技术领域technical field
本发明涉及土壤污染修复剂，具体为一种重金属污染土壤修复剂。The invention relates to a soil pollution remediation agent, in particular to a heavy metal polluted soil remediation agent.
背景技术Background technique
土壤是人类环境的重要组成部分，是不可缺少、不可再生的自然资源，是一切生物赖以生存的重要基础，是地球生态系统物质、能量交换与循环的重要场所。随着我国工业化、城市化的快速发展，污染物的大量排放、不合格农用物质的使用、矿产资源的不合理开采等，使得重金属不断的进入土壤环境中，当其累积超过一定量后就会造成土壤的污染，从而使土壤的环境污染问题日趋严重，尤其是土壤重金属污染问题。土壤重金属污染具有隐蔽性、长期性和不可逆性，污染物在土壤中的滞留时间长，植物或微生物难以降解，不仅可以导致土壤的退化、农作物受损，还会直接威胁人类的生命健康。近年来，同时随着环境恶化的加重，土壤的重金属污染问题也呈现出了日益复杂的趋势。大量的污染地块在存在着重金属污染的同时，也存在着严重的有毒有机物污染，给周围的居民和生态环境带来了严重的威胁。Soil is an important part of the human environment, an indispensable and non-renewable natural resource, an important basis for the survival of all living things, and an important place for the exchange and circulation of materials and energy in the earth's ecosystem. With the rapid development of industrialization and urbanization in our country, heavy metals will continue to enter the soil environment due to the massive discharge of pollutants, the use of unqualified agricultural materials, and the unreasonable mining of mineral resources. Soil pollution is caused, so that the problem of soil environmental pollution is becoming more and more serious, especially the problem of soil heavy metal pollution. Soil heavy metal pollution is concealed, long-term and irreversible. Pollutants stay in the soil for a long time, and it is difficult for plants or microorganisms to degrade. It can not only lead to soil degradation and damage to crops, but also directly threaten human life and health. In recent years, with the aggravation of environmental deterioration, the problem of heavy metal pollution in soil has also shown an increasingly complex trend. A large number of polluted plots not only have heavy metal pollution, but also serious toxic organic pollution, which has brought serious threats to the surrounding residents and the ecological environment.
目前，针对重金属污染土壤的修复技术主要有：换土法、原位或异位化学淋洗、热解吸法、玻璃化修复等等，其中，换土法，实施工程量大，投资费用高，破坏土体结构，并且对换出的污土再进行妥善处理才能防止二次污染，因此，不适宜大面积污染土壤的治理；原位或异位化学淋洗，该方法具有成本高昂，且用于淋洗土壤的试剂进入土壤后将造成二次污染；热解吸法，只能用于处理具有挥发性的重金属，如汞等，且处理过程中需要消耗大量的能量、经济成本较高；玻璃化修复，该方法修复效率高，但修复后的土壤需要填埋处理，修复成本高且修复后的土壤不可再农用。At present, the remediation technologies for heavy metal-contaminated soil mainly include: soil replacement method, in-situ or ex-situ chemical leaching, thermal desorption method, vitrification repair, etc. Among them, the soil replacement method requires a large amount of engineering and high investment costs , destroy the soil structure, and properly treat the contaminated soil to prevent secondary pollution. Therefore, it is not suitable for the treatment of large-scale contaminated soil; in-situ or ex-situ chemical leaching, this method has high cost, and The reagents used for washing the soil will cause secondary pollution after entering the soil; the thermal desorption method can only be used to deal with volatile heavy metals, such as mercury, etc., and the process requires a lot of energy consumption and high economic costs ; Vitrification repair, this method has high repair efficiency, but the repaired soil needs to be landfilled, the repair cost is high and the repaired soil can no longer be used for agriculture.
上述对受重金属污染土壤的修复方法，有些不能完全的彻底的消除土壤中的重金属，有些甚至带来新的污染物，均存在各种缺陷，因此，针对上述现状，设计一种去除重金属效果好的且不产生新的污染的土壤修复剂十分必要。Some of the above-mentioned remediation methods for heavy metal-contaminated soil cannot completely eliminate heavy metals in the soil, and some even bring new pollutants, all of which have various defects. Soil remediation agents that are safe and do not produce new pollution are very necessary.
发明内容Contents of the invention
本发明的目的是为了解决上述技术的不足，提供一种重金属污染土壤修复剂，将改性生物质炭与有机质、复合微生物菌剂结合使用，既能够吸附固定土壤中的重金属，又能够改善土壤结构，且修复过程不产生新的污染物，修复效果好。The purpose of the present invention is to solve the deficiencies of the above-mentioned technologies, and to provide a heavy metal-contaminated soil remediation agent, which uses modified biochar in combination with organic matter and composite microbial agents, which can not only absorb and fix heavy metals in the soil, but also improve the soil structure, and the repair process does not produce new pollutants, and the repair effect is good.
为实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种重金属污染土壤修复剂，由以下质量份的原料组成：A heavy metal contaminated soil remediation agent is composed of the following raw materials in parts by mass:
改性生物质炭50～65份、有机质20～30份、复合微生物菌剂6～15份、聚丙烯酰胺5～10份、有机肥12～20份、铁粉6～12份；50-65 parts of modified biochar, 20-30 parts of organic matter, 6-15 parts of compound microbial agent, 5-10 parts of polyacrylamide, 12-20 parts of organic fertilizer, 6-12 parts of iron powder;
所述改性生物质炭由生物质炭与硫化钠混合改性得到；The modified biochar is obtained by mixing and modifying biochar and sodium sulfide;
所述有机质由腐殖酸、腐殖酸钾、黄腐酸钾按照2～4:6～8:3的质量比混合得到；The organic matter is obtained by mixing humic acid, potassium humate, and potassium fulvic acid in a mass ratio of 2 to 4:6 to 8:3;
所述复合微生物菌剂由以下质量份的原料组成：蜡样芽孢杆菌1～4份，产气荚膜梭菌1～3份，蕈状芽孢杆菌1～5份，胶质芽孢杆菌2～3份，白腐真菌5～12份，柠檬酸杆菌2～5份，蛎灰链霉菌3～5份，铜绿假单胞杆菌1～4份。The composite microbial agent is composed of the following raw materials in parts by mass: 1 to 4 parts of Bacillus cereus, 1 to 3 parts of Clostridium perfringens, 1 to 5 parts of Bacillus mycoides, 2 to 3 parts of Bacillus colioids 5 to 12 parts of white rot fungi, 2 to 5 parts of Citrobacter, 3 to 5 parts of Streptomyces griseus, and 1 to 4 parts of Pseudomonas aeruginosa.
优选的，所述复合微生物菌剂中各个菌的有效活菌数均为1×109～3×109CFU/g。Preferably, the effective viable count of each bacteria in the composite microbial agent is 1×109 -3×109 CFU/g.
优选的，所述有机肥为生活垃圾、厨余垃圾混合畜禽粪便经发酵后的熟肥。Preferably, the organic fertilizer is fermented fermented domestic waste and kitchen waste mixed with livestock and poultry manure.
本发明还保护上述重金属污染土壤修复剂的制备方法，包括以下步骤：The present invention also protects the preparation method of the above-mentioned heavy metal contaminated soil remediation agent, comprising the following steps:
步骤一、将生物质炭于硫化钠溶液中浸泡35～40h，水洗，过滤，干燥，并在惰性气体氛围中于500～600℃煅烧1～3h，保温1～2h，得到改性生物质炭，备用；Step 1. Soak biochar in sodium sulfide solution for 35-40 hours, wash with water, filter, dry, and calcinate at 500-600°C for 1-3 hours in an inert gas atmosphere, and keep warm for 1-2 hours to obtain modified biochar ,spare;
将腐殖酸、腐殖酸钾、黄腐酸钾按照2～4:6～8:3的质量比混合得到有机质，备用；Mixing humic acid, potassium humate and potassium fulvic acid according to the mass ratio of 2 to 4:6 to 8:3 to obtain organic matter, set aside;
以质量份数计，将蜡样芽孢杆菌1～4份，产气荚膜梭菌1～3份，蕈状芽孢杆菌1～5份，胶质芽孢杆菌2～3份，白腐真菌5～12份，柠檬酸杆菌2～5份，蛎灰链霉菌3～5份，铜绿假单胞杆菌1～4份混合，得到复合微生物菌剂；In terms of mass parts, 1 to 4 parts of Bacillus cereus, 1 to 3 parts of Clostridium perfringens, 1 to 5 parts of Bacillus mycoides, 2 to 3 parts of Bacillus colioids, and 5 to 3 parts of white rot fungi 12 parts, 2 to 5 parts of Citrobacter, 3 to 5 parts of Streptomyces griseus, and 1 to 4 parts of Pseudomonas aeruginosa were mixed to obtain a composite microbial agent;
步骤二、称取步骤一得到的改性生物质炭60～65份，步骤一得到的有机质20～30份，复合微生物菌剂6～15份、聚丙烯酰胺5～10份、有机肥12～20份、铁粉6～12份，备用；Step 2. Weigh 60-65 parts of modified biochar obtained in step 1, 20-30 parts of organic matter obtained in step 1, 6-15 parts of composite microbial agent, 5-10 parts of polyacrylamide, 12-30 parts of organic fertilizer 20 parts, 6-12 parts of iron powder, set aside;
步骤三、将步骤二称取的复合微生物菌剂与水按照1:170～190的体积比混合得到复合微生物菌液，并与步骤二称取的改性生物质炭混合均匀，超声干燥，得到混合物；Step 3. Mix the composite microbial bacterial agent weighed in step 2 with water at a volume ratio of 1:170 to 190 to obtain a composite microbial bacterial liquid, and mix evenly with the modified biomass charcoal weighed in step 2, and dry it ultrasonically to obtain mixture;
步骤四、将步骤二称取的有机质、聚丙烯酰胺、有机肥、铁粉与步骤三得到的混合物混合均匀，得到重金属污染土壤修复剂。Step 4: Mix the organic matter, polyacrylamide, organic fertilizer, and iron powder weighed in Step 2 with the mixture obtained in Step 3 to obtain a heavy metal-contaminated soil remediation agent.
优选的，步骤一中，硫化钠溶液的质量分数为10～30％。Preferably, in step 1, the mass fraction of sodium sulfide solution is 10-30%.
优选的，步骤一中，生物质炭的制备过程为：将生物质原料与氧化钙按照20～22:1的质量比混合，并在惰性气体氛围中，于600～800℃热解1～3h，冷却得到生物质炭。Preferably, in step 1, the preparation process of biochar is as follows: the biomass raw material and calcium oxide are mixed according to the mass ratio of 20-22:1, and pyrolyzed at 600-800° C. for 1-3 hours in an inert gas atmosphere , cooling to obtain biochar.
优选的，生物质原料为农作物秸秆、花生壳、去籽向日葵盘、柳叶、稻壳、动物粪便和木屑中的一种或多种。Preferably, the biomass raw material is one or more of crop stalks, peanut shells, sunflower trays with seeds removed, willow leaves, rice husks, animal manure and wood chips.
优选的，步骤三中，超声干燥的条件为：超声功率为100～200W，超声频率为20kHz。Preferably, in step 3, the conditions for ultrasonic drying are: ultrasonic power is 100-200W, and ultrasonic frequency is 20kHz.
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1、本发明的生物质炭通过惰性气氛中热解生物质获得，在惰性气氛下制得的生物质炭孔隙率高，吸附性能好，且在生物质炭制备过程中添加氧化钙能够有效促进生物质炭的产量增加、孔道丰富，同时也能够使土壤pH值提高，从而使土壤表面负电荷增加，使土壤对重金属的亲和性增加，也能促使土壤中重金属形成氢氧化物或结合态沉淀或共沉淀；而且本发明对生物质炭进行了硫改性，显著增加了生物质炭表面含硫功能团数量，强化了对重金属的吸附力，而且含硫官能团能促进六价镉的还原，且稳定性极高，不会产生二次污染；1. The biochar of the present invention is obtained by pyrolyzing biomass in an inert atmosphere. The biochar prepared under an inert atmosphere has high porosity and good adsorption performance, and the addition of calcium oxide during the preparation of biochar can effectively promote The production of biochar increases, the pores are rich, and it can also increase the pH value of the soil, thereby increasing the negative charge on the soil surface, increasing the affinity of the soil for heavy metals, and also promoting the formation of hydroxides or bonded states of heavy metals in the soil. Precipitation or co-precipitation; and the present invention has carried out sulfur modification on the biochar, significantly increased the number of sulfur-containing functional groups on the surface of the bio-char, strengthened the adsorption of heavy metals, and the sulfur-containing functional groups can promote the reduction of hexavalent cadmium , and the stability is extremely high, and will not produce secondary pollution;
2、本发明以农作物秸秆等生物质为原料，充分利用资源，避免因其焚烧造成环境污染，而且将改性生物质炭与有机肥结合使用，具有改善土壤理化性质、调节土壤pH和提高土壤肥力的作用，使得修复剂既修复了重金属，又改善了土壤的性质；2. The present invention uses biomass such as crop stalks as raw materials, fully utilizes resources, avoids environmental pollution caused by incineration, and uses modified biochar in combination with organic fertilizers to improve soil physical and chemical properties, adjust soil pH and improve soil quality. The role of fertility makes the repair agent not only repair heavy metals, but also improve the properties of the soil;
3、本发明通过将改性生物质炭与有机质结合使用，能够吸附并固化重金属；重金属物质在土壤中以多种形态存在，例如镉包括可溶性镉离子形态、不溶性硫化镉和镉盐；本发明有机质中包括腐殖酸、腐殖酸钾和黄腐酸钾，腐殖酸钾可以使可溶性的镉离子形成氢氧化镉钝化在土壤中，同时释放钾肥，腐殖酸可以吸附不溶性的硫化镉和镉盐，此时改性生物质炭能够吸附土壤中的氢氧化镉；同时腐殖酸本身具有植物生长刺激作用，黄腐酸钾具有改良土壤结构，疏松土壤，提高土壤肥力，固氮、活化钾以及强化植物根系附着力和快速吸收能力的功效；3. The present invention can absorb and solidify heavy metals by combining the modified biomass charcoal with organic matter; heavy metals exist in various forms in the soil, for example, cadmium includes soluble cadmium ion forms, insoluble cadmium sulfide and cadmium salts; the present invention Organic matter includes humic acid, potassium humate and potassium fulvic acid. Potassium humate can passivate soluble cadmium ions to form cadmium hydroxide in the soil, and release potassium fertilizer at the same time. Humic acid can absorb insoluble cadmium sulfide and cadmium salt, at this time, the modified biochar can absorb cadmium hydroxide in the soil; at the same time, humic acid itself has a plant growth stimulating effect, and potassium fulvic acid can improve soil structure, loosen soil, improve soil fertility, fix nitrogen, activate Potassium and the effect of strengthening the adhesion and rapid absorption of plant roots;
4、本发明通过加入复合微生物菌剂，能够有效吸收镉、铅、锌等重金属；铁粉能够将镉、铬等物质还原为低毒或无毒状态；聚丙烯酰胺是高分子聚合物，有良好的水溶性，无毒、无腐蚀性、可以改善土壤的物理性能，增加土壤大团聚体数目，提高土壤导水性和含水量，减缓土壤流失，能让土壤与钝化剂充分接触；此外，聚丙烯酰胺具有羧基和酰胺基等活性基团，可通过与土壤颗粒表面的金属离子形成配位键，有稳定铬离子的协同作用。4. The present invention can effectively absorb heavy metals such as cadmium, lead, and zinc by adding a composite microbial agent; iron powder can reduce substances such as cadmium and chromium to a low-toxic or non-toxic state; polyacrylamide is a high molecular polymer, and has Good water solubility, non-toxic, non-corrosive, can improve the physical properties of the soil, increase the number of large soil aggregates, improve soil water conductivity and water content, slow down soil loss, and allow the soil to fully contact with the passivator; in addition, Polyacrylamide has active groups such as carboxyl and amide groups, which can form coordination bonds with metal ions on the surface of soil particles, and have a synergistic effect of stabilizing chromium ions.
具体实施方式Detailed ways
下面通过具体实施方式例对本发明进行详细描述。本发明的范围并不受限于该具体实施方式。The present invention will be described in detail below through specific implementation examples. The scope of the invention is not limited to this particular embodiment.
实施例1Example 1
本实施例提供一种重金属污染土壤修复剂，由以下质量份的原料组成：This embodiment provides a heavy metal contaminated soil remediation agent, consisting of the following raw materials in parts by mass:
改性生物质炭57份，有机质25份，复合微生物菌剂10份，聚丙烯酰胺7份，有机肥16份，铁粉9份；57 parts of modified biochar, 25 parts of organic matter, 10 parts of compound microbial agent, 7 parts of polyacrylamide, 16 parts of organic fertilizer, 9 parts of iron powder;
其中有机质由腐殖酸、腐殖酸钾、黄腐酸钾按照3:7:3的质量比混合得到；Wherein organic matter is obtained by mixing humic acid, potassium humate and potassium fulvic acid according to a mass ratio of 3:7:3;
其中复合微生物菌剂由以下质量份的原料组成：蜡样芽孢杆菌2.5份，产气荚膜梭菌2份，蕈状芽孢杆菌3份，胶质芽孢杆菌2.5份，白腐真菌8.5份，柠檬酸杆菌3.5份，蛎灰链霉菌4份，铜绿假单胞杆菌2.5份；复合微生物菌剂中各个菌的有效活菌数均为1×109CFU/g。Wherein the composite microbial bacterial agent consists of the following raw materials by mass: 2.5 parts of Bacillus cereus, 2 parts of Clostridium perfringens, 3 parts of Bacillus mycoides, 2.5 parts of Bacillus colloidus, 8.5 parts of white rot fungus, lemon There were 3.5 parts of Acidobacillus, 4 parts of Streptomyces griseus, and 2.5 parts of Pseudomonas aeruginosa; the effective number of viable bacteria of each bacteria in the composite microbial agent was 1×109 CFU/g.
本实施例还提供上述修复剂的制备方法，包括以下步骤：The present embodiment also provides the preparation method of above-mentioned restorative agent, comprises the following steps:
步骤一、将农作物秸秆与氧化钙按照20:1的质量比混合，并在氩气保护下于700℃热解2h，冷却得到生物质炭；将生物质炭于质量分数为20％的硫化钠溶液中浸泡37.5h，水洗，过滤，干燥，并在氩气氛围中于550℃煅烧2h，保温1h，得到改性生物质炭，备用；Step 1. Mix the crop straw and calcium oxide in a mass ratio of 20:1, and pyrolyze it at 700°C for 2 hours under the protection of argon, and cool to obtain biochar; mix the biochar with 20% sodium sulfide Soak in the solution for 37.5 hours, wash with water, filter, dry, and calcinate at 550°C for 2 hours in an argon atmosphere, and keep warm for 1 hour to obtain modified biochar, which is ready for use;
将腐殖酸、腐殖酸钾、黄腐酸钾按照3:7:3的质量比混合得到有机质，备用；Humic acid, potassium humate, and potassium fulvic acid are mixed according to a mass ratio of 3:7:3 to obtain organic matter, which is set aside;
步骤二、称取步骤一得到的改性生物质炭57份，步骤一得到的有机质25份，复合微生物菌剂10份，聚丙烯酰胺7份，有机肥16份，铁粉9份，备用；Step 2. Weigh 57 parts of modified biochar obtained in step 1, 25 parts of organic matter obtained in step 1, 10 parts of composite microbial bacterial agent, 7 parts of polyacrylamide, 16 parts of organic fertilizer, 9 parts of iron powder, and set aside;
步骤三、将步骤二称取的复合微生物菌剂与水按照1:180的体积比混合得到复合微生物菌液，并与步骤二称取的改性生物质炭混合均匀，超声干燥，得到混合物；Step 3, mixing the composite microbial bacterial agent weighed in step 2 with water according to a volume ratio of 1:180 to obtain a composite microbial bacterial liquid, and mixing evenly with the modified biomass charcoal weighed in step 2, and ultrasonically drying to obtain a mixture;
步骤四、将步骤二称取的有机质、聚丙烯酰胺、有机肥、铁粉与步骤三得到的混合物混合均匀，得到重金属污染土壤修复剂。Step 4: Mix the organic matter, polyacrylamide, organic fertilizer, and iron powder weighed in Step 2 with the mixture obtained in Step 3 to obtain a heavy metal-contaminated soil remediation agent.
实施例2Example 2
本实施例提供一种重金属污染土壤修复剂，由以下质量份的原料组成：This embodiment provides a heavy metal contaminated soil remediation agent, consisting of the following raw materials in parts by mass:
改性生物质炭50份，有机质20份，复合微生物菌剂6份，聚丙烯酰胺5份，有机肥12份，铁粉6份；50 parts of modified biochar, 20 parts of organic matter, 6 parts of compound microbial agent, 5 parts of polyacrylamide, 12 parts of organic fertilizer, 6 parts of iron powder;
其中有机质由腐殖酸、腐殖酸钾、黄腐酸钾按照2:6:3的质量比混合得到；Wherein the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvic acid in a mass ratio of 2:6:3;
其中复合微生物菌剂由以下质量份的原料组成：蜡样芽孢杆菌1份，产气荚膜梭菌1份，蕈状芽孢杆菌1份，胶质芽孢杆菌2份，白腐真菌5份，柠檬酸杆菌2份，蛎灰链霉菌3份，铜绿假单胞杆菌1份；复合微生物菌剂中各个菌的有效活菌数均为2×109CFU/g。Wherein the composite microbial bacterial agent consists of the following raw materials in parts by mass: 1 part of Bacillus cereus, 1 part of Clostridium perfringens, 1 part of Bacillus mycoides, 2 parts of Bacillus colloidus, 5 parts of white rot fungus, lemon 2 parts of Acidobacterium, 3 parts of Streptomyces griseus, 1 part of Pseudomonas aeruginosa; the effective number of viable bacteria of each bacteria in the composite microbial agent was 2×109 CFU/g.
本实施例还提供上述修复剂的制备方法，包括以下步骤：The present embodiment also provides the preparation method of above-mentioned restorative agent, comprises the following steps:
步骤一、将农作物秸秆与氧化钙按照22:1的质量比混合，并在氩气保护下于600℃热解3h，冷却得到生物质炭；将生物质炭于质量分数为10％的硫化钠溶液中浸泡40h，水洗，过滤，干燥，并在氩气氛围中于500℃煅烧3h，保温2h，得到改性生物质炭，备用；Step 1. Mix the crop straw and calcium oxide in a mass ratio of 22:1, and pyrolyze it at 600°C for 3 hours under the protection of argon, and cool to obtain biochar; mix the biochar with 10% sodium sulfide Soak in the solution for 40 hours, wash with water, filter, dry, and calcinate at 500°C for 3 hours in an argon atmosphere, and keep warm for 2 hours to obtain modified biochar, which is ready for use;
将腐殖酸、腐殖酸钾、黄腐酸钾按照2:6:3的质量比混合得到有机质，备用；Humic acid, potassium humate, and potassium fulvic acid are mixed according to a mass ratio of 2:6:3 to obtain organic matter, which is set aside;
步骤二、称取步骤一得到的改性生物质炭50份，步骤一得到的有机质20份，复合微生物菌剂6份，聚丙烯酰胺5份，有机肥12份，铁粉6份，备用；Step 2. Weigh 50 parts of modified biochar obtained in step 1, 20 parts of organic matter obtained in step 1, 6 parts of composite microbial bacterial agent, 5 parts of polyacrylamide, 12 parts of organic fertilizer, 6 parts of iron powder, and set aside;
步骤三、将步骤二称取的复合微生物菌剂与水按照1:170的体积比混合得到复合微生物菌液，并与步骤二称取的改性生物质炭混合均匀，超声干燥，得到混合物；Step 3, mixing the composite microbial bacterial agent weighed in step 2 with water according to a volume ratio of 1:170 to obtain a composite microbial bacterial liquid, and mixing evenly with the modified biomass charcoal weighed in step 2, and ultrasonically drying to obtain a mixture;
步骤四、将步骤二称取的有机质、聚丙烯酰胺、有机肥、铁粉与步骤三得到的混合物混合均匀，得到重金属污染土壤修复剂。Step 4: Mix the organic matter, polyacrylamide, organic fertilizer, and iron powder weighed in Step 2 with the mixture obtained in Step 3 to obtain a heavy metal-contaminated soil remediation agent.
实施例3Example 3
本实施例提供一种重金属污染土壤修复剂，由以下质量份的原料组成：This embodiment provides a heavy metal contaminated soil remediation agent, consisting of the following raw materials in parts by mass:
改性生物质炭65份，有机质30份，复合微生物菌剂15份，聚丙烯酰胺10份，有机肥20份，铁粉12份；65 parts of modified biochar, 30 parts of organic matter, 15 parts of compound microbial agent, 10 parts of polyacrylamide, 20 parts of organic fertilizer, 12 parts of iron powder;
其中有机质由腐殖酸、腐殖酸钾、黄腐酸钾按照4:8:3的质量比混合得到；Wherein the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvic acid in a mass ratio of 4:8:3;
其中复合微生物菌剂由以下质量份的原料组成：蜡样芽孢杆菌4份，产气荚膜梭菌3份，蕈状芽孢杆菌5份，胶质芽孢杆菌3份，白腐真菌12份，柠檬酸杆菌5份，蛎灰链霉菌5份，铜绿假单胞杆菌4份；复合微生物菌剂中各个菌的有效活菌数均为3×109CFU/g。Wherein the composite microbial bacterial agent is composed of the following raw materials in parts by mass: 4 parts of Bacillus cereus, 3 parts of Clostridium perfringens, 5 parts of Bacillus mycoides, 3 parts of Bacillus colloidus, 12 parts of white rot fungus, lemon 5 parts of Acidobacterium, 5 parts of Streptomyces griseus, 4 parts of Pseudomonas aeruginosa; the effective number of viable bacteria of each bacteria in the composite microbial agent was 3×109 CFU/g.
本实施例还提供上述修复剂的制备方法，包括以下步骤：The present embodiment also provides the preparation method of above-mentioned restorative agent, comprises the following steps:
步骤一、将农作物秸秆与氧化钙按照22:1的质量比混合，并在氩气保护下于800℃热解1h，冷却得到生物质炭；将生物质炭于质量分数为30％的硫化钠溶液中浸泡35h，水洗，过滤，干燥，并在氩气氛围中于600℃煅烧1h，保温2h，得到改性生物质炭，备用；Step 1. Mix the crop straw and calcium oxide at a mass ratio of 22:1, and pyrolyze it at 800°C for 1 hour under the protection of argon, and cool to obtain biochar; mix the biochar with 30% sodium sulfide Soak in the solution for 35 hours, wash with water, filter, dry, and calcinate at 600°C for 1 hour in an argon atmosphere, and keep warm for 2 hours to obtain modified biochar, which is ready for use;
将腐殖酸、腐殖酸钾、黄腐酸钾按照4:8:3的质量比混合得到有机质，备用；Humic acid, potassium humate, and potassium fulvic acid are mixed according to a mass ratio of 4:8:3 to obtain organic matter, which is set aside;
步骤二、称取步骤一得到的改性生物质炭65份，步骤一得到的有机质30份，复合微生物菌剂15份，聚丙烯酰胺10份，有机肥20份，铁粉12份，备用；Step 2. Weigh 65 parts of modified biochar obtained in step 1, 30 parts of organic matter obtained in step 1, 15 parts of composite microbial bacterial agent, 10 parts of polyacrylamide, 20 parts of organic fertilizer, 12 parts of iron powder, and set aside;
步骤三、将步骤二称取的复合微生物菌剂与水按照1:190的体积比混合得到复合微生物菌液，并与步骤二称取的改性生物质炭混合均匀，超声干燥，得到混合物；Step 3, mixing the composite microbial bacterial agent weighed in step 2 with water according to a volume ratio of 1:190 to obtain a composite microbial bacterial liquid, and mixing evenly with the modified biomass charcoal weighed in step 2, and ultrasonically drying to obtain a mixture;
步骤四、将步骤二称取的有机质、聚丙烯酰胺、有机肥、铁粉与步骤三得到的混合物混合均匀，得到重金属污染土壤修复剂。Step 4: Mix the organic matter, polyacrylamide, organic fertilizer, and iron powder weighed in Step 2 with the mixture obtained in Step 3 to obtain a heavy metal-contaminated soil remediation agent.
对比例1Comparative example 1
与实施例1的组成和制备方法相同，不同的是不加入复合微生物菌剂。The composition and preparation method are the same as in Example 1, except that no composite microbial agent is added.
对比例2Comparative example 2
与实施例1的组成和制备方法相同，不同的是加入的是生物质炭，也就是生物质炭不经过改性处理。The composition and preparation method are the same as in Example 1, except that the biochar is added, that is, the biochar is not modified.
对比例3Comparative example 3
实施例1的生物质炭。The biochar of embodiment 1.
对比例4Comparative example 4
实施例1的改性生物质炭。The modified biochar of Example 1.
本发明的实施例1～实施例3的修复剂具有良好的修复效果，我们将实施例1～实施例3的样品、对比例1～对比例4的样品进行了修复实验。The restorative agents of Examples 1 to 3 of the present invention have good repair effects. We have carried out repair experiments on the samples of Examples 1 to 3 and the samples of Comparative Examples 1 to 4.
首先我们进行了对重金属污染土壤的修复实验，首先将重金属污染的土壤分别置于7个相同的容器内，然后按照土壤重量5％的质量分别施加实施例1～实施例3以及对比例1～对比例4的样品，充分混合后加入去离子水，使土壤湿度为30～40％，然后每天加水使实验土壤的湿度不变，30d后采集土壤样品，进行重金属含量测试。表1为不同样品修复后土壤样品的重金属含量数据表。First of all, we carried out a repair experiment on heavy metal-contaminated soil. First, the heavy metal-contaminated soil was placed in 7 identical containers, and then the samples of Examples 1-3 and Comparative Examples 1-3 were applied according to the mass of 5% of the soil weight. For the sample of Comparative Example 4, after fully mixing, add deionized water to make the soil humidity 30-40%, then add water every day to keep the humidity of the experimental soil constant, and collect soil samples after 30 days for heavy metal content testing. Table 1 is the heavy metal content data table of soil samples after remediation of different samples.
表1不同样品修复后土壤样品的重金属含量数据表Table 1 Data table of heavy metal content of soil samples after remediation of different samples
从表1可以看出，本发明的重金属土壤修复剂对于重金属污染的土壤具有良好的修复效果。As can be seen from Table 1, the heavy metal soil remediation agent of the present invention has a good remediation effect on heavy metal polluted soil.
我们同时进行了修复后土壤对生长植物的影响实验，具体过程为：取过筛细土制备成400mg/kg的镉污染土壤，充分混合后，装入花盆中，每盆装土500g，加入去离子水使含水量为田间持水量的30％，平衡一个月后，分别施加实施例1～实施例3以及对比例1～对比例4的土壤修复剂。然后选取完整、健康、饱满的小麦种子，每盆播种30粒，播种深度2cm。将7个花盆于智能人工气候植物箱中培养，白天温度为25±2℃，全光照，晚上温度为18±2℃，黑暗，全天湿度为60～70％，隔一天浇一次水。生长一周后间苗，每盆留苗15株。生长30天后采集植株和根系土壤样品，测量植株和根系土壤中重金属镉的含量，结果见表2.At the same time, we also carried out the experiment of the effect of repaired soil on growing plants. The specific process is as follows: take sieved fine soil to prepare 400mg/kg cadmium-contaminated soil. The deionized water was used to make the water content 30% of the field water capacity, and after balancing for one month, the soil remediation agents of Examples 1-3 and Comparative Examples 1-4 were applied respectively. Then choose complete, healthy, plump wheat seeds, sow 30 grains in every pot, and the sowing depth is 2cm. Cultivate 7 flowerpots in an intelligent artificial climate plant box. The temperature during the day is 25±2°C in full light, and the temperature at night is 18±2°C in darkness. The humidity is 60-70% throughout the day and watered every other day. Thin out the seedlings after one week of growth, and keep 15 seedlings in each pot. Collect plant and root system soil samples after growing for 30 days, measure the content of heavy metal cadmium in plant and root system soil, the results are shown in Table 2.
表2修复后土壤种植小麦的镉含量Table 2 Cadmium content of wheat planted in soil after remediation
从表2可以看出，本发明的修复剂对土壤中镉有效态影响显著，本发明修复剂能够有效降低小麦体内的镉含量。As can be seen from Table 2, the restoration agent of the present invention has a significant impact on the available state of cadmium in the soil, and the restoration agent of the present invention can effectively reduce the cadmium content in wheat.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be It is regarded as the protection scope of the present invention.
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| CN201910615997.4ACN110283599B (en) | 2019-07-09 | 2019-07-09 | Heavy metal contaminated soil remediation agent and preparation method thereof |
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