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CN107434305A - A kind of water purification agent of rich defect carbon carrier fixation of microbe and preparation method thereof - Google Patents

A kind of water purification agent of rich defect carbon carrier fixation of microbe and preparation method thereof Download PDF

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CN107434305A
CN107434305A CN201710910358.1A CN201710910358A CN107434305A CN 107434305 A CN107434305 A CN 107434305A CN 201710910358 A CN201710910358 A CN 201710910358A CN 107434305 A CN107434305 A CN 107434305A
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water
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CN107434305B (en
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李洁
肖艳春
陈浩霖
黄婧
陈彪
张燕青
陈阳
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Fujian Academy Of Agricultural Sciences Agricultural Product Processing Research Institute
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Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/347Use of yeasts or fungi
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F2003/001Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C02F2003/003Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like

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  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
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Abstract

本发明属于微生物净水剂技术领域,具体涉及一种富缺陷碳载体固定微生物的净水剂及其制备方法。将富缺陷碳载体置于培养基中,同时将复合菌株接种至培养基,经振荡共培养制得净水剂。由于该净水剂的碳载体表面有含氧官能团,克服了一般炭载体的疏水性问题,且碳载体表面富含缺陷和二次孔隙结构,为吸附反应提供了更多的活性位点,提高了污染物的吸附效率;含有亲水性基团的富缺陷碳载体与微生物共培养有利于碳载体对微生物的吸附固定,同时载体碳上吸附的有机质和污染物分别被微生物高效利用和协同降解,所以该净水剂具有亲水但易于沉淀的特点、碳吸附与生物降解的双重净化作用等优点,非常适用于养殖厌氧污水的规模化处理。The invention belongs to the technical field of microbial water purifiers, and in particular relates to a water purifier for immobilizing microorganisms on a defect-rich carbon carrier and a preparation method thereof. The defect-rich carbon carrier is placed in the culture medium, and the compound strain is inoculated into the culture medium at the same time, and the water purifying agent is obtained through shaking co-cultivation. Because the surface of the carbon carrier of the water purifier has oxygen-containing functional groups, it overcomes the hydrophobicity problem of the general carbon carrier, and the surface of the carbon carrier is rich in defects and secondary pore structures, providing more active sites for the adsorption reaction and improving The adsorption efficiency of pollutants is improved; the co-cultivation of defect-rich carbon carriers containing hydrophilic groups and microorganisms is beneficial to the adsorption and fixation of microorganisms by carbon carriers, and at the same time, the organic matter and pollutants adsorbed on the carrier carbon are efficiently utilized and synergistically degraded by microorganisms, respectively. , so the water purifier has the characteristics of being hydrophilic but easy to precipitate, and has the advantages of double purification of carbon adsorption and biodegradation, and is very suitable for large-scale treatment of aquaculture anaerobic sewage.

Description

一种富缺陷碳载体固定微生物的净水剂及其制备方法A water purifying agent for immobilizing microorganisms on a defect-rich carbon carrier and its preparation method

技术领域technical field

本发明属于微生物净水剂技术领域,具体涉及一种富缺陷碳载体固定微生物的净水剂及其制备方法。The invention belongs to the technical field of microbial water purifiers, and in particular relates to a water purifier for immobilizing microorganisms on a defect-rich carbon carrier and a preparation method thereof.

技术背景technical background

畜牧业规模化发展中,统一的管理,降低了成本,提高了经济效益,但大量集中的污水排放引起的严重环境污染,急需治理。国内外对养殖污水处理方式主要有资源化利用和达标排放两大类,归纳为还田模式、自然处理模式及工业化处理3种模式,它们各有优缺点。我国养殖污水处理的目的是控制、减少其造成的危害,开展综合利用,最终实现减量化、资源化、无害化和达标排放的目标,减少对作物土壤质量和作物品质的影响,降低对水体、土壤环境和气候环境的潜在污染风险。In the large-scale development of animal husbandry, unified management has reduced costs and improved economic benefits, but serious environmental pollution caused by a large number of concentrated sewage discharges requires urgent treatment. At home and abroad, there are two main types of aquaculture sewage treatment methods: resource utilization and standard discharge, which can be classified into three types: returning to the field, natural treatment and industrial treatment, each of which has its own advantages and disadvantages. The purpose of my country's aquaculture sewage treatment is to control and reduce the harm caused by it, carry out comprehensive utilization, and finally achieve the goals of reduction, recycling, harmless and standard discharge, reduce the impact on crop soil quality and crop quality, and reduce the impact on crop soil quality. Potential pollution risks of water body, soil environment and climate environment.

近年来研究者们针对农业环境污染物的性质特征,对养殖污水的处理方法和工艺都进行了较系统的研究,分别利用了化学方法和生物方法对氮、磷、重金属离子及有机物分子进行吸附、分离及生物/化学降解,单一的处理方式一定程度上实现了减量化和资源化的目标,但很难达到完全无害化和国家排放标准。在研究过程中,活性炭通常被用作污水污染物的吸附剂,它对于污水的色度和浊度都能有所改观,同时含有大孔、中孔及微孔结构,故对于小分子和重金属离子也会发生吸附作用,亦可被压制成柱状小颗粒作为生物净水剂的载体用于畜禽类养殖厌氧沼液的净化处理,且单一菌株固定于碳载体形成的菌碳净水剂,其污水净化效果往往不如复合菌株形成的菌碳净化效果理想。公布号为CN 104261570 A的专利公开了一种畜禽养殖厌氧污水净化剂,由复合微生物菌株与活性炭载体组成,所述活性炭载体为煤质柱状活性炭,是以2-10目的煤质活性炭经过定型制成的实心圆柱状活性炭。所用的煤质活性炭以及市售的碳材料(活性炭AC、碳纳米管CNT、石墨GC等)均有着诸多优点,如孔隙度高、比表面大、稳定性好、无毒无污染-环境友好等;但其表面官能团较少,不含亲水性基团(-COOH、-OH),故净化剂在水中分散性较差,阻碍了与污水中污染物的充分接触,而且与含氢键及孤电子对的氨氮物质很难发生静电相互作用,不能完全发挥碳基载体对污染物的吸附作用,因此对碳材料的表面亲/疏水性的调控是显得非常必要。目前常用的方法是使用浓酸(浓HNO3、浓H2SO4)使惰性的炭表面活化并使表面炭氧化形成含氧官能团(-COOH、-OH、-C=O),同时产生有污染的氮氧化物及硫氧化物,造成二次污染;以及利用600-900℃左右高温状态下的碱在惰性气体环境中与碳发生反应,刻蚀出二次孔隙结构及表面活性位点,这些方法反应条件苛刻且要求反应容器耐酸碱及高温,在实际操作及应用过程中都存在许多不足。In recent years, according to the characteristics of agricultural environmental pollutants, researchers have conducted systematic research on the treatment methods and processes of aquaculture sewage, using chemical methods and biological methods to adsorb nitrogen, phosphorus, heavy metal ions and organic molecules. , separation and biological/chemical degradation, a single treatment method has achieved the goal of reduction and resource utilization to a certain extent, but it is difficult to achieve complete harmlessness and national emission standards. In the research process, activated carbon is usually used as an adsorbent for sewage pollutants. It can improve the color and turbidity of sewage, and it also contains macropores, mesopores and micropores, so it is suitable for small molecules and heavy metals. Ions can also undergo adsorption, and can also be pressed into small columnar particles as the carrier of biological water purifiers for the purification of anaerobic biogas slurry in livestock and poultry breeding, and a single bacterial strain is fixed on the carbon carrier to form a bacterial carbon water purifier , its sewage purification effect is often not as ideal as the bacterial carbon purification effect formed by compound strains. The patent with the publication number CN 104261570 A discloses an anaerobic sewage purifier for livestock and poultry breeding, which is composed of a composite microbial strain and an activated carbon carrier. Solid cylindrical activated carbon made by shaping. The coal-based activated carbon used and commercially available carbon materials (activated carbon AC, carbon nanotube CNT, graphite GC, etc.) have many advantages, such as high porosity, large specific surface, good stability, non-toxic and non-polluting-environmentally friendly, etc. ; but its surface has fewer functional groups and does not contain hydrophilic groups (-COOH, -OH), so the dispersion of the purifying agent in water is poor, which hinders full contact with pollutants in sewage, and has hydrogen bonds and Ammonia-nitrogen substances with lone electron pairs are difficult to interact electrostatically and cannot fully exert the adsorption effect of carbon-based supports on pollutants. Therefore, it is very necessary to control the surface affinity/hydrophobicity of carbon materials. At present, the commonly used method is to use concentrated acid (concentrated HNO 3 , concentrated H 2 SO 4 ) to activate the surface of inert carbon and oxidize the surface carbon to form oxygen-containing functional groups (-COOH, -OH, -C=O). Polluted nitrogen oxides and sulfur oxides cause secondary pollution; and use alkali at a high temperature of about 600-900°C to react with carbon in an inert gas environment to etch out secondary pore structures and surface active sites, These methods have harsh reaction conditions and require the reaction vessel to be resistant to acid, alkali and high temperature, and there are many deficiencies in the actual operation and application process.

发明内容Contents of the invention

本发明的目的在于针对现有技术的不足,提供一种富缺陷碳载体固定微生物的净水剂及其制备方法。所用的碳载体富含亲水性基团,使净化剂与水有了更好的相溶性,克服了一般炭载体的疏水性问题,并且更有利于微生物菌株的吸附固定,与污染物之间的接触性更好,提高了污染物的吸附效率,且因富含二次孔隙结构及表面活性位点,增加了对污染物的吸附。该富缺陷碳载体固定微生物的净水剂具有碳吸附与生物降解的双重净化作用,同时实现了微生物对有机质的循环利用和对污染物的协同高效降解。The object of the present invention is to provide a water purifier for immobilizing microorganisms on a defect-rich carbon carrier and a preparation method thereof in view of the deficiencies in the prior art. The carbon carrier used is rich in hydrophilic groups, which makes the purifier have better compatibility with water, overcomes the hydrophobicity problem of general carbon carriers, and is more conducive to the adsorption and fixation of microbial strains. The contact is better, the adsorption efficiency of pollutants is improved, and the adsorption of pollutants is increased due to the rich secondary pore structure and surface active sites. The water purifier for immobilizing microorganisms on the defect-rich carbon carrier has double purification functions of carbon adsorption and biodegradation, and simultaneously realizes the recycling of organic matter by microorganisms and the synergistic and efficient degradation of pollutants.

为实现上述发明目的,本发明采用如下技术方案:In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

一种富缺陷碳载体固定微生物的净水剂:将富缺陷碳载体置于Luria-Bertani培养基中,同时将复合菌株接种至Luria-Bertani培养基,经振荡共培养、烘干后,制得净水剂;所述的富缺陷碳载体的制备方法包括以下步骤:A water purifying agent for immobilizing microorganisms with defect-rich carbon carriers: the defect-rich carbon carrier is placed in Luria-Bertani medium, and the compound strain is inoculated into Luria-Bertani medium at the same time, co-cultivated by shaking and dried to obtain Water purifying agent; the preparation method of described defect-rich carbon carrier comprises the following steps:

(1)将90g NaOH和KOH的混合碱置于200 ml反应釜内胆中,置于 165℃下熔融2h,得澄清熔融碱液;(1) Put 90g of mixed alkali of NaOH and KOH in a 200 ml reactor liner, and melt it at 165°C for 2 hours to obtain a clarified molten alkali;

(2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应12小时,生成富缺陷粉末碳前驱体材料;(2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 12 hours to generate defect-rich powder carbon precursor materials;

(3)碳前驱体材料依次经水、无水乙醇洗涤后,于80℃干燥12h得粉末碳前驱体;(3) After the carbon precursor material was washed with water and absolute ethanol in sequence, it was dried at 80°C for 12 hours to obtain a powder carbon precursor;

(4)将粉末碳前驱体置于300℃马弗炉中煅烧2h,得多孔富缺陷碳粉末材料(总孔容积约0.05~0.06 cm3/g);(4) The powdered carbon precursor was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous and defect-rich carbon powder material (total pore volume about 0.05-0.06 cm 3 /g);

(5)将多孔富缺陷碳粉末材料分散于乙醇中,然后在分散液中滴入聚乙二醇,充分搅拌形成胶状物后,压制成型,制成微生物净水剂的碳载体。(5) Disperse the porous defect-rich carbon powder material in ethanol, then drop polyethylene glycol into the dispersion liquid, stir well to form a jelly, and press it to make the carbon carrier of the microbial water purifier.

所述的Luria-Bertani培养基的配方为:胰蛋白胨10g,酵母提取物5g,NaCl 10g,蒸馏水1000 mL,pH 7.0。The formula of the Luria-Bertani medium is: tryptone 10g, yeast extract 5g, NaCl 10g, distilled water 1000 mL, pH 7.0.

步骤(1)中所述的混合碱中NaOH和KOH的质量比为46.5:43.5。The mass ratio of NaOH and KOH in the mixed alkali described in step (1) is 46.5:43.5.

一种制备如上所述的富缺陷碳载体固定微生物的净水剂的方法:将10g富缺陷碳载体加入到50-150 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为1-2%,在4℃、150 rpm条件下振荡共培养48~72h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为7×108~6×109 CFU/g,菌碳结合率达到97.8%。A method for preparing a water purifying agent for immobilizing microorganisms with a rich-deficient carbon carrier as described above: 10g of a rich-defective carbon carrier is added to 50-150 ml Luria-Bertani medium, and Bacillus licheniformis , marsh red false Rhodop seudanonas palustris , Chlorella vulgaris , Streptococcus , Thiobacillus Thiooxidant were inoculated into Luria-Bertani medium at a mass ratio of 4:5:1:4:1, and the inoculation amount of the composite strain was 1 -2%, shake and co-culture at 4°C and 150 rpm for 48-72 hours, and finally remove the carbon carrier and dry it in a constant temperature box at 4°C to obtain the water purifier; the effective number of viable bacteria on the carbon carrier is 7×10 8 ~6×10 9 CFU/g, the bacterial carbon binding rate reached 97.8%.

在富缺陷碳载体与微生物共培养过程中,亲水性的革兰氏阴性菌(氧化硫杆菌/沼泽红假单胞菌)因细胞表面成份主要为脂多糖类而显电正性,可通过静电相互作用吸附固定于带负电基团的碳载体上;而革兰氏阳性菌(小球藻/芽孢杆菌/链球菌)的细胞壁由一层厚而致密的5个甘氨酸交联的肽聚糖和磷壁酸组成,表面的负电性使其呈现疏水性,在培养生长早期可利用其疏水性在营养液中扩散,获得多种资源以满足增殖需求,在生长进程中微生物疏水性下降使其可在水体自由浮游而免受环境胁迫,提高存活能力,进入生长后期微生物亲水性进一步增加,便于吸附固定于带负电基团的亲水性碳载体上,由此可见,含亲水性官能团的碳载体有利于微生物菌株的吸附固定。During the co-cultivation process of defect-rich carbon carriers and microorganisms, hydrophilic Gram-negative bacteria (Thiobacillus oxidans/Rhodopseudomonas palustris) are electropositive because the cell surface components are mainly lipopolysaccharides, which can It is adsorbed and fixed on the carbon carrier with negatively charged groups through electrostatic interaction; while the cell wall of Gram-positive bacteria (Chlorella/Bacillus/Streptococcus) is composed of a thick and dense layer of 5 glycine cross-linked peptide polymers Composed of sugar and teichoic acid, the negative charge on the surface makes it hydrophobic. In the early stage of culture and growth, its hydrophobicity can be used to diffuse in the nutrient solution, and a variety of resources can be obtained to meet the needs of proliferation. During the growth process, the hydrophobicity of microorganisms decreases so that It can float freely in water without environmental stress, improve survival ability, and further increase the hydrophilicity of microorganisms in the late growth stage, which is convenient for adsorption and fixation on hydrophilic carbon carriers with negatively charged groups. Carbon supports with functional groups are beneficial to the adsorption and immobilization of microbial strains.

一种如上所述的富缺陷碳载体固定微生物的净水剂保存于4℃条件下,使用前在常温下放置8-12小时恢复生物活性后在处理养殖厌氧污水方面的应用。A water purifier for immobilizing microorganisms on a defect-rich carbon carrier as described above is stored at 4°C and placed at room temperature for 8-12 hours before use to restore biological activity and is used in the treatment of aquaculture anaerobic sewage.

上述原料中采用的菌种可以由本领域技术人员通过常规菌种鉴定分离方法方便地从自然界分离得到的,或通过商业渠道公开购买的菌种。本发明采用的菌种可从中国微生物菌种网-北京北纳创联生物技术研究院等供应商处购买获得。The strains used in the above raw materials can be conveniently isolated from nature by those skilled in the art through conventional strain identification and isolation methods, or strains publicly purchased through commercial channels. The strains used in the present invention can be purchased from suppliers such as China Microbial Strains Network - Beijing Beina Chuanglian Biotechnology Research Institute.

上述菌种根据现有常规方法培养:Above-mentioned bacterial classification is cultivated according to existing routine method:

Ⅰ地衣芽孢杆菌的培养基:胰蛋白胨5g,酵母膏15g,K2HPO4 3g,葡萄糖2g,蒸馏水1000mL,pH 7.5;Ⅰ Medium for Bacillus licheniformis: tryptone 5g, yeast extract 15g, K 2 HPO 4 3g, glucose 2g, distilled water 1000mL, pH 7.5;

Ⅱ沼泽红假单胞菌的培养基:NH4Cl 1.0g,K2HPO4 0.5g,NaHCO3 3.0g,酵母膏2.0g,蒸馏水1000 mL,pH 7.2;Ⅱ Medium for Rhodopseudomonas palustris: 1.0g NH 4 Cl, 0.5g K 2 HPO 4 , 3.0g NaHCO 3 , 2.0g yeast extract, 1000 mL distilled water, pH 7.2;

Ⅲ 小球藻常用培养液配方:NH4NO3 50-100 mg,K2HPO4 5 mg,FeC6H5O7 0.1-0.5 mg,海水 1000 mL;Ⅲ Chlorella common culture solution formula: NH 4 NO 3 50-100 mg, K 2 HPO 4 5 mg, FeC 6 H 5 O 7 0.1-0.5 mg, seawater 1000 mL;

Ⅳ链球菌的培养基:牛肉粉10.0g,胰蛋白胨20.g,葡萄糖2.0g,NaHCO3 2.0g,NaCl2.0g,Na2HPO4 0.4g,蒸馏水1000 mL,pH值7.8;Streptococcus IV culture medium: beef powder 10.0g, tryptone 20.g, glucose 2.0g, NaHCO 3 2.0g, NaCl 2.0g, Na 2 HPO 4 0.4g, distilled water 1000 mL, pH 7.8;

Ⅴ氧化硫杆菌的培养基:胰蛋白胨 5.0g,KH2PO4 1.0g,MgSO4·7H2O 0.5g,葡萄糖10g,蒸馏水 1000 mL。Ⅴ Culture medium for Thiobacillus oxidans: 5.0 g of tryptone, 1.0 g of KH 2 PO 4 , 0.5 g of MgSO 4 ·7H 2 O, 10 g of glucose, and 1000 mL of distilled water.

本发明的有益效果在于:The beneficial effects of the present invention are:

1)将本发明微生物净水剂投放至养殖厌氧污水中,净水剂可利用微生物降解污水中大分子有机物,能去除污水中大部分的污染物,达到净化污水的目的;1) Put the microbial water purifier of the present invention into the aquaculture anaerobic sewage, the water purifier can use microorganisms to degrade the macromolecular organic matter in the sewage, remove most of the pollutants in the sewage, and achieve the purpose of purifying the sewage;

2)由于微生物净水剂的碳载体采用了有机化合物为原料,制备的碳载体表面含氧官能团(-OH、-COOH等)丰富,这些带电性基团与水中的氢质子/氢氧根离子发生静电相互作用,使碳载体与水有了更好的相溶性,克服了一般炭载体的疏水性问题,与污染物接触性更好;同时碳载体表面上的带电性基团会与氮、磷、硫的孤对电子发生静电作用,提高了对污染物的吸附效率;其次,300℃煅烧过程也提高了碳粉末的纯度和孔隙度,熔融的固体碱环境使碳材料获得表面缺陷和二次孔隙结构,为吸附反应提供了更多的活性位点,增加了对污染物的吸附;2) Since the carbon carrier of the microbial water purifier uses organic compounds as raw materials, the surface of the prepared carbon carrier is rich in oxygen-containing functional groups (-OH, -COOH, etc.), and these charged groups interact with the hydrogen protons/hydroxide ions in the water Electrostatic interaction occurs, which makes the carbon carrier and water have better compatibility, overcomes the hydrophobicity problem of general carbon carriers, and has better contact with pollutants; at the same time, the charged groups on the surface of the carbon carrier will interact with nitrogen, The lone pair electrons of phosphorus and sulfur have electrostatic interaction, which improves the adsorption efficiency of pollutants; secondly, the calcination process at 300 °C also improves the purity and porosity of carbon powder, and the molten solid alkali environment makes carbon materials obtain surface defects and The secondary pore structure provides more active sites for the adsorption reaction and increases the adsorption of pollutants;

3)通过将亲水性碳载体与微生物共培养,所制得的净水剂碳载体上有效活菌数为7×108~6×109 CFU/gCFU/g,菌碳结合率达到97.8%,提高了碳载体对微生物的吸附固定效率;3) By co-cultivating the hydrophilic carbon carrier and microorganisms, the effective number of viable bacteria on the carbon carrier of the prepared water purifier is 7×10 8 ~ 6×10 9 CFU/gCFU/g, and the bacterial carbon binding rate reaches 97.8 %, which improves the adsorption and fixation efficiency of carbon carrier to microorganisms;

4)该富缺陷碳载体固定微生物的净水剂由于定植于活性碳上的微生物将碳上吸附的有机质等作为营养物质高效降解,既净化了水质,又可将自身代谢的产物作为彼此利用的营养底物,提高微生物活性,促进微生物菌群对污染物协同降解,故具有碳吸附与生物降解的双重净化作用、亲水但易于沉淀的特点、净化效果稳定且易于处理等优点,非常适用于养殖厌氧污水的规模化处理。4) The water purifier for immobilizing microorganisms on the defect-rich carbon carrier, because the microorganisms colonized on the activated carbon can efficiently degrade the organic matter adsorbed on the carbon as nutrients, which not only purifies the water quality, but also uses the products of their own metabolism as mutual utilization Nutrient substrate, improve microbial activity, and promote the synergistic degradation of pollutants by microbial flora, so it has the advantages of double purification of carbon adsorption and biodegradation, hydrophilic but easy to precipitate, stable purification effect and easy handling, etc., very suitable for Large-scale treatment of aquaculture anaerobic wastewater.

具体实施方式detailed description

为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。In order to further disclose rather than limit the present invention, the present invention will be further described in detail below in conjunction with examples.

一种富缺陷碳载体固定微生物的净水剂的制备方法,具体步骤为:A kind of preparation method of the water purifying agent of rich defect carbon carrier immobilized microorganism, concrete steps are:

1、表面含亲水性官能团及缺陷的碳载体的制备1. Preparation of carbon supports with hydrophilic functional groups and defects on the surface

1)将NaOH+KOH=90g(NaOH:KOH=46.5:43.5,质量比)置于200 ml反应釜内胆中,置于165℃下熔融2h,得澄清熔融碱液;1) Put NaOH+KOH=90g (NaOH:KOH=46.5:43.5, mass ratio) in a 200 ml reactor liner and melt at 165°C for 2 hours to obtain clarified molten lye;

2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应 12小时,生成富缺陷粉末碳前驱体材料A;2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 12 hours to generate defect-rich powder carbon precursor material A;

3)将上述碳前驱体A用水洗涤至洗液pH值约为7,除去水溶性杂质,然后离心分离得下层沉淀;下层沉淀再用无水乙醇洗涤,除去不溶于水的有机杂质,最后离心的沉淀物于80℃干燥过夜,得富缺陷粉末碳前驱体样品A;3) Wash the above-mentioned carbon precursor A with water until the pH value of the washing solution is about 7, remove water-soluble impurities, and then centrifuge to obtain the lower precipitate; the lower precipitate is then washed with absolute ethanol to remove water-insoluble organic impurities, and finally centrifuged The precipitate was dried overnight at 80°C to obtain defect-rich powdery carbon precursor sample A;

4)将碳前驱体样品A置于300℃马弗炉中煅烧2h,得多孔富缺陷碳粉末B(总孔容积约0.05~0.06 cm3/g);4) The carbon precursor sample A was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous and defect-rich carbon powder B (total pore volume about 0.05-0.06 cm 3 /g);

5)将0.5-1.0克的多孔富缺陷碳粉末B置于玛瑙研钵内,加入2-4 ml乙醇,搅拌30分钟使碳粉末均匀分散于乙醇中,再加入1-2 ml聚乙二醇(PEG400),充分搅拌使粉末碳形成胶状物后放入到压片机的压片槽内(圆柱型、药片型)或耐压力的模具内,置于80℃的环境中干燥24小时,最后在10-15MPa压力下压制成型,制成微生物净水剂的碳载体。5) Put 0.5-1.0 g of porous defect-rich carbon powder B in an agate mortar, add 2-4 ml of ethanol, stir for 30 minutes to disperse the carbon powder evenly in ethanol, and then add 1-2 ml of polyethylene Glycol (PEG400), fully stirred to make the powder carbon into a jelly, put it into the tablet tank of the tablet press (cylindrical, tablet type) or a pressure-resistant mold, and dry it in an environment of 80 ° C for 24 Hours, and finally press molding under 10-15MPa pressure to make the carbon carrier of the microbial water purifying agent.

2、将10g富缺陷碳载体加入到50-150 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为1-2 %,在4℃、150rpm条件下振荡共培养48~72h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为7×108~6×109 CFU/g,菌碳结合率达到97.8%;4℃条件下保存的净水剂在使用前于常温下放置8-12小时恢复生物活性即可直接投放于污水。2. Add 10 g of defect-rich carbon carriers to 50-150 ml Luria-Bertani medium, and add Bacillus licheniformis , Rhodopseudomonas palustris , Chlorella vulgaris , Streptococcus , oxidized Thiobacillus Thiooxidant was inoculated into Luria-Bertani medium at a mass ratio of 4:5:1:4:1, the inoculum amount of the compound strain was 1-2%, and co-cultivated by shaking at 4°C and 150rpm for 48-72h. Finally, remove the carbon carrier and dry it in a constant temperature box at 4°C to obtain a water purifier; the effective number of viable bacteria on the carbon carrier is 7×10 8 to 6×10 9 CFU/g, and the bacterial carbon binding rate reaches 97.8 %; The water purifier stored at 4°C can be placed in the sewage directly for 8-12 hours before use to restore its biological activity.

实施例1Example 1

一种富缺陷碳载体固定微生物的净水剂的制备方法,具体步骤为:A kind of preparation method of the water purifying agent of rich defect carbon carrier immobilized microorganism, concrete steps are:

(1)表面含亲水性官能团及缺陷的碳载体的制备(1) Preparation of carbon supports with hydrophilic functional groups and defects on the surface

1)将NaOH+KOH=90g(NaOH:KOH=46.5:43.5,质量比)置于200 ml反应釜内胆中,置于165℃下熔融2h,得澄清熔融碱液;1) Put NaOH+KOH=90g (NaOH:KOH=46.5:43.5, mass ratio) in a 200 ml reactor liner and melt at 165°C for 2 hours to obtain clarified molten lye;

2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应 12小时,生成富缺陷粉末碳前驱体材料A;2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 12 hours to generate defect-rich powder carbon precursor material A;

3)将上述碳前驱体A用水洗涤至洗液pH值约为7,除去水溶性杂质,然后离心分离得下层沉淀;下层沉淀再用无水乙醇洗涤,除去不溶于水的有机杂质,最后离心的沉淀物于80℃干燥过夜,得富缺陷粉末碳前驱体样品A;3) Wash the above-mentioned carbon precursor A with water until the pH value of the washing solution is about 7, remove water-soluble impurities, and then centrifuge to obtain the lower precipitate; the lower precipitate is then washed with absolute ethanol to remove water-insoluble organic impurities, and finally centrifuged The precipitate was dried overnight at 80°C to obtain defect-rich powdery carbon precursor sample A;

4)将碳前驱体A置于300℃马弗炉中煅烧2h,得多孔富缺陷碳粉末材料B;4) The carbon precursor A was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous and defect-rich carbon powder material B;

5)将0.8克的多孔缺陷碳粉末B置于玛瑙研钵内,加入3 ml乙醇,搅拌30分钟使碳粉末均匀分散于乙醇中,再加入1.6 ml聚乙二醇(PEG400),充分搅拌使粉末碳形成胶状物后放入到压片机的压片槽内(圆柱型、药片型)或耐压力的模具内,置于80℃的环境中干燥24小时,最后在15 MPa压力下压制成型,制成微生物净水剂的碳载体。5) Put 0.8 g of porous defective carbon powder B in an agate mortar, add 3 ml of ethanol, stir for 30 minutes to disperse the carbon powder evenly in the ethanol, then add 1.6 ml of polyethylene glycol (PEG400), fully Stir to make the powder carbon into a jelly, put it into the tablet tank of the tablet press (cylindrical, tablet type) or a pressure-resistant mold, dry it in an environment of 80°C for 24 hours, and finally press it under a pressure of 15 MPa. Press down to form the carbon carrier of the microbial water purifier.

(2)将10g富缺陷碳载体加入到150 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为1%,在4℃、150 rpm条件下振荡共培养72h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为6×109 CFU/g,菌碳结合率达到97.8%;4℃条件下保存的净水剂在使用前于常温下放置10小时恢复生物活性即可直接投放于污水。(2) Add 10 g of defect-rich carbon carriers to 150 ml of Luria-Bertani medium, and add Bacillus licheniformis , Rhodopseudomonas palustris , Chlorella vulgaris , Streptococcus , sulfur oxide The bacillus Thiobacillus Thiooxidant was inoculated into Luria-Bertani medium at a mass ratio of 4:5:1:4:1, the inoculum amount of the compound strain was 1%, and the co-cultivation was shaken at 4°C and 150 rpm for 72 hours, and finally the carbon was removed. The carrier is dried in a constant temperature box at 4°C to obtain a water purifier; the effective number of viable bacteria on the carbon carrier is 6×10 9 CFU/g, and the bacterial carbon binding rate reaches 97.8%; the net The water agent can be placed in the sewage directly for 10 hours at room temperature to recover its biological activity before use.

实施例2Example 2

一种富缺陷碳载体固定微生物的净水剂的制备方法,具体步骤为:A kind of preparation method of the water purifying agent of rich defect carbon carrier immobilized microorganism, concrete steps are:

(1)表面含亲水性官能团及缺陷的碳载体的制备(1) Preparation of carbon supports with hydrophilic functional groups and defects on the surface

1)将NaOH+KOH=90g(NaOH:KOH=46.5:43.5,质量比)置于200 ml反应釜内胆中,置于180℃下熔融2h,得澄清熔融碱液;1) Put NaOH+KOH=90g (NaOH:KOH=46.5:43.5, mass ratio) in a 200 ml reactor liner and melt at 180°C for 2 hours to obtain clarified molten lye;

2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应 10小时,生成富缺陷粉末碳前驱体材料A;2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 10 hours to generate defect-rich powder carbon precursor material A;

3)将上述碳前驱体A用水洗涤至洗液pH值约为7,除去水溶性杂质,然后离心分离得下层沉淀;下层沉淀再用无水乙醇洗涤,除去不溶于水的有机杂质,最后离心的沉淀物于80℃干燥过夜,得富缺陷粉末碳前驱体样品A;3) Wash the above-mentioned carbon precursor A with water until the pH value of the washing solution is about 7, remove water-soluble impurities, and then centrifuge to obtain the lower precipitate; the lower precipitate is then washed with absolute ethanol to remove water-insoluble organic impurities, and finally centrifuged The precipitate was dried overnight at 80°C to obtain defect-rich powdery carbon precursor sample A;

4)将碳前驱体A置于300℃马弗炉中煅烧2h,得多孔富缺陷碳粉末材料B;4) The carbon precursor A was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous and defect-rich carbon powder material B;

5)将0.5克的多孔缺陷碳粉末B置于玛瑙研钵内,加入2ml乙醇,搅拌30分钟使碳粉末均匀分散于乙醇中,再加入1.0 ml滴聚乙二醇(PEG400),充分搅拌使粉末碳形成胶状物后放入到压片机的压片槽内(圆柱型、药片型)或耐压力的模具内,置于80℃的环境中干燥24小时,最后在10MPa压力下压制成型,制成微生物净水剂的碳载体。5) Put 0.5 g of porous defect carbon powder B in an agate mortar, add 2 ml of ethanol, stir for 30 minutes to disperse the carbon powder in the ethanol evenly, then add 1.0 ml of polyethylene glycol (PEG400) to fully Stir to make the powder carbon into a jelly, put it into the tablet tank of the tablet press (cylindrical type, tablet type) or a pressure-resistant mold, dry it in an environment of 80°C for 24 hours, and finally put it under a pressure of 10MPa Press molding to make the carbon carrier of the microbial water purifying agent.

(2)将10g富缺陷碳载体加入到100 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为2%,在4℃、150 rpm条件下振荡共培养60h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为1×109CFU/g,菌碳结合率达到97.4%;4℃条件下保存的净水剂在使用前于常温下放置10小时恢复生物活性即可直接投放于污水。(2) Add 10 g of defect-rich carbon carriers to 100 ml of Luria-Bertani medium, and add Bacillus licheniformis , Rhodopseudomonas palustris , Chlorella vulgaris , Streptococcus , sulfur oxide The bacillus Thiobacillus Thiooxidant was inoculated into Luria-Bertani medium at a mass ratio of 4:5:1:4:1, the inoculation amount of the compound strain was 2%, and the co-cultivation was shaken at 4°C and 150 rpm for 60 hours, and finally the carbon The carrier is dried in a constant temperature box at 4°C to obtain a water purifier; the effective number of viable bacteria on the carbon carrier is 1×10 9 CFU/g, and the bacterial carbon binding rate reaches 97.4%; the net The water agent can be placed in the sewage directly for 10 hours at room temperature to recover its biological activity before use.

实施例3Example 3

一种富缺陷碳载体固定微生物的净水剂的制备方法,具体步骤为:A kind of preparation method of the water purifying agent of rich defect carbon carrier immobilized microorganism, concrete steps are:

(1)表面含亲水性官能团及缺陷的碳载体的制备(1) Preparation of carbon supports with hydrophilic functional groups and defects on the surface

1)将NaOH+KOH=90g(NaOH:KOH=46.5:43.5,质量比)置于200 ml反应釜内胆中,置于200℃下熔融2h,得澄清熔融碱液;1) Put NaOH+KOH=90g (NaOH:KOH=46.5:43.5, mass ratio) in a 200 ml reactor liner and melt at 200°C for 2 hours to obtain clarified molten lye;

2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应 8小时,生成富缺陷粉末碳前驱体材料A;2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 8 hours to generate defect-rich powder carbon precursor material A;

3)将上述碳前驱体A用水洗涤至洗液pH值约为7,除去水溶性杂质,然后离心分离得下层沉淀;下层沉淀再用无水乙醇洗涤,除去不溶于水的有机杂质,最后离心的沉淀物于80℃干燥过夜,得富缺陷粉末碳前驱体样品A;3) Wash the above-mentioned carbon precursor A with water until the pH value of the washing solution is about 7, remove water-soluble impurities, and then centrifuge to obtain the lower precipitate; the lower precipitate is then washed with absolute ethanol to remove water-insoluble organic impurities, and finally centrifuged The precipitate was dried overnight at 80°C to obtain defect-rich powdery carbon precursor sample A;

4)将碳前驱体A置于300℃马弗炉中煅烧2h,得多孔富缺陷碳材料B;4) The carbon precursor A was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous and defect-rich carbon material B;

5)将1.0克的多孔缺陷碳粉末B置于玛瑙研钵内,加入4 ml乙醇,搅拌30分钟使碳粉末均匀分散于乙醇中,再加入2 ml聚乙二醇(PEG400),充分搅拌使粉末碳形成胶状物后放入到压片机的压片槽内(圆柱型、药片型)或耐压力的模具内,置于80℃的环境中干燥24小时,最后在15MPa压力下压制成型,制成微生物净水剂的碳载体。5) Put 1.0 g of porous defective carbon powder B in an agate mortar, add 4 ml of ethanol, stir for 30 minutes to disperse the carbon powder in the ethanol evenly, then add 2 ml of polyethylene glycol (PEG400), fully Stir to make the powder carbon into a jelly, then put it into the tablet tank of the tablet press (cylindrical type, tablet type) or a pressure-resistant mold, dry it in an environment of 80°C for 24 hours, and finally put it under a pressure of 15MPa Press molding to make the carbon carrier of the microbial water purifying agent.

(2)将10g富缺陷碳载体加入到50 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为1%,在4℃、150 rpm条件下振荡共培养48h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为7×108 CFU/g,菌碳结合率达到97.1%;4℃条件下保存的净水剂在使用前于常温下放置10小时恢复生物活性即可直接投放于污水。(2) Add 10 g of defect-rich carbon carriers to 50 ml of Luria-Bertani medium, and add Bacillus licheniformis , Rhodopseudomonas palustris , Chlorella vulgaris , Streptococcus , sulfur oxide The bacillus Thiobacillus Thiooxidant was inoculated into Luria-Bertani medium at a mass ratio of 4:5:1:4:1, the inoculation amount of the composite strain was 1%, and the co-cultivation was shaken at 4°C and 150 rpm for 48 hours, and finally the carbon was removed. The carrier is dried in a constant temperature box at 4°C to obtain a water purifier; the effective number of viable bacteria on the carbon carrier is 7×10 8 CFU/g, and the bacterial carbon binding rate reaches 97.1%; the net The water agent can be placed in the sewage directly for 10 hours at room temperature to recover its biological activity before use.

对比例1Comparative example 1

与实施例1-3基本相同,制得富缺陷碳载体固定微生物的净水剂,区别仅在于前三个步骤(1)中制备的碳载体不同,对比例1中为市面上出售的柱型活性炭载体(比表面约1100m2/g,孔容积为0.75 cm3/g)。Basically the same as in Example 1-3, the water purifying agent for immobilizing microorganisms with a rich and defective carbon carrier is prepared, the only difference is that the carbon carrier prepared in the first three steps (1) is different, and the column type sold in the market is used in Comparative Example 1 Activated carbon support (specific surface about 1100m 2 /g, pore volume 0.75 cm 3 /g).

性能测试:Performance Testing:

一、将不同形状的活性炭载体投入到养殖厌氧污水,对其吸附效果进行比较。分别称取100g各种形状的活性炭载体(即颗粒状煤质活性炭A、球状煤质活性炭B、圆柱状煤质活性炭C、富缺陷柱状碳D),投入到10L的养殖厌氧污水中,以未处理的养殖厌氧污水为对照,3.5d后分别测定其CODcr、BOD5、氨氮、总磷等技术指标,计算活性炭对养殖厌氧污水中各指标的吸附率。1. Put activated carbon carriers of different shapes into the aquaculture anaerobic sewage, and compare their adsorption effects. Weigh 100g of activated carbon carriers of various shapes (i.e. granular coal-based activated carbon A, spherical coal-based activated carbon B, cylindrical coal-based activated carbon C, and defect-rich columnar carbon D), and put them into 10L of aquaculture anaerobic sewage. The untreated aquaculture anaerobic sewage was used as a control, and its CODcr, BOD 5 , ammonia nitrogen, total phosphorus and other technical indicators were measured after 3.5 days, and the adsorption rate of activated carbon to each index in the aquaculture anaerobic sewage was calculated.

实验结果见表1-1。从实验结果可以看出,前三者中圆柱状煤质活性炭对养殖厌氧污水的吸附能力较佳,其COD、BOD5、氨氮、总磷等吸附率都高于前两者;本专利中富缺陷柱状碳吸附效果则优于A、B、C三者,且COD、BOD5、氨氮、总磷吸附率都有较明显提高,可见表面含氧官能团及表面缺陷协同促进了污染物的吸附,去污效果优于市售的不同形状活性炭。The experimental results are shown in Table 1-1. It can be seen from the experimental results that among the first three, the cylindrical coal-based activated carbon has the better adsorption capacity to the aquaculture anaerobic sewage, and its COD, BOD 5 , ammonia nitrogen, total phosphorus and other adsorption rates are higher than the first two; The adsorption effect of defective columnar carbon is better than that of A, B, and C, and the adsorption rates of COD, BOD 5 , ammonia nitrogen, and total phosphorus are all significantly improved. It can be seen that the surface oxygen-containing functional groups and surface defects synergistically promote the adsorption of pollutants. The decontamination effect is better than that of commercially available activated carbon of different shapes.

表1-1 不同形状的炭载体对养殖厌氧污水处理效果Table 1-1 The effect of different shapes of carbon carriers on the treatment of aquaculture anaerobic sewage

二、取五个大小及水质完全相同的养殖厌氧污水水槽(10 L)进行测试,第一个投放实施例1 的微生物净水剂;第二个投放实施例2的微生物净水剂;第三个投放实施例3的微生物净水剂;第四个投放对比例1的菌碳净水剂;第五个不投放任何净水剂,作为空白对照组。Two, take five aquaculture anaerobic sewage tanks (10 L) with exactly the same size and water quality for testing, the first puts the microbial water purifier of embodiment 1; the second puts the microbial water purifier of embodiment 2; the second Three of them were injected with the microbial water purifier of Example 3; the fourth was injected with the bacterial carbon water purifier of Comparative Example 1; the fifth was not injected with any water purifier, which was used as a blank control group.

将100 g净水剂分别投放至养殖厌氧污水水槽,3.5天后,对所有的养殖厌氧污水水槽进行水质测定。水质测量的依据为GB11607-89 中华人民共和国国家标准渔业水质标准和NY5051-2001 无公害食品淡水养殖用水水质,测定指标及数据如下表1-2、表1-3所示。100 g of water purifiers were put into the aquaculture anaerobic sewage tanks, and after 3.5 days, the water quality of all the aquaculture anaerobic sewage tanks was measured. The basis of water quality measurement is GB11607-89 National Standard Fishery Water Quality Standard of the People's Republic of China and NY5051-2001 Water Quality of Pollution-free Food Freshwater Aquaculture Water. The measurement indicators and data are shown in Table 1-2 and Table 1-3 below.

表1-2 3.5天后不同菌碳净化剂对污水指标浓度的作用效果Table 1-2 The effect of different bacterial carbon purifiers on the concentration of sewage indicators after 3.5 days

表1-3 3.5天后不同菌碳净化剂对污染物的去除效果Table 1-3 The removal effect of different bacterial carbon purifiers on pollutants after 3.5 days

由表中数据可以看出,实施例1-3 的各项水质指标均优于对比例1,更明显优于对照组。It can be seen from the data in the table that the various water quality indicators of Examples 1-3 are better than those of Comparative Example 1, and even more obviously better than that of the control group.

以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本领域的技术人员在本发明所揭露的技术范围内,可不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and any person skilled in the art may make changes or modifications without creative work within the technical scope disclosed in the present invention. Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope defined in the claims.

Claims (5)

1.一种富缺陷碳载体固定微生物的净水剂,其特征在于:将富缺陷碳载体置于Luria-Bertani培养基中,同时将复合菌株接种至Luria-Bertani培养基,经振荡共培养、烘干后,制得净水剂;所述的富缺陷碳载体的制备方法包括以下步骤:1. A water purifying agent rich in defective carbon carrier immobilizing microorganisms, characterized in that: the rich defective carbon carrier is placed in the Luria-Bertani substratum, and the compound bacterial strain is inoculated to the Luria-Bertani substratum simultaneously, through shaking co-cultivation, After drying, the water purifying agent is obtained; the preparation method of the defect-rich carbon carrier comprises the following steps: (1)将90g NaOH和KOH的混合碱置于200 ml反应釜内胆中,置于 165℃下熔融2h,得澄清熔融碱液;(1) Put 90g of mixed alkali of NaOH and KOH in a 200 ml reactor liner, and melt it at 165°C for 2 hours to obtain a clarified molten alkali; (2)以葡萄糖和尿素为原料,加入澄清熔融碱液中反应 12小时,生成富缺陷粉末碳前驱体材料;(2) Using glucose and urea as raw materials, add them to clarified molten lye and react for 12 hours to generate defect-rich powder carbon precursor materials; (3)碳前驱体材料依次经水、无水乙醇洗涤后,于80℃干燥12h得粉末碳前驱体;(3) After the carbon precursor material was washed with water and absolute ethanol in sequence, it was dried at 80°C for 12 hours to obtain a powder carbon precursor; (4)将粉末碳前驱体置于300℃马弗炉中煅烧2h,得到总孔容积为0.05~0.06 cm3/g的多孔富缺陷碳粉末材料;(4) The powdered carbon precursor was calcined in a muffle furnace at 300°C for 2 hours to obtain a porous defect-rich carbon powder material with a total pore volume of 0.05-0.06 cm 3 /g; (5)将多孔富缺陷碳粉末材料分散于乙醇中,然后在分散液中滴入聚乙二醇,充分搅拌形成胶状物后,压制成型,制成微生物净水剂的碳载体。(5) Disperse the porous defect-rich carbon powder material in ethanol, then drop polyethylene glycol into the dispersion liquid, stir well to form a jelly, and press it to make the carbon carrier of the microbial water purifier. 2.根据权利要求1所述的富缺陷碳载体固定微生物的净水剂,其特征在于:所述的Luria-Bertani培养基的配方为:胰蛋白胨10g,酵母提取物5g,NaCl 10g,蒸馏水1000 mL,pH 7.0。2. The water purifying agent for immobilizing microorganisms on rich and defective carbon carriers according to claim 1, characterized in that: the formula of the Luria-Bertani medium is: tryptone 10g, yeast extract 5g, NaCl 10g, distilled water 1000g mL, pH 7.0. 3.根据权利要求1所述的富缺陷碳载体固定微生物的净水剂,其特征在于:步骤(1)中所述的混合碱中NaOH和KOH的质量比为46.5:43.5。3 . The water purifier for immobilizing microorganisms with defect-rich carbon carriers according to claim 1 , wherein the mass ratio of NaOH to KOH in the mixed alkali described in step (1) is 46.5:43.5. 4.一种制备如权利要求1-3任一项所述的富缺陷碳载体固定微生物的净水剂的方法,其特征在于:将10g富缺陷碳载体加入到50-150 ml Luria-Bertani培养基中,并将地衣芽孢杆菌Bacillus licheniformis、沼泽红假单胞菌Rhodop seudanonas palustris、小球藻Chlorella vulgaris、链球菌Streptococcus、氧化硫杆菌Thiobacillus Thiooxidant按质量比为4:5:1:4:1接种至Luria-Bertani培养基中,复合菌株接种量为1-2 %,在4℃、150rpm条件下振荡培养48~72h,最后捞出碳载体置于4℃的恒温箱里烘干,即制得净水剂;碳载体上有效活菌数为7×108~6×109 CFU/g。4. A method for preparing a water purifying agent for immobilizing microorganisms with rich defective carbon carriers as claimed in any one of claims 1-3, characterized in that: 10g rich defective carbon carriers are added to 50-150 ml Luria-Bertani for cultivation In the base, Bacillus licheniformis , Rhodopseudomonas palustris , Chlorella vulgaris , Streptococcus , Thiobacillus Thiooxidant were inoculated at a mass ratio of 4:5:1:4:1 Into the Luria-Bertani medium, the inoculum amount of the compound strain is 1-2%, shake culture at 4°C and 150rpm for 48-72h, and finally remove the carbon carrier and place it in a constant temperature box at 4°C to dry it. Water purifying agent; the effective number of viable bacteria on the carbon carrier is 7×10 8 ~6×10 9 CFU/g. 5.一种如权利要求1-3任一项所述的富缺陷碳载体固定微生物的净水剂在处理养殖厌氧污水方面的应用。5. The application of a water purifying agent for immobilizing microorganisms on a defect-rich carbon carrier as described in any one of claims 1-3 in the treatment of aquaculture anaerobic sewage.
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