WO2022166297A1 - Heavy metal repair material having ion adsorption coupled to microbial mineralization, preparation method therefor and application thereof - Google Patents
Heavy metal repair material having ion adsorption coupled to microbial mineralization, preparation method therefor and application thereof Download PDFInfo
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- WO2022166297A1 WO2022166297A1 PCT/CN2021/130680 CN2021130680W WO2022166297A1 WO 2022166297 A1 WO2022166297 A1 WO 2022166297A1 CN 2021130680 W CN2021130680 W CN 2021130680W WO 2022166297 A1 WO2022166297 A1 WO 2022166297A1
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 41
- 230000000813 microbial effect Effects 0.000 title claims abstract description 32
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000010802 sludge Substances 0.000 claims abstract description 14
- 244000005700 microbiome Species 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012798 spherical particle Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 9
- 239000010881 fly ash Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract 3
- 150000002500 ions Chemical class 0.000 claims description 32
- 239000010865 sewage Substances 0.000 claims description 19
- 238000005067 remediation Methods 0.000 claims description 14
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 230000000243 photosynthetic effect Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000015424 sodium Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 230000003100 immobilizing effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 241000193395 Sporosarcina pasteurii Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the invention belongs to the interdisciplinary science and technology in the fields of environmental science, material science and microbiology, and relates to a heavy metal repair material with ion adsorption coupled with microbial mineralization, and a preparation method and application thereof.
- the resource treatment methods of dredging mud mainly include dehydration treatment, solidification stabilization treatment and heat treatment; after dehydration treatment, the volume of dredged sludge is reduced, which is easy to follow-up treatment; It enhances the bonding strength between soil particles, and has a physical and chemical stabilization effect on the polluted components in the sludge, which is suitable for large-scale sludge treatment. high value-added products.
- the above method realizes the resource utilization of sludge, there are generally problems such as high cost, complex process, secondary pollution, etc., and it is urgent to develop new methods and technologies for the safe and efficient utilization of sludge.
- Heavy metal pollution is another focus of social concern.
- specific carriers are used to adsorb and fix free heavy metal ions in water pollution treatment, and good results have been achieved.
- Using sludge to prepare porous ceramsite as a carrier can not only solve the problem of safe and efficient utilization of sludge, but also be used to repair heavy metal pollution, which has important research value and practical significance.
- the present invention provides a heavy metal repair material with ion adsorption coupled with microbial mineralization, and a preparation method and application thereof.
- the present invention adopts the following technical solutions to achieve: a heavy metal repair material with ion adsorption coupled with microbial mineralization and its preparation method and application, including the following steps:
- step (1) (2) preparing the synthetic slurry in step (1) into spherical particles with a particle diameter of 1-10 mm by a granulator;
- (3) spherical particle is placed in baking oven to be dried, after drying, place muffle furnace to carry out preheating, roasting to prepare porous carrier;
- the heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, and the heavy metal ion concentration in the sewage is monitored by stirring slowly.
- the proportion of each raw material by weight is: 30-70 parts of silt, 15-25 parts of clay, 10-20 parts of fly ash, 2-5 parts of binder, 1-5 parts of pore-forming agent, tetraoxide 1-5 parts of tri-iron, 1-10 parts of microbial powder.
- the sludge is river bottom sludge that has been dried and dehydrated to constant weight.
- the pore-forming agent is one or a combination of sodium bicarbonate, ammonium bicarbonate and sodium carbonate.
- the microbial powder is one or a combination of Bacillus colloidii, Bacillus pasteurii, photosynthetic bacteria, and Bacillus lysine.
- the drying temperature is 100 ⁇ 10° C. and the drying time is 12-24 hours; it is characterized in that the roasting temperature is 1050 ⁇ 50° C. and the roasting time is 5-10 minutes.
- the weight ratio of the microorganism powder to the porous carrier is (1-10):100.
- a heavy metal repair material with ion adsorption coupled with microbial mineralization the material is prepared by the above method.
- the present invention has the following advantages:
- waste river bottom silt to prepare porous carrier solves the problem of silt occupying land and polluting the environment. It not only provides a safe and economical method for silt utilization, but also provides raw materials for heavy metal pollution remediation, which greatly reduces the cost of environmental treatment. , with significant economic and social benefits;
- the porous carrier prepared by the river silt, the dense pore structure provides a natural space for fixing microorganisms, and creates a prerequisite for the preparation of multifunctional repair materials;
- the repair material prepared by immobilizing microorganisms on the porous carrier can quickly and effectively enrich free heavy metal ions, and at the same time convert free metal ions into stable minerals through microbial mineralization. High long-term stability.
- Fig. 1 is the relation between copper ion concentration and repair time in the sewage in embodiment one;
- Figure 2 shows the relationship between the copper ion concentration in the sewage and the repair time in Example 2.
- the invention provides a heavy metal repair material with ion adsorption coupled with microbial mineralization and a preparation method and application thereof.
- the method steps are as follows:
- the raw materials for preparing the repairing material are prepared by weight: 30 parts of river bottom silt dried and dehydrated to constant weight, 25 parts of clay, 23 parts of fly ash, 2 parts of sodium cellulose as a binder, and 2 parts of sodium bicarbonate as 5 parts of pore-forming agent, 5 parts of ferric oxide;
- the heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, the heavy metal sewage contains 19.80mg/L copper, the weight ratio of the remediation material and the sewage is 5:100, and the mixture is stirred slowly, and the ambient temperature is 35 °C.
- the magnetic carrier is the center to enrich free heavy metal ions, and through microbial mineralization, the free heavy metal ions are converted into stable minerals, and the trend of heavy metal ion concentration in sewage is monitored.
- the raw materials for preparing the repair material are prepared by weight: 50 parts of river bottom silt dried and dehydrated to constant weight, 15 parts of clay, 10 parts of fly ash, sodium cellulose, chitosan, gypsum and other mass ratios are mixed into 5 parts of binder, sodium bicarbonate, ammonium bicarbonate, sodium carbonate and other mass ratios are mixed into 5 parts of pore-forming agent and 5 parts of ferric oxide;
- the heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, the heavy metal sewage contains 19.80mg/L copper, the weight ratio of the remediation material and the sewage is 10:100, and the environment temperature is 35 °C.
- the magnetic carrier is the center to enrich free heavy metal ions, and through microbial mineralization, the free heavy metal ions are converted into stable minerals, and the trend of heavy metal ion concentration in sewage is monitored.
Abstract
The present invention relates to science and technology crossing in the field of environmental science, materials science, and microbiology. Disclosed are a heavy metal repair material having ion adsorption coupled to microbial mineralization, a preparation method therefor and an application thereof. The method comprises the steps of: uniformly mixing the sludge, the clay, the fly ash, a binder, a pore-forming agent, and triiron tetraoxide according to a certain proportion, and then grinding the mixture into powder, adding water and stirring to synthesize the slurry, preparing same into spherical particles having a particle size of 1-10 mm by means of a granulator, placing the spherical particles in a drying oven for drying, and then placing the dried spherical particles in a muffle furnace for preheating and calcining to prepare a porous carrier; and uniformly mixing the microbial powder with the porous carrier, and fully stirring the mixture under a negative pressure condition to obtain the heavy metal repair material of a carrier-immobilized microorganism. According to the present invention, the porous carrier-immobilized microorganism is prepared from the waste river bottom sludge; the heavy metal repair material has the dual functions of adsorption and mineralization, has fast heavy metal pollution repair speed and good heavy metal pollution repair effect, and is high in long-term stability; the cost of environmental governance is greatly reduced by taking wastes as raw materials.
Description
本发明属于环境科学、材料学、微生物学领域交叉的科学技术，涉及一种离子吸附耦合微生物矿化的重金属修复材料及其制备方法和应用。The invention belongs to the interdisciplinary science and technology in the fields of environmental science, material science and microbiology, and relates to a heavy metal repair material with ion adsorption coupled with microbial mineralization, and a preparation method and application thereof.
随着城市化进程不断加快，城市规模逐渐扩大，土地资源越来越稀缺，疏竣淤泥传统粗放的处理方法，不仅占用大量的土地资源，还将污染地下水和大气，引发二次污染。这些处理方法不能适应城市发展的需要，迫切需要寻找资源化、无害化的处理方法。疏凌游泥的资源化处理方法主要包括脱水处理、固化稳定化处理和热处理；经过脱水处理后，疏浚淤泥体积减小，易于后续处理；固化稳定化处理是指通过掺入水泥等固化材料，增强土颗粒之间的胶结强度，并对淤泥中的污染成分有物理化学稳定作用，适用于大规模的疏竣淤泥处理；热处理是通过高温熔融活化的方法，生产出水泥、烧结砖、陶粒等高附加值产品。尽管上述方法实现了淤泥的资源化利用，但普遍存在成本高、工艺复杂、二次污染等问题，亟需开发淤泥安全高效利用的新方法和新技术。With the continuous acceleration of urbanization and the gradual expansion of the scale of cities, land resources are becoming more and more scarce. The traditional and extensive treatment method of dredging and removing silt not only occupies a large amount of land resources, but also pollutes the groundwater and the atmosphere, causing secondary pollution. These treatment methods cannot meet the needs of urban development, and it is urgent to find resource-based and harmless treatment methods. The resource treatment methods of dredging mud mainly include dehydration treatment, solidification stabilization treatment and heat treatment; after dehydration treatment, the volume of dredged sludge is reduced, which is easy to follow-up treatment; It enhances the bonding strength between soil particles, and has a physical and chemical stabilization effect on the polluted components in the sludge, which is suitable for large-scale sludge treatment. high value-added products. Although the above method realizes the resource utilization of sludge, there are generally problems such as high cost, complex process, secondary pollution, etc., and it is urgent to develop new methods and technologies for the safe and efficient utilization of sludge.
重金属污染问题是社会关注的另一个焦点，目前在水污染处理中采用特定载体吸附固定游离态重金属离子，取得了良好的效果。若采用淤泥制备多孔陶粒作为载体，不仅可以解决淤泥安全高效利用问题，还可用于修复重金属污染，具有重要的研究价值和现实意义。Heavy metal pollution is another focus of social concern. At present, specific carriers are used to adsorb and fix free heavy metal ions in water pollution treatment, and good results have been achieved. Using sludge to prepare porous ceramsite as a carrier can not only solve the problem of safe and efficient utilization of sludge, but also be used to repair heavy metal pollution, which has important research value and practical significance.
发明内容SUMMARY OF THE INVENTION
技术问题：针对现有技术存在的不足，本发明提供一种离子吸附耦合微生物矿化的重金属修复材料及其制备方法和应用。Technical problem: In view of the deficiencies in the prior art, the present invention provides a heavy metal repair material with ion adsorption coupled with microbial mineralization, and a preparation method and application thereof.
技术方案：解决上述技术问题，本发明采用如下技术方案来实现：一种离子吸附耦合微生物矿化的重金属修复材料及其制备方法和应用，，包括以下步骤：Technical solution: To solve the above technical problems, the present invention adopts the following technical solutions to achieve: a heavy metal repair material with ion adsorption coupled with microbial mineralization and its preparation method and application, including the following steps:
(1)将淤泥、粘土、粉煤灰、粘结剂、造孔剂、四氧化三铁混合均匀后研磨至粉末状，加水拌合成浆体；(1) Mix silt, clay, fly ash, binder, pore-forming agent, and ferric oxide evenly, grind to powder, add water and mix to form a slurry;
(2)通过造粒机将步骤(1)中的合成浆体制备成粒径为1～10mm的球形颗粒；(2) preparing the synthetic slurry in step (1) into spherical particles with a particle diameter of 1-10 mm by a granulator;
(3)将球形颗粒置于烘箱中干燥，干燥后置于马弗炉进行预热、焙烧制备多孔 载体；(3) spherical particle is placed in baking oven to be dried, after drying, place muffle furnace to carry out preheating, roasting to prepare porous carrier;
(4)将微生物菌粉与多孔载体混合均匀，置于负压条件下充分拌合，拌合时间30～50分钟，获得载体固定微生物的重金属修复材料；(4) Mixing the microbial bacteria powder and the porous carrier evenly, fully mixing under the condition of negative pressure, the mixing time is 30-50 minutes, to obtain the heavy metal repair material with the carrier immobilizing the microorganisms;
(5)将载体固定微生物的重金属修复材料置于含重金属离子的污水中，缓慢搅拌，监测污水中重金属离子浓度。(5) The heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, and the heavy metal ion concentration in the sewage is monitored by stirring slowly.
优选的，各原材料按重量份配比为：淤泥30～70份，粘土15～25份，粉煤灰10～20份，粘结剂2～5份，造孔剂1～5份，四氧化三铁1～5份，微生物菌粉1～10份。Preferably, the proportion of each raw material by weight is: 30-70 parts of silt, 15-25 parts of clay, 10-20 parts of fly ash, 2-5 parts of binder, 1-5 parts of pore-forming agent, tetraoxide 1-5 parts of tri-iron, 1-10 parts of microbial powder.
优选的，所述淤泥为干燥脱水至恒重的河底淤泥。Preferably, the sludge is river bottom sludge that has been dried and dehydrated to constant weight.
优选的，所述造孔剂为碳酸氢钠、碳酸氢铵、碳酸钠中的一种或几种组合。Preferably, the pore-forming agent is one or a combination of sodium bicarbonate, ammonium bicarbonate and sodium carbonate.
优选的，所述微生物菌粉为胶质芽孢杆菌、巴氏芽孢杆菌、光合菌、赖氨酸芽孢杆菌中的一种或几种的组合。Preferably, the microbial powder is one or a combination of Bacillus colloidii, Bacillus pasteurii, photosynthetic bacteria, and Bacillus lysine.
优选的，步骤(3)中所述干燥温度100±10℃、干燥时间12～24小时；其特征在于，所述焙烧温度1050±50℃、焙烧时间5～10分钟。Preferably, in step (3), the drying temperature is 100±10° C. and the drying time is 12-24 hours; it is characterized in that the roasting temperature is 1050±50° C. and the roasting time is 5-10 minutes.
优选的，步骤(4)中所述微生物菌粉与多孔载体的重量比为(1～10)：100。Preferably, in step (4), the weight ratio of the microorganism powder to the porous carrier is (1-10):100.
一种离子吸附耦合微生物矿化的重金属修复材料的应用，所述离子吸附耦合微生物矿化的重金属修复材料与污水的重量比为(1～10):100混合。An application of a heavy metal repair material with ion adsorption coupled with microbial mineralization, wherein the weight ratio of the heavy metal repair material with ion adsorption coupled with microbial mineralization and sewage is (1-10):100.
一种离子吸附耦合微生物矿化的重金属修复材料，该材料由上述方法制备而成。A heavy metal repair material with ion adsorption coupled with microbial mineralization, the material is prepared by the above method.
有益效果：本发明与现有技术相比，具有以下优点：Beneficial effect: Compared with the prior art, the present invention has the following advantages:
1、采用废弃物河底淤泥制备多孔载体，解决了淤泥占用土地、污染环境的问题，不仅为淤泥利用提供了安全经济的方法，而且可以为重金属污染修复提供原材料，大大降低了环境治理的成本，经济社会效益显著；1. The use of waste river bottom silt to prepare porous carrier solves the problem of silt occupying land and polluting the environment. It not only provides a safe and economical method for silt utilization, but also provides raw materials for heavy metal pollution remediation, which greatly reduces the cost of environmental treatment. , with significant economic and social benefits;
2、采用河道淤泥制备的多孔载体，致密的孔道结构为固定微生物提供了天然的空间，为多功能的修复材料的制备创造了前提条件；2. The porous carrier prepared by the river silt, the dense pore structure provides a natural space for fixing microorganisms, and creates a prerequisite for the preparation of multifunctional repair materials;
3、多孔载体固定微生物制备的修复材料，可快速有效富集游离态重金属离子，同时通过微生物矿化将游离态金属离子转化为稳定的矿物，兼具吸附矿化双重功能，修复速度快、效果好、长期稳定性高。3. The repair material prepared by immobilizing microorganisms on the porous carrier can quickly and effectively enrich free heavy metal ions, and at the same time convert free metal ions into stable minerals through microbial mineralization. High long-term stability.
图1为实施例一中污水中铜离子浓度与修复时间的关系；Fig. 1 is the relation between copper ion concentration and repair time in the sewage in embodiment one;
图2为实施例二中污水中铜离子浓度与修复时间的关系。Figure 2 shows the relationship between the copper ion concentration in the sewage and the repair time in Example 2.
本发明提供一种离子吸附耦合微生物矿化的重金属修复材料及其制备方法和应用，方法步骤如下：The invention provides a heavy metal repair material with ion adsorption coupled with microbial mineralization and a preparation method and application thereof. The method steps are as follows:
实例一：Example one:
(1)将制备修复材料的原材料按重量份配制：干燥脱水至恒重的河底淤泥30份，粘土25份，粉煤灰23份，纤维素钠为粘结剂2份，碳酸氢钠为造孔剂5份，四氧化三铁5份；(1) The raw materials for preparing the repairing material are prepared by weight: 30 parts of river bottom silt dried and dehydrated to constant weight, 25 parts of clay, 23 parts of fly ash, 2 parts of sodium cellulose as a binder, and 2 parts of sodium bicarbonate as 5 parts of pore-forming agent, 5 parts of ferric oxide;
(2)将淤泥、粘土、粉煤灰、粘结剂纤维素钠、造孔剂碳酸氢钠、四氧化三铁混合均匀后研磨至粉末状，加水拌合成浆体，通过造粒机制备粒径为1～10mm的球形颗粒，将球形颗粒置于烘箱中干燥，干燥温度110℃、干燥时间24小时，干燥后置于马弗炉进行预热、焙烧，焙烧温度1050℃、焙烧时间10分钟，自然冷却至常温即获得多孔载体；(2) Mix the sludge, clay, fly ash, sodium cellulose as a binder, sodium bicarbonate as a pore-forming agent, and ferric tetroxide evenly, then grind it to a powdery state, add water and mix it into a slurry, and prepare granules by a granulator. Spherical particles with a diameter of 1 to 10 mm are dried in an oven at a drying temperature of 110 °C and a drying time of 24 hours. After drying, they are placed in a muffle furnace for preheating and roasting. The roasting temperature is 1050 °C and the roasting time is 10 minutes. , the porous carrier is obtained by natural cooling to room temperature;
(3)将光合菌粉10份与多孔载体100份混合均匀，置于负压条件下充分拌合，拌合时间50分钟，获得载体固定微生物的重金属修复材料；(3) 10 parts of photosynthetic bacteria powder and 100 parts of porous carrier are mixed uniformly, placed under negative pressure condition and fully mixed, and the mixing time is 50 minutes to obtain the heavy metal repair material of the carrier-fixed microorganism;
(4)将载体固定微生物的重金属修复材料置于含重金属离子的污水中，重金属污水含19.80mg/L铜，修复材料与污水的重量比为5:100，缓慢搅拌，环境温度35℃，以磁性载体为中心富集游离态重金属离子，并通过微生物矿化将游离态重金属离子转化为稳定的矿物，监测污水中重金属离子浓度变化趋势。(4) The heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, the heavy metal sewage contains 19.80mg/L copper, the weight ratio of the remediation material and the sewage is 5:100, and the mixture is stirred slowly, and the ambient temperature is 35 °C. The magnetic carrier is the center to enrich free heavy metal ions, and through microbial mineralization, the free heavy metal ions are converted into stable minerals, and the trend of heavy metal ion concentration in sewage is monitored.
实例二：Example two:
(1)将制备修复材料的原材料按重量份配制：干燥脱水至恒重的河底淤泥50份，粘土15份，粉煤灰10份，纤维素钠、壳聚糖、石膏等质量比例混合为粘结剂5份，碳酸氢钠、碳酸氢铵、碳酸钠等质量比例混合为造孔剂5份，四氧化三铁5份；(1) The raw materials for preparing the repair material are prepared by weight: 50 parts of river bottom silt dried and dehydrated to constant weight, 15 parts of clay, 10 parts of fly ash, sodium cellulose, chitosan, gypsum and other mass ratios are mixed into 5 parts of binder, sodium bicarbonate, ammonium bicarbonate, sodium carbonate and other mass ratios are mixed into 5 parts of pore-forming agent and 5 parts of ferric oxide;
(2)将淤泥、粘土、粉煤灰、粘结剂、造孔剂、四氧化三铁混合均匀后研磨至粉末状，加水拌合成浆体，通过造粒机制备粒径为1～10mm的球形颗粒，将球形颗粒置于烘箱中干燥，干燥温度110℃、干燥时间24小时，干燥后置于马弗炉进行预热、焙烧，焙烧温度1050℃、焙烧时间10分钟，自然冷却至常温即获得多孔载体；(2) Mix silt, clay, fly ash, binder, pore-forming agent, and ferric oxide evenly, then grind to powder, add water and mix to form a slurry, and prepare a pellet with a particle size of 1 to 10 mm by a granulator. Spherical particles, the spherical particles are dried in an oven, the drying temperature is 110 ° C, and the drying time is 24 hours. After drying, they are placed in a muffle furnace for preheating and roasting. The roasting temperature is 1050 ° C and the roasting time is 10 minutes. Natural cooling to room temperature obtain a porous carrier;
(3)将胶质芽孢杆菌、巴氏芽孢杆菌、光合菌、赖氨酸芽孢杆菌等质量比例混 合为微生物菌粉10份，与多孔载体100份混合均匀，置于负压条件下充分拌合，拌合时间50分钟，获得载体固定微生物的重金属修复材料；(3) Mix the mass ratio of Bacillus colloid, Bacillus pasteuri, photosynthetic bacteria, Bacillus lysine into 10 parts of microbial bacteria powder, mix it with 100 parts of porous carrier evenly, and fully mix under negative pressure conditions , the mixing time is 50 minutes, and the heavy metal repair material with the carrier immobilized microorganisms is obtained;
(4)将载体固定微生物的重金属修复材料置于含重金属离子的污水中，重金属污水含19.80mg/L铜，修复材料与污水的重量比为10:100，缓慢搅拌，环境温度35℃，以磁性载体为中心富集游离态重金属离子，并通过微生物矿化将游离态重金属离子转化为稳定的矿物，监测污水中重金属离子浓度变化趋势。(4) The heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, the heavy metal sewage contains 19.80mg/L copper, the weight ratio of the remediation material and the sewage is 10:100, and the environment temperature is 35 ℃. The magnetic carrier is the center to enrich free heavy metal ions, and through microbial mineralization, the free heavy metal ions are converted into stable minerals, and the trend of heavy metal ion concentration in sewage is monitored.
由附图1及图2中污水中铜离子浓度与修复时间的关系数据可知，本发明所述材料在重金属污水修复上具有较佳的效果，可以在50小时内去除污水中带份的重金属污染物。It can be seen from the relationship data between the copper ion concentration and the repair time in the sewage in the accompanying drawings 1 and 2 that the material of the present invention has a better effect in the repair of heavy metal sewage, and can remove the heavy metal pollution in the sewage within 50 hours. thing.
Claims (10)
- 一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，包括以下步骤：A method for preparing a heavy metal repair material with ion adsorption coupled with microbial mineralization, characterized in that it comprises the following steps:(1)将淤泥、粘土、粉煤灰、粘结剂、造孔剂、四氧化三铁混合均匀后研磨至粉末状，加水拌合成浆体；(1) Mix silt, clay, fly ash, binder, pore-forming agent, and ferric oxide evenly, grind to powder, add water and mix to form a slurry;(2)通过造粒机将步骤(1)中的合成浆体制备成粒径为1～10mm的球形颗粒；(2) preparing the synthetic slurry in step (1) into spherical particles with a particle diameter of 1-10 mm by a granulator;(3)将球形颗粒置于烘箱中干燥，干燥后置于马弗炉进行预热、焙烧制备多孔载体；(3) the spherical particles are placed in an oven to be dried, and after drying, they are placed in a muffle furnace for preheating and roasting to prepare a porous carrier;(4)将微生物菌粉与多孔载体混合均匀，置于负压条件下充分拌合，拌合时间30～50分钟，获得载体固定微生物的重金属修复材料；(4) Mixing the microbial bacteria powder and the porous carrier evenly, fully mixing under the condition of negative pressure, the mixing time is 30-50 minutes, to obtain the heavy metal repair material with the carrier immobilizing the microorganisms;(5)将载体固定微生物的重金属修复材料置于含重金属离子的污水中，缓慢搅拌，监测污水中重金属离子浓度。(5) The heavy metal remediation material with the carrier immobilized microorganisms is placed in the sewage containing heavy metal ions, and the heavy metal ion concentration in the sewage is monitored by stirring slowly.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，各原材料按重量份配比为：淤泥30～70份，粘土15～25份，粉煤灰10～20份，粘结剂2～5份，造孔剂1～5份，四氧化三铁1～5份，微生物菌粉1～10份。The method for preparing a heavy metal remediation material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the proportion of each raw material by weight is: 30-70 parts of silt, 15-25 parts of clay, and pulverized coal. 10-20 parts of ash, 2-5 parts of binder, 1-5 parts of pore-forming agent, 1-5 parts of ferric oxide, 1-10 parts of microbial powder.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，所述淤泥为干燥脱水至恒重的河底淤泥。The method for preparing a heavy metal remediation material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the sludge is river bottom sludge that has been dried and dehydrated to a constant weight.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，所述粘结剂为纤维素钠、壳聚糖、石膏中的一种或几种组合。The method for preparing a heavy metal repair material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the binder is one or more combinations of sodium cellulose, chitosan and gypsum .
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，所述造孔剂为碳酸氢钠、碳酸氢铵、碳酸钠中的一种或几种组合。The method for preparing a heavy metal repair material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the pore-forming agent is one or more of sodium bicarbonate, ammonium bicarbonate and sodium carbonate combination.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，所述微生物菌粉为胶质芽孢杆菌、巴氏芽孢杆菌、光合菌、赖氨酸芽孢杆菌中的一种或几种的组合。The method for preparing a heavy metal remediation material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the microbial powder is Bacillus colloid, Bacillus pasteuri, photosynthetic bacteria, lysine spores Bacillus one or a combination of several.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，步骤(3)中所述干燥温度100±10℃、干燥时间12～24小时；其特征在于，所述焙烧温度1050±50℃、焙烧时间5～10分钟。The method for preparing a heavy metal remediation material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the drying temperature in step (3) is 100±10°C and the drying time is 12-24 hours; That is, the calcination temperature is 1050±50°C, and the calcination time is 5-10 minutes.
- 根据权利要求1所述的一种离子吸附耦合微生物矿化的重金属修复材料的制备方法，其特征在于，步骤(4)中所述微生物菌粉与多孔载体的重量比为(1～10)：100。The method for preparing a heavy metal remediation material with ion adsorption coupled with microbial mineralization according to claim 1, wherein the weight ratio of the microbial powder to the porous carrier in step (4) is (1-10): 100.
- 一种离子吸附耦合微生物矿化的重金属修复材料的应用，其特征在于，所述离子吸附耦合微生物矿化的重金属修复材料与污水的重量比为(1～10):100混合。An application of a heavy metal remediation material with ion adsorption coupled with microbial mineralization, characterized in that the weight ratio of the ion adsorption coupled with microbial mineralization heavy metal restoration material with sewage is (1-10):100.
- 一种离子吸附耦合微生物矿化的重金属修复材料，其特征在于，该材料由权利要求1至8任一项所述的方法制备而成。A heavy metal remediation material with ion adsorption coupled with microbial mineralization, characterized in that the material is prepared by the method according to any one of claims 1 to 8.
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| CN113209944A (en) * | 2021-05-21 | 2021-08-06 | 浙江华东建设工程有限公司 | Heavy metal passivator for immobilizing microorganisms on attapulgite-based carrier and preparation method thereof |
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