WO2022253355A1 - Strengthening method for recycled aggregate using biological deposition - Google Patents

Strengthening method for recycled aggregate using biological deposition Download PDF

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WO2022253355A1
WO2022253355A1 PCT/CN2022/099669 CN2022099669W WO2022253355A1 WO 2022253355 A1 WO2022253355 A1 WO 2022253355A1 CN 2022099669 W CN2022099669 W CN 2022099669W WO 2022253355 A1 WO2022253355 A1 WO 2022253355A1
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solution
soaking
recycled aggregate
bacterial
culture solution
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PCT/CN2022/099669
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French (fr)
Chinese (zh)
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冯春花
朱建平
崔卜文
杜明星
张文艳
郭晖
宗旭东
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河南理工大学
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Priority to SE2251564A priority Critical patent/SE2251564A1/en
Publication of WO2022253355A1 publication Critical patent/WO2022253355A1/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
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02Treatment
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • the invention belongs to the technical field of building materials, and in particular relates to a method for strengthening recycled aggregates using biological deposition.
  • the reduction of water absorption and the increase of apparent density are based on the reduction of the porosity of recycled aggregates.
  • the improvement of aggregate pore structure can further improve the working performance of recycled concrete.
  • the reduction of porosity also improves the performance of recycled concrete. Excessive water absorption will make the interface transition zone of recycled concrete rich in water, which will affect the mechanical properties and durability of the specimen; on the other hand, the crushing value of recycled aggregate is much higher than that of natural aggregate, while The hardness of recycled aggregate directly affects the mechanical properties of recycled concrete. Based on the above two points, the present invention focuses on improving the water absorption and crushing index of the recycled aggregate.
  • the invention patent with the application number CN113683330A provides a preparation method and system for strengthening recycled aggregates
  • the application number CN111153618A discloses a preparation device and method for strengthening recycled aggregates through microbial mineralization.
  • the above methods can strengthen regeneration Aggregate, but the existing methods are mostly limited to the use of spraying means, it is difficult for organisms to completely enter all the holes and survive effectively, thereby effectively improving the pore structure of recycled aggregates, and in addition, complex devices cause high reinforcement costs for recycled aggregates , which violates the purpose of strengthening recycled aggregates.
  • the purpose of the present invention is to provide a method for strengthening recycled aggregates using biological deposition to solve/improve that the calcium carbonate generated by biomineralization deposition during traditional soaking treatment cannot be targeted to repair holes, and the spray treatment equipment is complex and costly. High, difficult to large-scale industrial application of at least one of the current status of the problem.
  • the present invention provides the following technical solution: a method for strengthening recycled aggregates utilizing biological deposition, comprising the following steps:
  • (1) Filling and soaking first soak the regenerated aggregate in the bacterial solution in a vacuum environment, then take out the regenerated aggregate from the bacterial solution, soak it in the mineralization culture solution, and place the regenerated bone after soaking The material is taken out, cleaned, and dried; the soaking time of the regenerated aggregate in the bacterial solution is 20-60min, and the vacuum degree of the vacuum environment is 0.6-0.8Mpa; the mass ratio of the regenerated aggregate to the bacterial solution is 2 : 1 ⁇ 2:1.2, the mass ratio of described mineralization culture fluid and described bacterial fluid is 1:1;
  • the bacillus includes colloid bacillus and subtilis bacillus, and the ratio of the effective number of viable bacteria of the two kinds of bacteria is 3:7-7:3.
  • the method for strengthening recycled aggregates using biodeposition of the present invention can be more targeted on the areas where recycled aggregates need to be repaired to obtain a better repair effect, and industrially produced bacterial powder is used to greatly reduce the process.
  • the cost makes Microbial Mineralized Precipitation (MICP) technology more widely used.
  • the invention utilizes the recycled aggregate strengthening method of biological deposition to reduce the cost of the current microbial mineralization deposition (MICP) technology and optimizes the strengthening effect of the MICP technology on the recycled aggregate, and the strengthening process is more targeted for the repair of the recycled aggregate, thereby
  • the pore structure and basic properties of the recycled aggregate are significantly changed, the water absorption of the recycled aggregate is reduced by about 30%, and the crushing index is improved by about 16%.
  • Fig. 1 is the SEM figure of the calcite calcium carbonate that fills the interstices of recycled aggregate obtained after the treatment of comparative example 1 that comparative example 1 of the present invention provides; ;
  • Fig. 2 is the XRD pattern of the calcite calcium carbonate that fills the gap of recycled aggregate obtained after the comparative example 1 treatment provided by the comparative example 1 of the present invention
  • Fig. 3 is the comparison chart of the crushing value and water absorption ratio of the recycled aggregates obtained by the methods of Example 1 and Comparative Examples 1 to 3 respectively provided by the present invention
  • Fig. 4 is the scanning electron micrograph of the surface morphology of the recycled aggregate obtained by the method of Example 1 and Comparative Examples 1-3 respectively provided by the present invention; wherein, (a) is obtained after the treatment of Comparative Example 1 The scanning electron micrograph of the recycled aggregate, (b) is the scanning electron micrograph of the recycled aggregate obtained after the comparative example 2 treatment, (c) is the scanning electron microscopic image of the recycled aggregate obtained after the comparative example 3 treatment, (d ) is a scanning electron micrograph of the recycled aggregate obtained after the treatment of Example 1;
  • Fig. 5 is a comparison chart of the mineralization rate provided by the present invention after being treated with the mineralization liquid of Experimental Examples 1-3 respectively.
  • the present invention aims at the defects existing in the current recycled aggregate bio-augmentation technology, and makes up for the fact that the biologically generated calcium carbonate in the traditional immersion treatment cannot repair the holes in a targeted manner, and the spraying treatment equipment is complicated, the cost is high, and it is difficult for large-scale industrial application. , to provide a method for strengthening recycled aggregates using biodeposition, so as to solve or alleviate at least one of the above-mentioned problems.
  • (1) Filling and soaking first soak the recycled aggregate in the bacterial solution in a vacuum environment, then take out the recycled aggregate from the bacterial solution, soak it in the mineralization culture solution, take out the recycled aggregate after soaking, and wash , dry; (2) repair soaking: soak the recycled aggregate treated in step (1) in the mixed culture solution of bacteria solution and mineralization culture solution; the bacteria solution contains bacillus.
  • the recycled aggregate strengthening method using biological deposition provided by the present invention, during the filling and soaking treatment, the recycled aggregate is soaked in the bacterial solution in a vacuum environment, and the bacterial solution can better fill the internal pore structure of the recycled aggregate, and the microbial Calcium carbonate is mineralized and deposited in the pores of the attached mortar to fill the pore structure, which is named filling soaking; during repairing soaking, microorganisms focus on repairing the surface of the recycled aggregate, named repairing soaking.
  • the main function of Bacillus is to induce the generation of calcium carbonate to fill the cavity.
  • the production of calcium carbonate is concentrated around the bacteria, and the mineralized culture solution provides calcium ions and nutrients for the bacteria to survive and produce calcium carbonate.
  • the main purpose of repairing and soaking is to make the bacteria survive in a suitable environment. Nucleation site patching.
  • the contact between mineralized culture fluid and bacteria during filling and soaking is not more effective than that of repairing soaking, so the activity of bacteria is not as good as that of repairing soaking, but the advantage of filling and soaking is that the repairing position is very targeted, and the calcium carbonate produced is in the position that needs to be repaired , the biological activity is better when repairing and soaking, and the speed of producing calcium carbonate is faster, but it is not targeted for the repair of aggregates, so we choose to fill and soak to repair the large internal defects of the aggregate, and then repair and soak to strengthen the recycled aggregate. .
  • step (1) the soaking time of the recycled aggregate in the bacterial solution is 20-60 minutes (for example, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes).
  • step (1) the mass ratio of the recycled aggregate to the bacterial solution is 2:1 to 2:1.2 (for example, 2:1, 2:1.1 or 2:1.2), and the mass ratio of the mineralized culture solution to the bacterial solution is 1:1.
  • step (1) the vacuum degree of the vacuum environment is 0.6-0.8Mpa.
  • step (2) the mass ratio of the recycled aggregate to the mixed culture solution is 1.5:2 to 3:2 (for example, 1.5:2, 2:2, 2.5:2 or 3:2), and the bacteria solution in the mixed culture solution is mixed with The mass ratio of mineralized culture medium is 1:1.
  • the mass ratio of the recycled aggregate to the mixed culture solution in step (2) is 1:1 to 1:1.2 (for example, 1:1.2, 1:1.1, or 1:1)
  • Bacillus comprises colloid bacillus and bacillus subtilis, and the effective number ratio of two kinds of bacteria used is 3:7-7:3 (for example, 3:7, 5:7, 7:7 or 7:3 ), the metabolic effects of the two bacteria co-induced the production of calcium carbonate precipitates during the mineralization process.
  • the Bacillus colloidum is derived from the Bacillus colloidus powder, and the effective number of viable bacteria in the Bacillus coliformum powder is 1 ⁇ 10 10 cfu/g bacterial powder.
  • the Bacillus subtilis comes from the Bacillus subtilis powder, and the effective number of viable bacteria of the Bacillus subtilis powder is 2 ⁇ 10 11 cfu/g bacteria powder.
  • the bacterial liquid is prepared according to the following method: dissolve the bacterial powder in deionized water, stir, adjust the pH, and filter after standing still to obtain the bacterial liquid.
  • the stirring time is 5-15min (for example, 5min, 10min or 15min)
  • the pH of the bacterial liquid is adjusted to 9.5-10.5 (for example, 9.5, 10 or 10.5) with NaOH, and the standing time is ⁇ 30min .
  • the bacterial concentration of the bacterial liquid is 2 ⁇ 10 8 -4 ⁇ 10 8 cfu/mL (for example, 2 ⁇ 10 8 cfu/mL, 3 ⁇ 10 8 cfu/mL or 4 ⁇ 10 8 cfu/mL).
  • the mineralizing nutrient solution comprises 4-6 (for example 4, 5 or 6) parts by weight of yeast extract powder, 3-5 (for example 3, 4 or 5) parts by weight of peptone, 45-55 parts of calcium chloride (for example 45, 50 or 55 ) parts by weight, calcium lactate 18-22 (eg 18, 20 or 22) parts by weight and 500 parts by weight.
  • calcium chloride and calcium lactate are mainly used to provide calcium ions, and calcium lactate can also serve as a carbon source in addition to providing calcium sources.
  • the mineralized nutrient solution is prepared according to the following method: dissolving yeast, peptone, calcium chloride and calcium lactate in deionized water, adjusting the pH, standing still and filtering to obtain the mineralized nutrient solution.
  • step (1) the immersion of the regenerated aggregate in the mineralization culture solution is carried out in a ventilated environment at 25-35°C (such as 25°C, 30°C or 35°C), and the immersion time is 14 days; in step (2), the regenerated bone
  • the immersion of the material in the mixed culture solution is carried out in a ventilated environment at 25-35°C (such as 25°C, 30°C or 35°C), and the soaking time is 7-14d (for example, 7d, 8d, 9d, 10d, 11d, 12d, 13d or 14d).
  • the above-mentioned two-step immersion treatment can not get a good repair effect when the curing time is short.
  • the solution basically loses minerals. ability to deposit calcium carbonate.
  • the bacteria solution used in the following examples was prepared according to the following method: 6.0 g of Bacillus colloidus bacteria powder (the number of effective viable bacteria was 6 ⁇ 10 10 cfu) and 0.7 g of Bacillus subtilis ( The number of effective viable bacteria is 1.4 ⁇ 10 11 cfu) dissolved in 500 g of deionized water, stirred for 10 minutes, added NaOH to adjust the pH to 10, allowed to stand for 30 minutes, and then filtered to obtain the above bacteria solution.
  • the mineralized culture solution used in the following examples is prepared according to the following method: 5 g of yeast extract powder, 4 g of peptone, 50 g of calcium chloride and 20 g of calcium lactate are dissolved in 500 g of deionized water, and NaOH is added to adjust pH to 10.0, let it stand for 30 minutes and then filter to obtain the above mineralization culture solution.
  • the first repair soaking select the particle size of the recycled aggregate to be 9.5, prepare a mixed culture solution according to the mass ratio of the mineralized culture solution and the bacterial solution at a ratio of 1:1, and then follow the mass ratio of the mixed culture solution and the recycled aggregate to Soak the recycled aggregate directly at a ratio of 1:1, put it in a ventilated environment at 25-35°C for 14 days, take it out, wash it, and dry it in an oven at 40°C;
  • the change rate of calcium ion concentration before and after the mineralization reaction is the mineralization rate of the mineralization solution, that is, the ability of the solution to produce calcium carbonate.
  • the mineralization rate of the mineralization solution after the mineralization reaction in Experimental Examples 1-3 is shown in Figure 5.
  • the mineralization capacity of the solution determines the amount of calcium carbonate generated.
  • Calcium carbonate is a raw material for repairing and strengthening recycled aggregates.
  • the solution has a higher mineralization rate under the synergistic effect of the two bacteria, which helps to improve the biodeposition strengthening effect on the recycled aggregate.

Abstract

The present invention relates to a strengthening method for a recycled aggregate using biological deposition, comprising the following steps: (1) filling and soaking: in a vacuum environment, soaking a recycled aggregate in a bacterial solution, then taking out the recycled aggregate from the bacterial solution, soaking in a mineralized culture solution, taking out the recycled aggregate after the soaking is finished, and cleaning and drying; (2) repairing and soaking: taking out the recycled aggregate treated in step (1), cleaning and drying, then soaking in a mixed culture solution of the bacterial solution and the mineralized culture solution; wherein the bacterial solution contains bacillus. In the present invention, the strengthening method for a recycled aggregate using biological deposition can better target areas needing to be repaired of the recycled aggregate, thereby obtaining a better repairing effect, and a bacterial powder produced by industrial production is used to greatly reduce process costs, so that the microbial mineralization deposition (MICP) technology has a wider application range.

Description

一种利用生物沉积的再生骨料强化方法A Renewable Aggregate Strengthening Method Utilizing Biodeposition 技术领域technical field
本发明属于建筑材料技术领域,具体涉及一种利用生物沉积的再生骨料强化方法。The invention belongs to the technical field of building materials, and in particular relates to a method for strengthening recycled aggregates using biological deposition.
背景技术Background technique
数据统计,截至到2019年,中国的建筑垃圾占到城市垃圾的十分之四。就建筑行业的可持续发展来看,从建筑垃圾中重新回收建筑材料来缓解天然建筑材料短缺和用于填埋建筑垃圾的土地资源短缺的现状,有着重要的意义。然而,再生骨料本身的性能大大劣于天然骨料。再生骨料性能较差的原因在于其表面附着大量的老旧砂浆和破碎过程产生的微裂纹,这造成了再生骨料具有远高于天然骨料的吸水率和压碎值。再生骨料的强化技术通常基于降低再生骨料的吸水率与压碎指标,提高再生骨料的表观密度和硬度来进行。一方面,吸水率的降低、表观密度的升高是基于再生骨料孔隙率的降低,骨料孔结构的改善能进一步提高再生混凝土的工作性能,此外,孔隙率的降低也改善了再生混凝土的界面过渡区,过高的吸水率会使再生混凝土界面过渡区富水,进而影响试件的力学性能和耐久性;另一方面,再生骨料的压碎值远高于天然骨料,而再生骨料的硬度直接影响了再生混凝土的力学性能。基于以上两点,本发明着重于改善再生骨料的吸水率和压碎指标。According to statistics, as of 2019, construction waste in China accounted for four tenths of urban waste. As far as the sustainable development of the construction industry is concerned, it is of great significance to recycle construction materials from construction waste to alleviate the shortage of natural construction materials and the shortage of land resources for landfill construction waste. However, the performance of recycled aggregate itself is significantly inferior to that of natural aggregate. The reason for the poor performance of recycled aggregates is that a large amount of old mortar is attached to the surface and microcracks generated during the crushing process, which cause recycled aggregates to have much higher water absorption and crushing values than natural aggregates. The strengthening technology of recycled aggregate is usually based on reducing the water absorption and crushing index of recycled aggregate, and increasing the apparent density and hardness of recycled aggregate. On the one hand, the reduction of water absorption and the increase of apparent density are based on the reduction of the porosity of recycled aggregates. The improvement of aggregate pore structure can further improve the working performance of recycled concrete. In addition, the reduction of porosity also improves the performance of recycled concrete. Excessive water absorption will make the interface transition zone of recycled concrete rich in water, which will affect the mechanical properties and durability of the specimen; on the other hand, the crushing value of recycled aggregate is much higher than that of natural aggregate, while The hardness of recycled aggregate directly affects the mechanical properties of recycled concrete. Based on the above two points, the present invention focuses on improving the water absorption and crushing index of the recycled aggregate.
目前我国在强化再生骨料的研究领域已取得了一定的进展。申请号为CN113683330A的发明专利提供了一种强化再生骨料的制备方法及制备系统,申请号为CN111153618A公开了一种微生物矿化强化再生骨料的制备装置及制备方法,以上方法均能强化再生骨料,但是现有方法多局限于使用喷淋的手段,生物难以完全进入所有孔洞并有效生存,从而有效改善再生骨料的孔结构,此外,复杂的装置造成再生骨料的强化成本较高,这违背再生骨料强化处理的目的。At present, some progress has been made in the research field of strengthening recycled aggregate in our country. The invention patent with the application number CN113683330A provides a preparation method and system for strengthening recycled aggregates, and the application number CN111153618A discloses a preparation device and method for strengthening recycled aggregates through microbial mineralization. The above methods can strengthen regeneration Aggregate, but the existing methods are mostly limited to the use of spraying means, it is difficult for organisms to completely enter all the holes and survive effectively, thereby effectively improving the pore structure of recycled aggregates, and in addition, complex devices cause high reinforcement costs for recycled aggregates , which violates the purpose of strengthening recycled aggregates.
发明内容Contents of the invention
本发明的目的在于提供一种利用生物沉积的再生骨料强化方法,以解决/改善传统浸泡处理时生物矿化沉积生成的碳酸钙无法有针对性地修补孔洞,而喷淋处理设备复杂,成本较高,难以大规模工业应用的现状中的至少一项问题。The purpose of the present invention is to provide a method for strengthening recycled aggregates using biological deposition to solve/improve that the calcium carbonate generated by biomineralization deposition during traditional soaking treatment cannot be targeted to repair holes, and the spray treatment equipment is complex and costly. High, difficult to large-scale industrial application of at least one of the current status of the problem.
为了实现上述目的,本发明提供如下技术方案:一种利用生物沉积的再生骨料强化方法,包括下述步骤:In order to achieve the above object, the present invention provides the following technical solution: a method for strengthening recycled aggregates utilizing biological deposition, comprising the following steps:
(1)填充浸泡:先在真空环境下将再生骨料浸泡于菌液中,之后将所述再生骨料从所述菌液中取出,浸泡于矿化培养液中,浸泡结束后将再生骨料取出,清洗,干燥;所述再生骨料在菌液中浸泡的时间为20~60min,所述真空环境的真空度为0.6~0.8Mpa;所述再生骨料与菌液的质量比为2:1~2:1.2,所述矿化培养液与所述菌液的质量比为1:1;(1) Filling and soaking: first soak the regenerated aggregate in the bacterial solution in a vacuum environment, then take out the regenerated aggregate from the bacterial solution, soak it in the mineralization culture solution, and place the regenerated bone after soaking The material is taken out, cleaned, and dried; the soaking time of the regenerated aggregate in the bacterial solution is 20-60min, and the vacuum degree of the vacuum environment is 0.6-0.8Mpa; the mass ratio of the regenerated aggregate to the bacterial solution is 2 : 1~2:1.2, the mass ratio of described mineralization culture fluid and described bacterial fluid is 1:1;
(2)修补浸泡:将经步骤(1)处理后的再生骨料取出,清洗、干燥后浸泡于所述菌液和矿化培养液的混合培养液中;所述菌液中含有芽孢杆菌;所述再生骨料与所述混合培养液的质量比为1:1~1:1.2;所述混合培养液中菌液与所述矿化培养液的质量比为1:1;(2) Soaking for repairing: taking out the regenerated aggregate treated in step (1), cleaning and drying, and soaking in the mixed culture solution of the bacteria solution and the mineralization culture solution; the bacteria solution contains bacillus; The mass ratio of the regenerated aggregate to the mixed culture solution is 1:1 to 1:1.2; the mass ratio of the bacteria solution in the mixed culture solution to the mineralized culture solution is 1:1;
所述芽孢杆菌包括胶质芽孢杆菌和枯草芽孢杆菌,两种菌的有效活菌数之比为3:7-7:3。The bacillus includes colloid bacillus and subtilis bacillus, and the ratio of the effective number of viable bacteria of the two kinds of bacteria is 3:7-7:3.
有益效果:本发明的利用生物沉积的再生骨料强化方法可以更有针对性地作用于再生骨料需要修补的区域,得到更好的修复效果,且采用工业生产的菌粉来大幅度降低工艺成本,使微生物矿化沉积(MICP)技术获得更广泛的应用。Beneficial effects: The method for strengthening recycled aggregates using biodeposition of the present invention can be more targeted on the areas where recycled aggregates need to be repaired to obtain a better repair effect, and industrially produced bacterial powder is used to greatly reduce the process. The cost makes Microbial Mineralized Precipitation (MICP) technology more widely used.
本发明利用生物沉积的再生骨料强化方法降低了目前微生物矿化沉积(MICP)技术成本且优化了MICP技术对再生骨料的强化效果,强化过程对于再生骨料的修复更有针对性,从而显著改变再生骨料的孔结构和基本性能,修复后再生骨料的吸水率降低30%左右,压碎指标改进16%左右。The invention utilizes the recycled aggregate strengthening method of biological deposition to reduce the cost of the current microbial mineralization deposition (MICP) technology and optimizes the strengthening effect of the MICP technology on the recycled aggregate, and the strengthening process is more targeted for the repair of the recycled aggregate, thereby The pore structure and basic properties of the recycled aggregate are significantly changed, the water absorption of the recycled aggregate is reduced by about 30%, and the crushing index is improved by about 16%.
附图说明Description of drawings
图1为本发明对比例1提供的经对比例1处理后得到的填充再生骨料空隙的方解石碳酸钙的SEM图;其中,图1中的右图为左图的放大图(放大10倍);Fig. 1 is the SEM figure of the calcite calcium carbonate that fills the interstices of recycled aggregate obtained after the treatment of comparative example 1 that comparative example 1 of the present invention provides; ;
图2为本发明对比例1提供的经对比例1处理后得到的填充再生骨料空隙的方解石碳酸钙的XRD图;Fig. 2 is the XRD pattern of the calcite calcium carbonate that fills the gap of recycled aggregate obtained after the comparative example 1 treatment provided by the comparative example 1 of the present invention;
图3为本发明提供的分别经实施例1与对比例1~3的方法处理后得到的再生骨料的压碎值和吸水率对比例图;Fig. 3 is the comparison chart of the crushing value and water absorption ratio of the recycled aggregates obtained by the methods of Example 1 and Comparative Examples 1 to 3 respectively provided by the present invention;
图4为本发明提供的分别经实施例1与对比例1~3的方法处理后得到的再生骨料的表面形貌的扫描电镜图;其中,(a)为经对比例1处理后得到的再生骨料的扫描电镜图,(b)为经对比例2处理后得到的再生骨料的扫描电镜图,(c)为经对比例3处理后得到的再生骨料的扫描电镜图,(d)为经实施例1处理后得到的再生骨料的扫描电镜图;Fig. 4 is the scanning electron micrograph of the surface morphology of the recycled aggregate obtained by the method of Example 1 and Comparative Examples 1-3 respectively provided by the present invention; wherein, (a) is obtained after the treatment of Comparative Example 1 The scanning electron micrograph of the recycled aggregate, (b) is the scanning electron micrograph of the recycled aggregate obtained after the comparative example 2 treatment, (c) is the scanning electron microscopic image of the recycled aggregate obtained after the comparative example 3 treatment, (d ) is a scanning electron micrograph of the recycled aggregate obtained after the treatment of Example 1;
图5为本发明提供的分别经实验例1-3矿化液处理后的矿化率对比图。Fig. 5 is a comparison chart of the mineralization rate provided by the present invention after being treated with the mineralization liquid of Experimental Examples 1-3 respectively.
具体实施方式Detailed ways
下面将结合实施例来详细说明本发明。需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。The present invention will be described in detail below in conjunction with examples. It should be noted that, in the case of no conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.
本发明针对目前再生骨料生物增强技术存在的缺陷,弥补传统浸泡处理时生物生成的碳酸钙无法有针对性地修补孔洞,而喷淋处理设备复杂,成本较高,难以大规模工业应用的现状,提供一种利用生物沉积的再生骨料强化方法,以解决或缓解上述中的至少一项问题。The present invention aims at the defects existing in the current recycled aggregate bio-augmentation technology, and makes up for the fact that the biologically generated calcium carbonate in the traditional immersion treatment cannot repair the holes in a targeted manner, and the spraying treatment equipment is complicated, the cost is high, and it is difficult for large-scale industrial application. , to provide a method for strengthening recycled aggregates using biodeposition, so as to solve or alleviate at least one of the above-mentioned problems.
本发明提供的利用生物沉积的再生骨料强化方法中,包括下述步骤:In the recycled aggregate strengthening method provided by the present invention utilizing biodeposition, comprise the following steps:
(1)填充浸泡:先在真空环境下将再生骨料浸泡于菌液中,之后将再生骨料从菌液中取出,浸泡于矿化培养液中,浸泡结束后将再生骨料取出,清洗,干燥;(2)修补浸泡:将经步骤(1)处理后的再生骨料浸泡于菌液和矿化培养液的混合培养液中;菌液中含有芽孢杆菌。(1) Filling and soaking: first soak the recycled aggregate in the bacterial solution in a vacuum environment, then take out the recycled aggregate from the bacterial solution, soak it in the mineralization culture solution, take out the recycled aggregate after soaking, and wash , dry; (2) repair soaking: soak the recycled aggregate treated in step (1) in the mixed culture solution of bacteria solution and mineralization culture solution; the bacteria solution contains bacillus.
本发明提供的利用生物沉积的再生骨料强化方法中,填充浸泡处理时,通过在真空环境下将再生骨料浸泡于菌液中,菌液能更好地填充再生骨料内部孔隙结构,微生物于附着砂浆的孔隙中矿化沉积生成碳酸钙,填补孔结构,命名为填充浸泡;修补浸泡时微生物着重修复再生骨料的表面,命名为修补浸泡。In the recycled aggregate strengthening method using biological deposition provided by the present invention, during the filling and soaking treatment, the recycled aggregate is soaked in the bacterial solution in a vacuum environment, and the bacterial solution can better fill the internal pore structure of the recycled aggregate, and the microbial Calcium carbonate is mineralized and deposited in the pores of the attached mortar to fill the pore structure, which is named filling soaking; during repairing soaking, microorganisms focus on repairing the surface of the recycled aggregate, named repairing soaking.
其中,芽孢杆菌的主要作用是诱导生成碳酸钙填充空洞,碳酸钙的产生 集中关于细菌的周围,矿化培养液提供钙离子和营养物质,以供细菌生存和制造碳酸钙,填充浸泡主要是大幅度提高再生骨料内部的孔洞的细菌浓度,使细菌在空洞内壁附着,之后产生的碳酸钙可以填充内部的孔,修补浸泡的主要目的是使细菌在适宜环境中生存,骨料表面作为细菌的成核位点修补。填充浸泡时矿化培养液和细菌并没有修补浸泡时接触的更加有效,因此细菌的活性不如修补浸泡,但是填充浸泡的优点是修补位置很有针对性,产生的碳酸钙都在需要修补的位置,修补浸泡时生物的活性更好产生碳酸钙的速度更快但是对于骨料的修补不具有针对性,因此我们选择先进行填充浸泡修补骨料内部大缺陷,再进行修补浸泡来增强再生骨料。Among them, the main function of Bacillus is to induce the generation of calcium carbonate to fill the cavity. The production of calcium carbonate is concentrated around the bacteria, and the mineralized culture solution provides calcium ions and nutrients for the bacteria to survive and produce calcium carbonate. Increase the concentration of bacteria in the holes inside the recycled aggregate to make the bacteria adhere to the inner wall of the hole, and then the calcium carbonate produced can fill the inner holes. The main purpose of repairing and soaking is to make the bacteria survive in a suitable environment. Nucleation site patching. The contact between mineralized culture fluid and bacteria during filling and soaking is not more effective than that of repairing soaking, so the activity of bacteria is not as good as that of repairing soaking, but the advantage of filling and soaking is that the repairing position is very targeted, and the calcium carbonate produced is in the position that needs to be repaired , the biological activity is better when repairing and soaking, and the speed of producing calcium carbonate is faster, but it is not targeted for the repair of aggregates, so we choose to fill and soak to repair the large internal defects of the aggregate, and then repair and soak to strengthen the recycled aggregate. .
步骤(1)中,再生骨料在菌液中浸泡的时间为20~60min(例如,20min、30min、40min、50min或60min)。In step (1), the soaking time of the recycled aggregate in the bacterial solution is 20-60 minutes (for example, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes).
步骤(1)中,再生骨料与菌液的质量比为2:1~2:1.2(例如,2:1、2:1.1或2:1.2),矿化培养液与菌液的质量比为1:1。In step (1), the mass ratio of the recycled aggregate to the bacterial solution is 2:1 to 2:1.2 (for example, 2:1, 2:1.1 or 2:1.2), and the mass ratio of the mineralized culture solution to the bacterial solution is 1:1.
步骤(1)中,真空环境的真空度为0.6~0.8Mpa。In step (1), the vacuum degree of the vacuum environment is 0.6-0.8Mpa.
步骤(2)中再生骨料与混合培养液的质量比为1.5:2~3:2(例如,1.5:2、2:2、2.5:2或3:2),混合培养液中菌液与矿化培养液的质量比为1:1。In step (2), the mass ratio of the recycled aggregate to the mixed culture solution is 1.5:2 to 3:2 (for example, 1.5:2, 2:2, 2.5:2 or 3:2), and the bacteria solution in the mixed culture solution is mixed with The mass ratio of mineralized culture medium is 1:1.
本发明优选实施例中,步骤(2)中再生骨料与混合培养液的质量比为1:1~1:1.2(例如,1:1.2、1:1.1、或1:1)In a preferred embodiment of the present invention, the mass ratio of the recycled aggregate to the mixed culture solution in step (2) is 1:1 to 1:1.2 (for example, 1:1.2, 1:1.1, or 1:1)
芽孢杆菌包括胶质芽孢杆菌和枯草芽孢杆菌,所使用的两种菌的有效活菌数比为3:7-7:3(例如,3:7、5:7、7:7或7:3),矿化过程中两种细菌的代谢作用共同诱导碳酸钙沉淀的产生。Bacillus comprises colloid bacillus and bacillus subtilis, and the effective number ratio of two kinds of bacteria used is 3:7-7:3 (for example, 3:7, 5:7, 7:7 or 7:3 ), the metabolic effects of the two bacteria co-induced the production of calcium carbonate precipitates during the mineralization process.
胶质芽孢杆菌来自胶质芽孢杆菌菌粉,胶质芽孢杆菌菌粉的有效活菌数为1×10 10cfu/g菌粉。 The Bacillus colloidum is derived from the Bacillus colloidus powder, and the effective number of viable bacteria in the Bacillus coliformum powder is 1×10 10 cfu/g bacterial powder.
枯草芽孢杆菌来自枯草芽孢杆菌菌粉,枯草芽孢杆菌菌粉的有效活菌数为2×10 11cfu/g菌粉。 The Bacillus subtilis comes from the Bacillus subtilis powder, and the effective number of viable bacteria of the Bacillus subtilis powder is 2×10 11 cfu/g bacteria powder.
菌液按照下述方法配制得到:将菌粉溶解于去离子水中,搅拌,调节pH,静置后过滤,即得菌液。The bacterial liquid is prepared according to the following method: dissolve the bacterial powder in deionized water, stir, adjust the pH, and filter after standing still to obtain the bacterial liquid.
配制菌液时,搅拌的时间为5~15min(例如,5min、10min或15min),采用NaOH将菌液的pH调节至9.5~10.5(例如,9.5、10或10.5),静置的时间≥30min。When preparing the bacterial liquid, the stirring time is 5-15min (for example, 5min, 10min or 15min), the pH of the bacterial liquid is adjusted to 9.5-10.5 (for example, 9.5, 10 or 10.5) with NaOH, and the standing time is ≥30min .
菌液的细菌浓度为2×10 8-4×10 8cfu/mL(例如2×10 8cfu/mL、3×10 8cfu/mL或4×10 8cfu/mL)。 The bacterial concentration of the bacterial liquid is 2×10 8 -4×10 8 cfu/mL (for example, 2×10 8 cfu/mL, 3×10 8 cfu/mL or 4×10 8 cfu/mL).
矿化营养液包括酵母浸粉4~6(例如4、5或6)重量份、蛋白胨3~5(例如3、4或5)重量份、氯化钙45~55(例如45、50或55)重量份、乳酸钙18~22(例如18、20或22)重量份和500重量份。其中,氯化钙和乳酸钙主要用于提供钙离子,乳酸钙除提供钙源外,还可起到提供碳源的作用。The mineralizing nutrient solution comprises 4-6 (for example 4, 5 or 6) parts by weight of yeast extract powder, 3-5 (for example 3, 4 or 5) parts by weight of peptone, 45-55 parts of calcium chloride (for example 45, 50 or 55 ) parts by weight, calcium lactate 18-22 ( eg 18, 20 or 22) parts by weight and 500 parts by weight. Among them, calcium chloride and calcium lactate are mainly used to provide calcium ions, and calcium lactate can also serve as a carbon source in addition to providing calcium sources.
矿化营养液按照下述方法配制得到:将酵母、蛋白胨、氯化钙和乳酸钙溶解于去离子水中,调节pH,静置后过滤,即得矿化培养液。The mineralized nutrient solution is prepared according to the following method: dissolving yeast, peptone, calcium chloride and calcium lactate in deionized water, adjusting the pH, standing still and filtering to obtain the mineralized nutrient solution.
配制矿化营养液时,采用NaOH将矿化培养液的pH调节至9.5~10.5(例如,9.5、10或10.5),静置的时间≥30min。When preparing the mineralized nutrient solution, use NaOH to adjust the pH of the mineralized culture solution to 9.5-10.5 (for example, 9.5, 10 or 10.5), and let it stand for more than 30 minutes.
步骤(1)中,再生骨料在矿化培养液中的浸泡在25~35℃(例如25℃、30℃或35℃)通风环境中进行,浸泡时间为14d;步骤(2)中再生骨料在混合培养液的浸泡在25~35℃(例如25℃、30℃或35℃)通风环境中进行,浸泡时间为7~14d(例如,7d、8d、9d、10d、11d、12d、13d或14d)。上述两步浸泡处理,养护时间较短时不能得到较好的修复效果,养护时间超过7~14d(例如,7d、8d、9d、10d、11d、12d、13d或14d)后,溶液基本丧失矿化沉积碳酸钙的能力。In step (1), the immersion of the regenerated aggregate in the mineralization culture solution is carried out in a ventilated environment at 25-35°C (such as 25°C, 30°C or 35°C), and the immersion time is 14 days; in step (2), the regenerated bone The immersion of the material in the mixed culture solution is carried out in a ventilated environment at 25-35°C (such as 25°C, 30°C or 35°C), and the soaking time is 7-14d (for example, 7d, 8d, 9d, 10d, 11d, 12d, 13d or 14d). The above-mentioned two-step immersion treatment can not get a good repair effect when the curing time is short. After the curing time exceeds 7-14d (for example, 7d, 8d, 9d, 10d, 11d, 12d, 13d or 14d), the solution basically loses minerals. ability to deposit calcium carbonate.
下面通过具体实施例对本发明的利用生物沉积的再生骨料强化方法进行详细说明。The method for strengthening recycled aggregates using biological deposition of the present invention will be described in detail below through specific examples.
下面实施例中,各原材料用量及来源如下表1所示:In the following examples, the amount and source of each raw material are shown in Table 1 below:
表1 所用原材料来源Table 1 Sources of raw materials used
Figure PCTCN2022099669-appb-000001
Figure PCTCN2022099669-appb-000001
下述实施例(或对比例)中用到的菌液按照下述方法配制得到:将胶质芽孢杆菌菌粉6.0g(有效活菌数为6×10 10cfu)和枯草芽孢杆菌0.7g(有效活菌数为1.4×10 11cfu)溶解于500g去离子水中,搅拌10min,加入NaOH调节pH至10,静置30min后过滤,即得上述菌液。 The bacteria solution used in the following examples (or comparative examples) was prepared according to the following method: 6.0 g of Bacillus colloidus bacteria powder (the number of effective viable bacteria was 6×10 10 cfu) and 0.7 g of Bacillus subtilis ( The number of effective viable bacteria is 1.4×10 11 cfu) dissolved in 500 g of deionized water, stirred for 10 minutes, added NaOH to adjust the pH to 10, allowed to stand for 30 minutes, and then filtered to obtain the above bacteria solution.
下述实施例(或对比例)用到的矿化培养液按照下述方法配制得到:将酵母浸粉5g、蛋白胨4g、氯化钙50g和乳酸钙20g溶解于500g去离子水中,加入NaOH调节pH至10.0,静置30min后过滤,即得上述矿化培养液。The mineralized culture solution used in the following examples (or comparative examples) is prepared according to the following method: 5 g of yeast extract powder, 4 g of peptone, 50 g of calcium chloride and 20 g of calcium lactate are dissolved in 500 g of deionized water, and NaOH is added to adjust pH to 10.0, let it stand for 30 minutes and then filter to obtain the above mineralization culture solution.
实施例1Example 1
本实施例的利用生物沉积的再生骨料强化方法包括下述步骤:The regeneration aggregate strengthening method utilizing biological deposition in this embodiment includes the following steps:
(1)填充浸泡:选择再生骨料粒径为9.5~16mm,按照菌液和再生骨料质量比为1:2的比例将菌液加入再生骨料中,置于30℃,真空度为0.8Mpa的真空干燥箱中浸泡30min,将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液中,置于25~35℃通风环境中,养护14d后取出洗净,置于40℃的烘箱中烘干;(1) Filling and soaking: select the particle size of the recycled aggregate to be 9.5-16mm, add the bacterial solution to the recycled aggregate according to the mass ratio of the bacterial solution and the recycled aggregate at a ratio of 1:2, place it at 30°C, and the vacuum degree is 0.8 Soak in a vacuum drying oven of Mpa for 30 minutes, take the recycled aggregate out of the bacterial solution, and then soak it in the mineralized culture solution with a mass ratio of 1:1 to the bacterial solution, and place it in a ventilated environment at 25-35°C for 14 days. Take it out and wash it, and dry it in an oven at 40°C;
(2)修补浸泡:按照矿化培养液和菌液质量比1:1的比例配制混合培养液,然后按照混合培养液和再生骨料质量比为1:1的比例,将经步骤(1)处理得到的再生骨料浸泡于混合培养液中,置于25~35℃通风环境中养护14d;(2) Repair soaking: prepare mixed culture solution according to the mass ratio of mineralization culture solution and bacterial solution of 1:1, and then follow the step (1) according to the ratio of mixed culture solution and recycled aggregate mass ratio of 1:1 Soak the processed recycled aggregate in the mixed culture solution, and place it in a ventilated environment at 25-35°C for 14 days;
之后,取出再生骨料,洗净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其吸水率、表观密度和压碎值,测试结果如表2。After that, take out the recycled aggregate, wash it, put it in an oven at 40°C and dry it to constant weight, weigh the quality change of the recycled aggregate before and after strengthening, and calculate according to GB/T14685-2011 "Pebbles and gravel for construction". It is stipulated to test its water absorption, apparent density and crushing value, and the test results are shown in Table 2.
表2 实施例1制备得到的生物沉积强化再生骨料(9.5~16mm粒径)的基本性能Table 2 Basic properties of the biodeposition-enhanced recycled aggregate (9.5-16mm particle size) prepared in Example 1
Figure PCTCN2022099669-appb-000002
Figure PCTCN2022099669-appb-000002
实施例2Example 2
本实施例的利用生物沉积的再生骨料强化方法包括下述步骤:The regeneration aggregate strengthening method utilizing biological deposition in this embodiment includes the following steps:
(1)填充浸泡:选择再生骨料粒径为9.5~16mm,按照菌液和再生骨料质量比为1.2:2的比例将菌液加入再生骨料中,置于30℃,真空度为0.8Mpa 的真空干燥箱中浸泡30min;将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液中,置于25~35℃通风环境中养护,14d后取出洗净,置于40℃的烘箱中烘干;(1) Filling and soaking: select the particle size of the recycled aggregate to be 9.5-16mm, add the bacterial solution to the recycled aggregate according to the ratio of the mass ratio of the bacterial solution to the recycled aggregate of 1.2:2, place it at 30°C, and the vacuum degree is 0.8 Soak in a vacuum drying oven of Mpa for 30 minutes; take the recycled aggregate out of the bacterial solution and then soak it in the mineralized culture solution with a mass ratio of 1:1 to the bacterial solution, and place it in a ventilated environment at 25-35°C for 14 days Take it out and wash it, and dry it in an oven at 40°C;
(2)修补浸泡:按照矿化培养液和菌液质量比1:1的比例配制混合培养液,然后按照混合培养液和再生骨料质量比为1.2:1的比例,将经步骤(1)处理得到的再生骨料浸泡于混合培养液中,置于25~35℃通风环境中养护14d;(2) Repair soaking: prepare mixed culture solution according to the mass ratio of mineralized culture solution and bacterial solution of 1:1, and then follow the step (1) according to the ratio of mixed culture solution and recycled aggregate mass ratio of 1.2:1 Soak the processed recycled aggregate in the mixed culture solution, and place it in a ventilated environment at 25-35°C for 14 days;
之后取出再生骨料,洗净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其增重、吸水率、表观密度和压碎值,测试结果如表3。After that, take out the recycled aggregate, wash it, and dry it in an oven at 40°C until it reaches a constant weight. Weigh the change in the quality of the recycled aggregate before and after strengthening, and calculate according to the relevant regulations in GB/T14685-2011 "Pebbles and Crushed Stones for Construction". Test its weight gain, water absorption, apparent density and crushing value, and the test results are shown in Table 3.
表3 实施例2制备得到的生物沉积强化再生骨料(9.5~16mm粒径)的基本性能Table 3 Basic properties of biodeposition-enhanced recycled aggregate (9.5-16mm particle size) prepared in Example 2
Figure PCTCN2022099669-appb-000003
Figure PCTCN2022099669-appb-000003
实施例3Example 3
本实施例的利用生物沉积的再生骨料强化方法包括下述步骤:The regeneration aggregate strengthening method utilizing biological deposition in this embodiment includes the following steps:
(1)填充浸泡:选择再生骨料粒径为4.75~9.5mm,按照菌液和再生骨料质量比为1:2的比例将菌液加入再生骨料中,置于30℃,真空度为0.8Mpa的真空干燥箱中浸泡30min,将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液中,置于25~35℃通风环境中,养护14d后取出洗净,置于40℃的烘箱中烘干;(1) Filling and soaking: select the particle size of the recycled aggregate to be 4.75-9.5mm, add the bacterial solution to the recycled aggregate according to the mass ratio of the bacterial solution and the recycled aggregate at a ratio of 1:2, place it at 30°C, and the vacuum degree is Soak in a 0.8Mpa vacuum drying oven for 30 minutes, take the regenerated aggregate out of the bacterial solution, and then soak it in a mineralized culture solution with a mass ratio of 1:1 to the bacterial solution, and place it in a ventilated environment at 25-35°C for curing. After 14 days, take it out and wash it, and dry it in an oven at 40°C;
(2)修补浸泡:按照矿化培养液和菌液质量比1:1的比例配制混合培养液,然后按照混合培养液和再生骨料质量比为1:1的比例,将经步骤(1)处理得到的再生骨料浸泡于混合培养液中,置于25~35℃通风环境中养护14d后取出洗净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其增重、吸水率、表观密度和压碎值,测试结果如表4。(2) Repair soaking: prepare mixed culture solution according to the mass ratio of mineralization culture solution and bacterial solution of 1:1, and then follow the step (1) according to the ratio of mixed culture solution and recycled aggregate mass ratio of 1:1 The processed recycled aggregates were soaked in the mixed culture solution, placed in a ventilated environment at 25-35°C for 14 days, then taken out and washed, dried in an oven at 40°C to constant weight, and the weight of the recycled aggregates before and after strengthening was weighed. Change, and test its weight gain, water absorption, apparent density and crushing value according to the relevant regulations in GB/T14685-2011 "Pebbles and Gravels for Construction". The test results are shown in Table 4.
表4 实施例3制备得到的生物沉积强化再生骨料(4.75~9.5mm粒径)的基本性能Table 4 Basic properties of the biodeposition-enhanced recycled aggregate (4.75-9.5mm particle size) prepared in Example 3
Figure PCTCN2022099669-appb-000004
Figure PCTCN2022099669-appb-000004
实施例4Example 4
本实施例的利用生物沉积的再生骨料强化方法包括下述步骤:The regeneration aggregate strengthening method utilizing biological deposition in this embodiment includes the following steps:
(1)填充浸泡:选择再生骨料粒径为16~19mm,按照菌液和再生骨料质量比为1:2的比例将菌液加入再生骨料中,置于真空干燥箱(真空度为0.6Mpa)中浸泡30min,将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液中,置于25~35℃通风环境中养护14d后取出洗净,置于40℃的烘箱中烘干;(1) Filling and soaking: select the particle size of the recycled aggregate to be 16-19mm, add the bacterial solution to the recycled aggregate according to the mass ratio of the bacterial solution and the recycled aggregate at a ratio of 1:2, and place it in a vacuum drying oven (vacuum degree is 0.6Mpa) for 30 minutes, take out the recycled aggregate from the bacterial solution, then soak it in the mineralized culture solution with a mass ratio of 1:1 to the bacterial solution, place it in a ventilated environment at 25-35°C for 14 days, take it out and wash it. Clean and dry in an oven at 40°C;
(2)修补浸泡:按照矿化培养液和菌液质量比1:1的比例配制混合培养液,然后按照混合培养液和再生骨料质量比为1:1的比例,将经步骤(1)处理得到的再生骨料浸泡于混合培养液中,置于25~35℃通风环境中养护14d;(2) Repair soaking: prepare mixed culture solution according to the mass ratio of mineralization culture solution and bacterial solution of 1:1, and then follow the step (1) according to the ratio of mixed culture solution and recycled aggregate mass ratio of 1:1 Soak the processed recycled aggregate in the mixed culture solution, and place it in a ventilated environment at 25-35°C for 14 days;
之后,取出再生骨料,洗净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其增重、吸水率、表观密度和压碎值,测试结果如表5。After that, take out the recycled aggregate, wash it, put it in an oven at 40°C and dry it to constant weight, weigh the quality change of the recycled aggregate before and after strengthening, and calculate according to GB/T14685-2011 "Pebbles and gravel for construction". It is stipulated to test its weight gain, water absorption, apparent density and crushing value, and the test results are shown in Table 5.
表5 实施例4制备得到的生物沉积强化再生骨料(16~19mm粒径)的基本性能Table 5 Basic properties of the biodeposition-enhanced recycled aggregate (16-19mm particle size) prepared in Example 4
Figure PCTCN2022099669-appb-000005
Figure PCTCN2022099669-appb-000005
对比例1Comparative example 1
对再生骨料进行去离子水浸泡处理,具体步骤如下:Soak the recycled aggregate in deionized water, the specific steps are as follows:
选择3种粒径范围分别为4.75~9.5、9.5~16和16~19的再生骨料,将上述3种再生骨料分别加入与再生骨料质量比为1:1的去离子水中,置于25~35℃通风环境中浸泡再生骨料,浸泡时间为28d;浸泡结束后取出再生骨料,冲洗干净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其增重、吸水率、表观密度和压碎值,测试结果如表6。Three kinds of recycled aggregates with particle sizes ranging from 4.75 to 9.5, 9.5 to 16 and 16 to 19 were selected, and the above three recycled aggregates were added to deionized water with a mass ratio of 1:1 to the recycled aggregate, and placed in Soak the recycled aggregate in a ventilated environment at 25-35°C for 28 days; after soaking, take out the recycled aggregate, rinse it, and dry it in an oven at 40°C to constant weight, and weigh the quality change of the recycled aggregate before and after strengthening , and test its weight gain, water absorption, apparent density and crushing value according to the relevant regulations in GB/T14685-2011 "Pebbles and Gravels for Construction". The test results are shown in Table 6.
表6 去离子水浸泡后再生骨料的基本性能Table 6 Basic properties of recycled aggregates soaked in deionized water
Figure PCTCN2022099669-appb-000006
Figure PCTCN2022099669-appb-000006
Figure PCTCN2022099669-appb-000007
Figure PCTCN2022099669-appb-000007
对比例2Comparative example 2
对再生骨料进行两次修补浸泡处理,具体步骤如下:Repair and soak the recycled aggregate twice, the specific steps are as follows:
(1)第一次修补浸泡:选择再生骨料粒径为9.5,按照矿化培养液和菌液质量比1:1的比例配制混合培养液,然后按照混合培养液和再生骨料质量比为1:1的比例直接浸泡再生骨料,置于25~35℃通风环境中养护14d后取出洗净,置于40℃的烘箱中烘干;(1) The first repair soaking: select the particle size of the recycled aggregate to be 9.5, prepare a mixed culture solution according to the mass ratio of the mineralized culture solution and the bacterial solution at a ratio of 1:1, and then follow the mass ratio of the mixed culture solution and the recycled aggregate to Soak the recycled aggregate directly at a ratio of 1:1, put it in a ventilated environment at 25-35°C for 14 days, take it out, wash it, and dry it in an oven at 40°C;
(2)第二次修补浸泡:再次重复上述步骤,浸泡再生骨料并置于25~35℃通风环境中养护14d(具体方法同上述步骤(1))。养护结束后将再生骨料清洗干净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关规定测试其增重、吸水率、表观密度和压碎值,测试结果如表7。(2) The second repair soaking: Repeat the above steps again, soak the recycled aggregate and place it in a ventilated environment at 25-35°C for 14 days (the specific method is the same as the above step (1)). After curing, clean the recycled aggregate, put it in an oven at 40°C and dry it to constant weight, weigh the quality change of the recycled aggregate before and after strengthening, and calculate according to GB/T14685-2011 "Pebbles and Gravels for Construction" It is stipulated to test its weight gain, water absorption, apparent density and crushing value, and the test results are shown in Table 7.
表7 两次修补浸泡后再生骨料基本性能Table 7 Basic properties of recycled aggregate after two repair immersions
Figure PCTCN2022099669-appb-000008
Figure PCTCN2022099669-appb-000008
对比例3Comparative example 3
对再生骨料进行两次填充浸泡处理,具体步骤如下:Fill and soak the recycled aggregate twice, the specific steps are as follows:
(1)第一次填充浸泡:选择再生骨料粒径为9.5~16mm,按照菌液和再生骨料质量比为1:2的比例将菌液加入再生骨料中,置于真空干燥箱(真空度为0.8MPa)中浸泡30min后取出;将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液,置于25~35℃通风环境中养护14d后取出洗净,置于40℃的烘箱中烘干;(1) Filling and soaking for the first time: select the particle size of the recycled aggregate to be 9.5-16mm, add the bacterial solution to the recycled aggregate according to the mass ratio of the bacterial solution and the recycled aggregate at a ratio of 1:2, and place it in a vacuum drying oven ( Take it out after immersing in a vacuum (0.8MPa) for 30 minutes; take out the recycled aggregate from the bacterial solution, then soak it in the mineralized culture solution with a mass ratio of 1:1 to the bacterial solution, and place it in a ventilated environment at 25-35°C for curing After 14 days, take it out and wash it, and dry it in an oven at 40°C;
(2)第二次填充浸泡:将经上述步骤(1)处理得到的再生骨料按照菌液和再生骨料质量比为1:2的比例将菌液加入菌液中,置于真空干燥箱(真空度为0.8MPa)中浸泡30min后取出;将再生骨料从菌液中取出后再浸泡于和菌液质量比为1:1的矿化培养液,置于25~35℃通风环境中养护14d。养护结束后将再生骨料清洗干净,置于40℃的烘箱中干燥至恒重,称取强化前后再生骨料质量的变化,并根据GB/T14685-2011《建筑用卵石、碎石》内有关 规定测试其增重、吸水率、表观密度和压碎值,测试结果如表8。(2) Filling and soaking for the second time: Add the recycled aggregate obtained by the above step (1) into the bacterial solution according to the mass ratio of the bacterial solution and the recycled aggregate at a ratio of 1:2, and place it in a vacuum drying oven (vacuum degree is 0.8MPa) and take it out after soaking for 30min; Take out the recycled aggregate from the bacteria solution and then soak it in the mineralized culture solution with a mass ratio of 1:1 to the bacteria solution, and place it in a ventilated environment at 25-35°C Conservation 14d. After curing, clean the recycled aggregate, put it in an oven at 40°C and dry it to constant weight, weigh the quality change of the recycled aggregate before and after strengthening, and calculate according to GB/T14685-2011 "Pebbles and Gravels for Construction" It is stipulated to test its weight gain, water absorption, apparent density and crushing value, and the test results are shown in Table 8.
表8 两次填充浸泡后再生骨料基本性能Table 8 Basic properties of recycled aggregates after two filling immersions
Figure PCTCN2022099669-appb-000009
Figure PCTCN2022099669-appb-000009
实验例Experimental example
实验例1Experimental example 1
将胶质芽孢杆菌菌粉6.0g(有效活菌数为6×10 10cfu)和枯草芽孢杆菌0.7g(有效活菌数为1.4×10 11cfu)溶解于500g去离子水中,搅拌10min,加入NaOH调节pH至10,静置30min后过滤,过滤后的菌液和矿化培养液按照1:1的质量比混合(得到本实验例的矿化液),取少量矿化液使用ICP(电感耦合等离子体)测试其钙离子浓度,将剩余溶液在37℃的无菌实验室中养护14d后,再次测试矿化液的钙离子浓度,测试结果如表9。矿化反应前后钙离子浓度变化率为矿化液的矿化率,即溶液产生碳酸钙的能力。 Dissolve 6.0g of Bacillus colloidus powder (the effective number of viable bacteria is 6×10 10 cfu) and 0.7g of Bacillus subtilis (the effective number of viable bacteria is 1.4×10 11 cfu) in 500g of deionized water, stir for 10min, add Adjust the pH to 10 with NaOH, filter after standing for 30min, mix the filtered bacterial solution and mineralized culture solution according to the mass ratio of 1:1 (to obtain the mineralized solution of this experimental example), take a small amount of mineralized solution and use ICP (inductor Coupled plasma) to test its calcium ion concentration, after curing the remaining solution in a sterile laboratory at 37°C for 14 days, the calcium ion concentration of the mineralization solution was tested again, and the test results are shown in Table 9. The change rate of calcium ion concentration before and after the mineralization reaction is the mineralization rate of the mineralization solution, that is, the ability of the solution to produce calcium carbonate.
表9 实验例1制备得到的混合溶液钙离子浓度Table 9 The calcium ion concentration of the mixed solution prepared in Experimental Example 1
Figure PCTCN2022099669-appb-000010
Figure PCTCN2022099669-appb-000010
将14d后的矿化产物置于温度为40℃、真空度为0.06Mpa的真空干燥箱中干燥,干燥时间为24h,制得填充骨料孔隙的重要成分——方解石型碳酸钙。其SEM和XRD测试的结果分别如图1和2所示。The mineralized product after 14 days was dried in a vacuum drying oven at a temperature of 40 °C and a vacuum degree of 0.06 MPa for 24 hours to obtain calcite-type calcium carbonate, an important component for filling aggregate pores. The results of the SEM and XRD tests are shown in Figures 1 and 2, respectively.
实验例2:Experimental example 2:
与实验例1的区别仅在于,所采用的芽孢杆菌全部为胶质芽孢杆菌菌粉(有效活菌数为2×10 11cfu),其余均与实验例1保持一致。采用实验例2的配比矿化反应后得到的混合溶液的钙离子浓度见表10: The only difference from Experimental Example 1 is that all the bacillus used are Bacillus colloidus powder (the effective number of viable bacteria is 2×10 11 cfu), and the rest are consistent with Experimental Example 1. The calcium ion concentration of the mixed solution obtained after adopting the proportioning mineralization reaction of Experimental Example 2 is shown in Table 10:
表10 实验例2制备得到的混合溶液钙离子浓度Calcium ion concentration of the mixed solution prepared in Table 10 Experimental Example 2
Figure PCTCN2022099669-appb-000011
Figure PCTCN2022099669-appb-000011
Figure PCTCN2022099669-appb-000012
Figure PCTCN2022099669-appb-000012
实验例3:Experimental example 3:
与实验例1的区别仅在于,所采用的芽孢杆菌全部为枯草芽孢杆菌菌粉,质量为1g(有效活菌数为2×10 11cfu),其余均与实验例1保持一致。采用实验例3的配比矿化反应后得到的混合溶液的钙离子浓度见表11: The only difference from Experimental Example 1 is that all the bacillus used are Bacillus subtilis powder, with a mass of 1 g (the effective number of viable bacteria is 2×10 11 cfu), and the rest are consistent with Experimental Example 1. The calcium ion concentration of the mixed solution obtained after adopting the proportioning mineralization reaction of Experimental Example 3 is shown in Table 11:
表11 实验例3制备得到的混合溶液钙离子浓度Table 11 Calcium ion concentration of the mixed solution prepared in Experimental Example 3
Figure PCTCN2022099669-appb-000013
Figure PCTCN2022099669-appb-000013
综上所述:(1)对实施例1以及对比例1~3的吸水率和压碎值的检测结果进行汇总,结果如说明书附图图3所示。To sum up: (1) Summarize the testing results of water absorption and crushing values of Example 1 and Comparative Examples 1-3, and the results are shown in Figure 3 of the accompanying drawing.
由图3可知,采用对比例2(两次修补浸泡)和对比例3(两次填充浸泡)的方式对再生骨料进行处理时,再生骨料的性能有所提高(相对于对比例1对再生骨料进行去离子水浸泡处理),但效果相对有限;而实施例1(对再生骨料先进行填充浸泡,再进行修补浸泡)对再生骨料的生物沉积强化效果明显更好,经过实施例1的处理,再生骨料的吸水率相较于对比例1降低了20%左右,压碎值相较于对比例1降低了16.4%左右。It can be seen from Figure 3 that when the recycled aggregate is treated with the methods of Comparative Example 2 (twice repair soaking) and Comparative Example 3 (twice filling soaking), the performance of the recycled aggregate is improved (compared to Comparative Example 1 for Regenerated aggregates are soaked in deionized water), but the effect is relatively limited; and embodiment 1 (filling and soaking the recycled aggregates first, and then repairing and soaking) has a significantly better biodeposition strengthening effect on the recycled aggregates. With the treatment of Example 1, the water absorption of the recycled aggregate decreased by about 20% compared with Comparative Example 1, and the crushing value decreased by about 16.4% compared with Comparative Example 1.
(2)经对比例1~3及实施例1处理后得到的再生骨料的扫描电镜结果如图4所示,其中:(a)为经对比例1处理后得到的再生骨料的扫描电镜图,(b)为经对比例2处理后得到的再生骨料的扫描电镜图,(c)为经对比例3处理后得到的再生骨料的扫描电镜图,(d)为经实施例1处理后得到的再生骨料的扫描电镜图。(2) The scanning electron microscope results of the recycled aggregate obtained after the treatment of Comparative Examples 1 to 3 and Example 1 are shown in Figure 4, wherein: (a) is the scanning electron microscope of the recycled aggregate obtained after the treatment of Comparative Example 1 Figure, (b) is the scanning electron micrograph of the recycled aggregate obtained after the treatment of Comparative Example 2, (c) is the scanning electron micrograph of the recycled aggregate obtained after the treatment of Comparative Example 3, (d) is the scanning electron micrograph of the recycled aggregate obtained after the treatment of Comparative Example 2 Scanning electron micrographs of recycled aggregates obtained after treatment.
由图4可知,对比例1处理后的再生骨料表面结构疏松;对比例2处理后骨料表面被覆盖,但因为两次均为修补浸泡,根据晶体成核理论,二次浸泡时产生的碳酸钙更倾向于以一次浸泡产生的碳酸钙为晶种成核,因此碳酸钙产生的速率较快且形状较为松散;对比例3处理后再生骨料的孔洞中填充着碳酸钙,但骨料表面仍是疏松的结构,骨料的表面形貌并未得到改善;实施例1处理后再生骨料表面被完全覆盖着生物沉积产生的碳酸钙沉淀,球形 的碳酸钙之间紧密连接,少数生长速度较快的碳酸钙依附于球形的碳酸钙表面,骨料表面形貌得到明显改善。It can be seen from Figure 4 that the surface structure of the recycled aggregate after the treatment in Comparative Example 1 is loose; the surface of the aggregate after the treatment in Comparative Example 2 is covered, but because the two times are repair soaking, according to the crystal nucleation theory, the secondary soaking produced Calcium carbonate is more inclined to nucleate with the calcium carbonate produced by one soaking, so the rate of calcium carbonate production is faster and the shape is looser; the pores of the recycled aggregate after treatment in Comparative Example 3 are filled with calcium carbonate, but the aggregate The surface is still a loose structure, and the surface morphology of the aggregate has not been improved; after the treatment in Example 1, the surface of the recycled aggregate is completely covered with calcium carbonate precipitates produced by biodeposition, and the spherical calcium carbonate is closely connected, and a few growth The faster calcium carbonate is attached to the surface of the spherical calcium carbonate, and the surface morphology of the aggregate is significantly improved.
(3)实验例1-3中矿化液分别经矿化反应后的矿化率如图5,溶液的矿化能力决定着生成碳酸钙的量,碳酸钙是修补、增强再生骨料的原材料,溶液矿化率越高生成碳酸钙的量越多,碳酸钙的生成依赖于细菌的生理活动,图5表明,与单一种细菌的菌液相比,当两种细菌复掺使用时,在两种细菌的协同作用下溶液具有更高的矿化率,有助于改善对再生骨料的生物沉积强化效果。(3) The mineralization rate of the mineralization solution after the mineralization reaction in Experimental Examples 1-3 is shown in Figure 5. The mineralization capacity of the solution determines the amount of calcium carbonate generated. Calcium carbonate is a raw material for repairing and strengthening recycled aggregates. , the higher the mineralization rate of the solution, the more calcium carbonate will be produced, and the formation of calcium carbonate depends on the physiological activities of bacteria. The solution has a higher mineralization rate under the synergistic effect of the two bacteria, which helps to improve the biodeposition strengthening effect on the recycled aggregate.

Claims (9)

  1. 一种利用生物沉积的再生骨料强化方法,其特征在于,包括下述步骤:A method for strengthening recycled aggregates utilizing biological deposition, characterized in that it comprises the following steps:
    (1)填充浸泡:先在真空环境下将再生骨料浸泡于菌液中,之后将所述再生骨料从所述菌液中取出,浸泡于矿化培养液中,浸泡结束后将再生骨料取出,清洗,干燥;所述再生骨料在菌液中浸泡的时间为20~60min,所述真空环境的真空度为0.6~0.8Mpa;所述再生骨料与菌液的质量比为2:1~2:1.2,所述矿化培养液与所述菌液的质量比为1:1;(1) Filling and soaking: first soak the regenerated aggregate in the bacterial solution in a vacuum environment, then take out the regenerated aggregate from the bacterial solution, soak it in the mineralization culture solution, and place the regenerated bone after soaking The material is taken out, cleaned, and dried; the soaking time of the regenerated aggregate in the bacterial solution is 20-60min, and the vacuum degree of the vacuum environment is 0.6-0.8Mpa; the mass ratio of the regenerated aggregate to the bacterial solution is 2 : 1~2:1.2, the mass ratio of described mineralization culture fluid and described bacterial fluid is 1:1;
    (2)修补浸泡:将经步骤(1)处理后的再生骨料取出,清洗、干燥后浸泡于所述菌液和矿化培养液的混合培养液中;所述菌液中含有芽孢杆菌;所述再生骨料与所述混合培养液的质量比为1:1~1:1.2;所述混合培养液中菌液与所述矿化培养液的质量比为1:1;(2) Soaking for repairing: taking out the regenerated aggregate treated in step (1), cleaning and drying, and soaking in the mixed culture solution of the bacteria solution and the mineralization culture solution; the bacteria solution contains bacillus; The mass ratio of the regenerated aggregate to the mixed culture solution is 1:1 to 1:1.2; the mass ratio of the bacteria solution in the mixed culture solution to the mineralized culture solution is 1:1;
    所述芽孢杆菌包括胶质芽孢杆菌和枯草芽孢杆菌,两种菌的有效活菌数之比为3:7-7:3。The bacillus includes colloid bacillus and subtilis bacillus, and the ratio of the effective number of viable bacteria of the two kinds of bacteria is 3:7-7:3.
  2. 根据权利要求1所述的利用生物沉积的再生骨料强化方法,其特征在于,The method for strengthening recycled aggregates utilizing biological deposition according to claim 1, characterized in that,
    所述胶质芽孢杆菌来自胶质芽孢杆菌菌粉,所述胶质芽孢杆菌菌粉的有效活菌数为1×10 10cfu/g菌粉; The colloidal bacillus is from the colloidal bacillus bacteria powder, and the effective number of viable bacteria of the colloidal bacillus bacteria powder is 1×10 10 cfu/g bacteria powder;
    所述枯草芽孢杆菌来自枯草芽孢杆菌菌粉,所述枯草芽孢杆菌菌粉的有效活菌数为2×10 11cfu/g菌粉。 The Bacillus subtilis is derived from Bacillus subtilis powder, and the effective number of viable bacteria in the Bacillus subtilis powder is 2×10 11 cfu/g bacteria powder.
  3. 根据权利要求1所述的利用生物沉积的再生骨料强化方法,其特征在于,所述菌液按照下述方法配制得到:将菌粉溶解于去离子水中,搅拌,调节pH,静置后过滤,即得所述菌液。The method for strengthening recycled aggregates utilizing biodeposition according to claim 1, wherein the bacterial solution is prepared according to the following method: dissolving bacterial powder in deionized water, stirring, adjusting pH, and filtering after standing , to obtain the bacterial liquid.
  4. 根据权利要求3所述的利用生物沉积的再生骨料强化方法,其特征在于,配制所述菌液时,所述搅拌的时间为5~15min,采用NaOH将所述菌液的pH调节至9.5~10.5,所述静置的时间≥30min。According to claim 3, the regeneration aggregate strengthening method utilizing biological deposition is characterized in that, when preparing the bacterial solution, the stirring time is 5-15 minutes, and NaOH is used to adjust the pH of the bacterial solution to 9.5 ~10.5, the standing time ≥30min.
  5. 根据权利要求1所述的利用生物沉积的再生骨料强化方法,其特征在 于,所述菌液的细菌浓度为2×10 8~4×10 8cfu/mL。 The method for strengthening recycled aggregates using biological deposition according to claim 1, characterized in that the bacterial concentration of the bacterial solution is 2×10 8 -4×10 8 cfu/mL.
  6. 根据权利要求1所述的利用生物沉积的再生骨料强化方法,其特征在于,所述矿化营养液包括酵母浸粉4~6重量份、蛋白胨3~5重量份、氯化钙45~55重量份、乳酸钙18~22重量份和水500重量份。According to claim 1, the regeneration aggregate strengthening method utilizing biological deposition is characterized in that the mineralized nutrient solution includes 4-6 parts by weight of yeast extract powder, 3-5 parts by weight of peptone, 45-55 parts by weight of calcium chloride parts by weight, 18-22 parts by weight of calcium lactate and 500 parts by weight of water.
  7. 根据权利要求6所述的利用生物沉积的再生骨料强化方法,其特征在于,所述矿化营养液按照下述方法配制得到:将所述酵母、蛋白胨、氯化钙和乳酸钙溶解于去离子水中,调节pH,静置后过滤,即得所述矿化培养液。According to claim 6, the regeneration aggregate strengthening method utilizing biological deposition is characterized in that, the mineralized nutrient solution is prepared according to the following method: dissolving the yeast, peptone, calcium chloride and calcium lactate in desiccated In ionized water, adjust the pH, filter after standing still, and obtain the mineralized culture solution.
  8. 根据权利要求7所述的利用生物沉积的再生骨料强化方法,其特征在于,配制所述矿化营养液时,采用NaOH将所述矿化培养液的pH调节至9.5~10.5,所述静置的时间≥30min。The method for strengthening recycled aggregates using biodeposition according to claim 7, characterized in that when preparing the mineralized nutrient solution, NaOH is used to adjust the pH of the mineralized culture solution to 9.5-10.5, and the static Set time ≥ 30min.
  9. 根据权利要求1-8任一项所述的利用生物沉积的再生骨料强化方法,其特征在于,步骤(1)中,所述再生骨料在矿化培养液中的浸泡在25~35℃通风环境中进行,浸泡时间为7~14d;According to any one of claims 1-8, the method for strengthening recycled aggregates using biological deposition is characterized in that, in step (1), the soaking of the recycled aggregates in the mineralization culture solution is carried out at 25-35°C Carried out in a ventilated environment, the soaking time is 7-14 days;
    和/或,and / or,
    步骤(2)中所述再生骨料在混合培养液的浸泡在25~35℃通风环境中进行,浸泡时间为7~14d。The soaking of the regenerated aggregate in the mixed culture solution in the step (2) is carried out in a ventilated environment at 25-35° C., and the soaking time is 7-14 days.
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