续注入菌液至不能再注入为止；其中泵入时间以刚好灌满模型为标准。(7) Circulating perfusion of bacterial solution: After reacting for 5 hours in step (6), re-pump fresh bacterial solution into the specimen model, and continue to inject the bacterial solution after the full reaction until it can no longer be injected; where the pumping time is just to fill Full model is standard.
(8)最终胶结8次后形成微生物改性充填材料试样。(8) After 8 times of final cementation, a sample of microbial modified filling material is formed.
以上所用的模型尺寸为7cm×7cm×7cm。The size of the model used above is 7cm × 7cm × 7cm.
如图3所示，为本发明制备所得的产物，由于微生物附着在煤矸石13和粉煤灰15表面，因此矿化产物碳酸钙14也生成在同样的位置。约7天后待泵入的菌液中芽孢杆菌营养物质消耗殆尽，芽孢杆菌会相继死亡，同时留下了矿化产物碳酸钙。经过菌液的循环灌注，矿化产物会结合在一起，将煤矸石和粉煤灰黏连成一个整体。传统煤矸石充 填材料的抗压轻度为2.0MPa左右，而通过该创新方法制得的新型微生物改性充填材料，其抗压强度明显提高，达到2.5MPa。整个反应在室温下进行，50℃以下均可发生该反应，并未伴随有明显的放热吸热过程。此创新方法充填效果更佳，提高了矿井生产的安全系数，所使用的材料成本低廉，反应无污染，有效利用了煤矸石等固体废弃物，达到了保护环境的目的，具有良好的推广前景和应用价值。As shown in FIG. 3, for the product prepared in the present invention, since the microorganisms adhere to the surfaces of coal gangue 13 and fly ash 15, the mineralized product calcium carbonate 14 is also generated at the same position. After about 7 days, the Bacillus nutrients in the bacterial liquid to be pumped are exhausted, and the Bacillus will die one after another, while the mineralized product calcium carbonate is left. After the circulation of the bacterial liquid, the mineralized products will be combined together, and the coal gangue and fly ash will be adhered into a whole. The compressive lightness of traditional coal gangue filling materials is about 2.0 MPa, and the compressive strength of the new microbial modified filling materials produced by this innovative method is significantly increased to 2.5 MPa. The whole reaction is carried out at room temperature, and the reaction can occur below 50 ° C without obvious exothermic and endothermic processes. This innovative method has better filling effect, improves the safety factor of mine production, the materials used are low in cost, the reaction is non-polluting, and the solid wastes such as coal gangue are effectively used to achieve the purpose of protecting the environment and has good promotion prospects and Value.
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only the preferred embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present invention, several improvements and retouches can be made. These improvements and retouches also It should be regarded as the protection scope of the present invention.

Claims (7)

  1. 一种应用于井下充填的微生物改性充填材料，其特征在于：由煤矸石结构材料和胶结材料组成，其中：A microbial modified packing material used for underground filling, which is characterized by being composed of coal gangue structure material and cementing material, wherein:
    煤矸石结构材料由煤矸石和粉煤灰按照40～45:1的重量比组成；Coal gangue structural material is composed of coal gangue and fly ash in a weight ratio of 40 to 45: 1;
    胶结材料由芽孢杆菌培养液、尿素-氯化钙混合液按照1:9～12的体积比组成；The cementing material is composed of Bacillus culture solution and urea-calcium chloride mixture according to the volume ratio of 1: 9 ～ 12;
    所述煤矸石结构材料和胶结材料的重量比为5.6～7.2:1。The weight ratio of the coal gangue structure material to the cement material is 5.6 to 7.2: 1.
  2. 根据权利要求1所述的微生物改性充填材料，其特征在于：所述的煤矸石结构材料，其煤矸石粒径在10mm以下。The microbial modified filling material according to claim 1, characterized in that the particle size of the coal gangue structure material is less than 10mm.
  3. 根据权利要求1所述的微生物改性充填材料，其特征在于：所述的芽孢杆菌培养液的制备包括菌种活化过程、种子培养过程、发酵过程三个步骤，该三个步骤涉及活化培养基、种子培养基、发酵培养基，其用量分别为20ml、1L、1L。The microbial modified filling material according to claim 1, characterized in that: the preparation of the Bacillus culture solution includes three steps: a bacterial species activation process, a seed culture process, and a fermentation process, and the three steps involve an activation medium , Seed medium, fermentation medium, the dosage is 20ml, 1L, 1L.
  4. 根据权利要求3所述的微生物改性充填材料，其特征在于：The microbial modified filling material according to claim 3, characterized in that:
    活化培养基是LB固体斜面培养基，用于芽孢杆菌的活化；The activation medium is an LB solid slant medium used for the activation of Bacillus;
    种子培养基为液体培养基，每1L中包含的成分有：0.15g NH 4Cl、0.02g KH 2PO 4、0.2g KCl、0.15g MgCl 2·6H 2O、0.01g MnSO 4·2H 2O、0.2g酵母提取物、4.28g柠檬酸三钠、3.5g NaHCO 3及5.8g Na 2CO 3，余下为水，自然pH，用于促进芽孢的生成和富集； The seed medium is a liquid medium, and the components contained in each 1L are: 0.15g NH 4 Cl, 0.02g KH 2 PO 4 , 0.2g KCl, 0.15g MgCl 2 · 6H 2 O, 0.01g MnSO 4 · 2H 2 O , 0.2g yeast extract, 4.28g trisodium citrate, 3.5g NaHCO 3 and 5.8g Na 2 CO 3 , the rest is water, natural pH, used to promote the formation and enrichment of spores;
    发酵培养基每1L中成分包括LB培养基和0.1g MnSO 4·2H 2O作为诱导物。 The components of the fermentation medium per liter include LB medium and 0.1 g MnSO 4 · 2H 2 O as inducers.
  5. 根据权利要求1所述的微生物改性充填材料，其特征在于：所述尿素-氯化钙混合溶液为尿素和CaCl 2混合组成的溶液，每200ml混合溶液中包括15g尿素、9g CaCl 2，余下为水。 The microbial modified filling material according to claim 1, characterized in that the urea-calcium chloride mixed solution is a solution composed of urea and CaCl 2 , and each 200 ml of the mixed solution includes 15g of urea and 9g of CaCl 2 . For water.
  6. 根据权利要求1～5任一所述的微生物改性充填材料的制备方法，其特征在于：包括以下步骤：The method for preparing a microbial modified filling material according to any one of claims 1 to 5, characterized in that it includes the following steps:
    (1)芽孢杆菌菌种的活化：取斜面上的芽孢杆菌单菌落于新鲜LB斜面，35℃恒温培养48h；(1) Activation of Bacillus species: take the single Bacillus colonies on the inclined surface on a fresh LB inclined surface and incubate at a constant temperature of 35 ℃ for 48h;
    (2)种子液的培养：在该斜面挑取单菌落接种进液体种子培养基中，转速200rpm，35℃培养过夜；(2) Cultivation of seed liquid: pick a single colony on the slant to inoculate into liquid seed medium, rotate at 200 rpm, and culture at 35 ° C overnight;
    (3)发酵液的制备：按7％接种量取种子培养液于发酵培养液中摇瓶培养，150rpm，35℃培养72h，制得菌液；(3) Preparation of fermentation broth: take seed culture broth in the fermentation broth at 7% inoculation volume, shake the flask in the fermentation broth, incubate at 150 rpm, 35 ° C for 72h, and prepare the bacterial broth
    (4)结构材料的准备：选取10mm以下的煤矸石和粉煤灰，放置在试件模型上；(4) Preparation of structural materials: select coal gangue and fly ash under 10mm and place them on the specimen model;
    (5)菌液的灌注：采用蠕动泵以3ml/min的速率向试件模型中泵入培养好的菌液， 灌注时间为3-5min；(5) Perfusion of bacterial solution: a peristaltic pump is used to pump the cultured bacterial solution into the specimen model at a rate of 3ml / min, and the perfusion time is 3-5min;
    (6)混合溶液的灌注：步骤(5)完成1h后，以9ml/min速率向试件模型中注入尿素-氯化钙混合溶液，其中泵入时间以刚好灌满模型为标准；(6) Perfusion of mixed solution: After step (5) is completed for 1 h, the urea-calcium chloride mixed solution is injected into the specimen model at a rate of 9 ml / min, where the pumping time is based on just filling the model;
    (7)菌液的循环灌注：步骤(6)反应5h后，重新向试件模型中泵入新鲜菌液；待充分反应后继续注入菌液至不能再注入为止，其中泵入时间以刚好灌满模型为标准；(7) Circulating perfusion of bacterial solution: After reacting for 5 hours in step (6), re-pump fresh bacterial solution into the specimen model; after full reaction, continue to inject bacterial solution until it can no longer be injected, in which the pumping time is just to fill Full model is standard;
    (8)最终胶结形成微生物改性充填材料试样。(8) The final cementation forms a sample of microbial modified filling material.
  7. 根据权利要求6所述的微生物改性充填材料的制备方法，其特征在于：步骤(4)所用的模型尺寸为7cm×7cm×7cm。The method for preparing a microorganism-modified filling material according to claim 6, wherein the size of the model used in step (4) is 7cm × 7cm × 7cm.
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CN108675689A (en) * 2018-03-23 2018-10-19 重庆大学 A kind of calcification ecological brick and its production method
CN108530013A (en) * 2018-04-26 2018-09-14 李珠 The manufacturing method of microorganism heat preservation construction material
CN109320192A (en) * 2018-11-06 2019-02-12 中国矿业大学 A kind of modified filler of microorganism and preparation method

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US20230097415A1 (en) * 2021-01-28 2023-03-30 Shanxi University Method for ecological filling with mixed coal gangue and fly ash
US11795106B2 (en) * 2021-01-28 2023-10-24 Shanxi University Method for ecological filling with mixed coal gangue and fly ash
CN114506176A (en) * 2022-02-21 2022-05-17 万禾隆（厦门）家居用品有限公司 Method for making novel sculpture handicraft

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