技术领域technical field
本发明属于土木工程、环境工程、环境岩土工程技术领域，具体说来，涉及一种复合重金属污染场地修复的固化剂及制备和应用方法。The invention belongs to the technical fields of civil engineering, environmental engineering and environmental geotechnical engineering, and specifically relates to a curing agent for remediation of composite heavy metal polluted sites and a preparation and application method.
背景技术Background technique
工业污染场地重金属污染呈现为重金属种类复杂、酸度大以及含量高等特点。在重金属 污染场地的修复过程中，固化稳定化技术被广泛采用。固化稳定化技术是将固化剂与重金属 污染土壤充分搅拌均匀，通过物理包裹、化学吸附和结晶沉淀等手段，达到封闭污染物，减 少环境风险的目的。常用的固化剂主要包括水泥和磷矿粉等材料，对重金属固化稳定化具有 良好的效果，但存在着生产过程中耗能大、污染严重、成本高等缺点。Heavy metal pollution in industrially polluted sites is characterized by complex types of heavy metals, high acidity, and high content. In the remediation process of heavy metal-contaminated sites, solidification stabilization technology is widely used. Solidification and stabilization technology is to fully mix the solidification agent and heavy metal-contaminated soil evenly, and achieve the purpose of sealing pollutants and reducing environmental risks through physical packaging, chemical adsorption and crystallization and precipitation. Commonly used curing agents mainly include materials such as cement and phosphate rock powder, which have a good effect on the curing and stabilization of heavy metals, but there are disadvantages such as large energy consumption, serious pollution, and high cost in the production process.
综上所述，传统固化剂存在许多缺点，需要减少水泥和磷酸盐材料的使用，寻找一种既能固化稳定化重金属，同时低成本、环境友好且材料来源广泛的新型固化剂成为环 保科技工作者关注的焦点。To sum up, traditional curing agents have many disadvantages. It is necessary to reduce the use of cement and phosphate materials. Finding a new curing agent that can cure and stabilize heavy metals while being low-cost, environmentally friendly and has a wide range of material sources has become an environmental protection technology task. focus of attention.
发明内容Contents of the invention
技术问题：本发明要解决的技术问题是：提供一种用于复合重金属污染土的固化剂及 制备和应用方法，该固化剂能够显著降低重金属污染土对周围环境的危害，适用于重金属 含量高且污染物复杂的污染场地，污染土壤修复后可作为环境友好型材料资源化利用， 大幅度降低污染场地二次开发利用中的环境风险；同时，还提供该固化剂的制备方法和 应用方法，该固化剂原材料易于获取、制备简单、成本低廉、使用方便、效果稳定，可 在复合重金属污染场地中大规模推广应用。Technical problem: The technical problem to be solved by the present invention is to provide a curing agent for composite heavy metal-contaminated soil and its preparation and application method. The curing agent can significantly reduce the harm of heavy metal-contaminated soil to the surrounding environment, and is suitable for For polluted sites with complex pollutants, the contaminated soil can be used as an environmentally friendly material resource after remediation, greatly reducing the environmental risk in the secondary development and utilization of the polluted site; at the same time, the preparation method and application method of the curing agent are also provided. The raw material of the curing agent is easy to obtain, simple to prepare, low in cost, convenient to use and stable in effect, and can be popularized and applied on a large scale in compound heavy metal polluted sites.
技术方案：为解决上述技术问题，本发明的一种用于复合重金属污染土的固化剂按照 重量百分比，由以下组分组成：Technical solution: In order to solve the above-mentioned technical problems, a kind of curing agent for composite heavy metal polluted soil of the present invention consists of the following components according to weight percentage:
石灰粉：10％～30％Lime powder: 10% to 30%
粉煤灰粉：20％～50％Fly ash powder: 20% to 50%
活化钢渣粉：30％～50％；Activated steel slag powder: 30% to 50%;
磷酸二氢钾粉：0.5％～2％。Potassium dihydrogen phosphate powder: 0.5% to 2%.
其中，所述的石灰粉通过以下方式制成：将工业级石灰在烘箱内以100～150℃的温 度烘干，至质量不变，冷却后磨细过孔径小于0.075mm筛，然后放入温度为140～160℃的电炉内煅烧0.5～1小时后，得到石灰粉。Wherein, the lime powder is made by the following method: dry the industrial grade lime in an oven at a temperature of 100-150°C until the quality remains unchanged, grind it through a sieve with a pore size less than 0.075mm after cooling, and then put it into a temperature Lime powder is obtained after calcining in an electric furnace at 140-160°C for 0.5-1 hour.
所述的粉煤灰粉体通过以下方式制成：将国家标准二级以上粉煤灰过筛，取粒径小 于2mm的组分放置在烘箱内，通入温度为100～150℃的气流烘干，使其含水率降低至2％以下，冷却后过孔径小于0.075mm筛，在经过500～700℃电炉煅烧1～2小时后，得 到粉煤灰粉体。The fly ash powder is made by the following method: sieve the fly ash of the national standard level two or above, take the components with a particle size of less than 2mm, place them in an oven, and pass them into an airflow with a temperature of 100-150°C for drying. Drying to reduce the moisture content to below 2%, passing through a sieve with a hole diameter of less than 0.075mm after cooling, and calcining in an electric furnace at 500-700°C for 1-2 hours to obtain fly ash powder.
所述的磷酸二氢钾粉通过以下方法制备而成：将工业级磷酸二氢钾放置于烘箱内， 通过温度为100～150℃的气流烘干，使其含水率低于2％，研磨并过孔径小于0.075mm筛，得到磷酸二氢钾粉体。The potassium dihydrogen phosphate powder is prepared by the following method: put industrial-grade potassium dihydrogen phosphate in an oven, and dry it by air flow at a temperature of 100-150°C to make the moisture content lower than 2%, grind and Pass through a sieve with a pore size less than 0.075 mm to obtain potassium dihydrogen phosphate powder.
所述的活化钢渣粉通过以下方法制备而成：将钢渣粉和水玻璃溶液按照固液比5:1～10:1的比例进行混合，在温度30～35℃下，震荡搅拌搅拌12～24小时静置36～72小时后，将混合料置于烘箱内，通入温度为100～250℃的气流烘干，使其含水率小于2％， 然后球磨并过孔径小于0.075mm筛，制得活化钢渣粉。The activated steel slag powder is prepared by the following method: mix the steel slag powder and water glass solution according to the ratio of solid to liquid ratio of 5:1 to 10:1, and shake and stir at a temperature of 30 to 35°C for 12 to 24 hours. After standing still for 36-72 hours, put the mixture in an oven, pass it into an air stream at a temperature of 100-250°C and dry it so that the moisture content is less than 2%, then ball mill it and pass it through a sieve with a pore size of less than 0.075mm to obtain Activated steel slag powder.
所述的钢渣粉通过以下方法制得：将水淬转炉钢渣进行破碎并过2mm筛，通过温度为100～200℃的气流烘干，使其含水率低于2％，然后研磨并过200目筛，再经过600～ 700℃电炉煅烧2～3小时后，得到钢渣粉。The steel slag powder is prepared by the following method: crushing water-quenched converter steel slag and passing it through a 2mm sieve, drying it through an air flow at a temperature of 100-200°C to make its moisture content lower than 2%, and then grinding it and passing it through a 200-mesh Sieve, and then calcined in an electric furnace at 600-700°C for 2-3 hours to obtain steel slag powder.
本发明的用于复合重金属污染土的固化剂的制备方法包括以下步骤：将石灰粉、粉煤 灰粉、活化钢渣粉和磷酸二氢钾粉进行混合，其中各组分的重量百分比为：石灰粉：10％～30％、粉煤灰粉：20％～50％、活化钢渣粉：30％～50％、磷酸二氢钾粉：0.5％～2％；采用干法搅拌1～2小时，使混合均匀后过孔径小于0.075mm筛，得到所述固化剂。The preparation method of the curing agent for composite heavy metal polluted soil of the present invention comprises the following steps: mixing lime powder, fly ash powder, activated steel slag powder and potassium dihydrogen phosphate powder, wherein the weight percentage of each component is: lime powder: 10% to 30%, fly ash powder: 20% to 50%, activated steel slag powder: 30% to 50%, potassium dihydrogen phosphate powder: 0.5% to 2%; use dry stirring for 1 to 2 hours, The curing agent is obtained by passing through a sieve with a hole diameter of less than 0.075mm after mixing evenly.
本发明用于复合重金属污染土的固化剂的应用方法是将所述固化剂与重金属污染土 进行原位拌和，固化剂质量占污染土干土质量的5％～10％，污染土壤含水率控制在15％～35％之间。The application method of the solidifying agent used for compounding heavy metal-contaminated soil in the present invention is to carry out in-situ mixing of the solidifying agent and heavy metal-contaminated soil, the mass of the solidifying agent accounts for 5% to 10% of the dry soil mass of the polluted soil, and the moisture content of the polluted soil is controlled Between 15% and 35%.
所述的重金属污染土小于0.075mm土颗粒含量大于65％，其中重金属铅含量大于2000mg/kg，重金属锌含量大于2000mg/kg，重金属镉含量大于500mg/kg。The content of soil particles smaller than 0.075 mm in the heavy metal polluted soil is greater than 65%, wherein the content of heavy metal lead is greater than 2000 mg/kg, the content of heavy metal zinc is greater than 2000 mg/kg, and the content of heavy metal cadmium is greater than 500 mg/kg.
有益效果：与现有药剂对重金属的固化稳定化效果相比，本发明的技术方案具有以 下有益效果：Beneficial effect: Compared with the solidification and stabilization effect of the existing medicament on heavy metals, the technical solution of the present invention has the following beneficial effects:
1)重金属固化效果好。受限，石灰碱激发钢渣和粉煤灰形成无定形的三维网状结构， 将重金属牢牢包裹，使其固化效果优异。其次，磷酸二氢钾可以有效固定重金属，形成磷酸盐沉淀，增加重金属的固化效果。1) Heavy metal curing effect is good. Restricted, lime alkali stimulates steel slag and fly ash to form an amorphous three-dimensional network structure, which tightly wraps heavy metals and makes it excellent in curing effect. Secondly, potassium dihydrogen phosphate can effectively fix heavy metals, form phosphate precipitation, and increase the solidification effect of heavy metals.
2)有效利用废物原料，环境友好型固化剂。首先，钢渣和粉煤灰作为一种工业废渣， 被大规模的生产和堆积，已经造成了严重的环境污染，通过对钢渣和粉煤灰的激发，大大提升了钢渣和粉煤灰的利用价值，变废为宝，以废治废。其次，通过添加磷酸二氢钾， 增强该固化剂对重金属的固化效果。2) Effective use of waste raw materials, environmentally friendly curing agent. First of all, as a kind of industrial waste, steel slag and fly ash have been produced and accumulated on a large scale, which has caused serious environmental pollution. By stimulating steel slag and fly ash, the utilization value of steel slag and fly ash has been greatly improved , turning waste into treasure, treating waste with waste. Secondly, by adding potassium dihydrogen phosphate, the curing effect of the curing agent on heavy metals is enhanced.
3)耐用性能好。传统固化剂易受二氧化碳侵蚀及酸雨侵蚀的影响，从而减弱其固化 效果。本发明中的固化剂能够有效克服上述缺点，由于生成的重金属磷酸盐类沉淀，其在复杂环境下溶解度较低，并且在钢渣和粉煤灰经过石灰激发后水化产物C-A-S-H凝胶 的包裹作用下，可以大幅减少重金属沉淀与酸碱溶液的接触；另外钢渣本身具有极强的 酸缓冲能力及吸收二氧化碳的能力，在二氧化碳侵蚀作用下，生成CaCO3晶体进一步填 充固化土的孔隙，有效减少酸性溶液的入渗，进一步增强固化土在复杂环境下的稳定性。3) Good durability. Traditional curing agents are susceptible to carbon dioxide erosion and acid rain erosion, thus weakening their curing effect. The curing agent in the present invention can effectively overcome the above-mentioned shortcomings. Due to the precipitation of heavy metal phosphates, its solubility is low in complex environments, and the encapsulation of the hydration product C-A-S-H gel after the steel slag and fly ash are excited by lime It can greatly reduce the contact between heavy metal precipitation and acid-base solution; in addition, steel slag itself has a strong acid buffer capacity and the ability to absorb carbon dioxide. Under the action of carbon dioxide erosion, CaCO3 crystals are generated to further fill the pores of solidified soil, effectively reducing The infiltration further enhances the stability of the solidified soil in complex environments.
具体实施方式Detailed ways
下面结合实施例，对本发明的技术方案进行详细的说明。The technical solution of the present invention will be described in detail below in conjunction with the embodiments.
本发明的一种用于复合重金属污染土的固化剂按照重量百分比，由以下组分组成：A kind of solidifying agent that is used for composite heavy metal polluted soil of the present invention is made up of following components according to weight percentage:
石灰粉：10％～30％Lime powder: 10% to 30%
粉煤灰：20％～50％Fly ash: 20% to 50%
钢渣粉：30％～50％；Steel slag powder: 30% to 50%;
磷酸二氢钾粉：0.5％～2％；Potassium dihydrogen phosphate powder: 0.5% to 2%;
水玻璃：1％～6％。Water glass: 1% to 6%.
上述固化剂中的石灰粉通过以下方式制成：将工业级石灰在烘箱内以100～150℃的 温度烘干，至质量不变，冷却后磨细过200目筛，然后放入温度为140～160℃的电炉内煅烧0.5～1小时后，得到石灰粉。The lime powder in the above-mentioned curing agent is made by the following method: dry the industrial-grade lime in an oven at a temperature of 100-150°C until the quality remains unchanged, grind it through a 200-mesh sieve after cooling, and then put it into the oven at a temperature of 140 Lime powder is obtained after calcining in an electric furnace at ~160°C for 0.5 to 1 hour.
上述固化剂中的粉煤灰粉体通过以下方式制成：将国家标准二级以上粉煤灰过筛， 取粒径小于2mm的组分放置在烘箱内，通入温度为100～150℃的气流烘干，使其含水率降低至2％以下，冷却后过200目筛，在经过500～700℃电炉煅烧1～2小时后，得到 粉煤灰粉体。The fly ash powder in the above-mentioned curing agent is made by the following method: sieve the fly ash above the national standard level two, take the components with a particle size of less than 2mm and place them in the oven, and pass them into the oven at a temperature of 100-150°C. Airflow drying reduces the moisture content to less than 2%, passes through a 200-mesh sieve after cooling, and is calcined in an electric furnace at 500-700°C for 1-2 hours to obtain fly ash powder.
上述固化剂的活化钢渣粉通过以下方法制备而成：首先将工业级硅酸钠粉体和工业 级氢氧化钠粉体按照模数为1.2～1.5配置成水玻璃溶液并搅拌均匀，含水率为30％～50％； 将钢渣研磨并过200目筛，得到钢渣粉。然后将钢渣粉和水玻璃溶液按照固液比5:1～10:1 的比例进行混合，在温度30～35℃下，震荡搅拌搅拌12～24小时静置36～72小时后，将 混合料置于烘箱内，通入温度为100～250℃的气流烘干，使其含水率小于2％，然后球磨 并过200目筛，制得活化钢渣粉。The activated steel slag powder of the above curing agent is prepared by the following method: first, the industrial grade sodium silicate powder and industrial grade sodium hydroxide powder are prepared into a water glass solution according to the modulus of 1.2 to 1.5 and stirred evenly, and the water content is 30% to 50%; Grinding steel slag and passing it through a 200-mesh sieve to obtain steel slag powder. Then mix the steel slag powder and water glass solution according to the ratio of solid-to-liquid ratio of 5:1 to 10:1, shake and stir for 12 to 24 hours at a temperature of 30 to 35°C, and let the mixture stand for 36 to 72 hours. Put it in an oven, pass it into an air flow at a temperature of 100-250°C to dry it, make its moisture content less than 2%, then ball mill it and pass it through a 200-mesh sieve to obtain activated steel slag powder.
上述固化剂的钢渣粉由以下方法制备而成：将水淬转炉进行破碎并过2mm筛，将过筛后的钢渣粉放置于烘箱内，通过温度为100～150℃的气流烘干，使其含水率低于2％， 然后研磨并过200目筛，再经过500～700℃电炉煅烧1～2小时后，得到钢渣粉。The steel slag powder of the above curing agent is prepared by the following method: crush the water-quenched converter and pass through a 2mm sieve, place the sieved steel slag powder in an oven, and dry it by airflow at a temperature of 100-150°C to make it The water content is lower than 2%, then ground and passed through a 200-mesh sieve, and then calcined in an electric furnace at 500-700°C for 1-2 hours to obtain steel slag powder.
上述固化剂的磷酸二氢钾粉通过以下方法制备而成：将工业级磷酸二氢钾放置于烘 箱内，通过温度为100～150℃的气流烘干，使其含水率低于2％，研磨并过0.075mm筛，得到磷酸二氢钾粉体。The potassium dihydrogen phosphate powder of the above-mentioned curing agent is prepared by the following method: put the industrial-grade potassium dihydrogen phosphate in an oven, and dry it by airflow at a temperature of 100-150°C to make the moisture content lower than 2%, and grind And pass through a 0.075mm sieve to obtain potassium dihydrogen phosphate powder.
上述用于重金属污染场地修复的固化剂的制备方法包括以下步骤：The preparation method of the curing agent for the restoration of heavy metal-contaminated sites includes the following steps:
1)将石灰粉、粉煤灰粉、活化钢渣粉以及磷酸二氢钾粉进行混合，其中各组分的重量百分比为：石灰粉：10％～30％、粉煤灰粉：20％～50％、活化钢渣粉：30％～50％、 磷酸二氢钾粉：0.5％～2％。1) Mix lime powder, fly ash powder, activated steel slag powder and potassium dihydrogen phosphate powder, wherein the weight percentage of each component is: lime powder: 10% to 30%, fly ash powder: 20% to 50% %, activated steel slag powder: 30% to 50%, potassium dihydrogen phosphate powder: 0.5% to 2%.
2)采用干法搅拌1～2小时，使混合均匀后过200目筛，得到固化剂。2) Stir for 1 to 2 hours by dry method, make the mixture uniform and pass through a 200-mesh sieve to obtain a curing agent.
上述用于重金属污染场地修复的固化剂的应用方法为：将固化剂与重金属污染土壤 进行混合搅拌，固化剂掺量占污染土壤的干重质量比为5～15％，搅拌时污染土壤含水率 控制在15～35％之间。The application method of the above-mentioned curing agent for the restoration of heavy metal-contaminated sites is as follows: mixing and stirring the curing agent and the heavy metal-contaminated soil. Control it between 15 and 35%.
作为优选例，所述的重金属污染土壤小于0.075mm土颗粒含量大于60％，其中重金属铅含量大于2 500mg/kg，重金属锌含量大于2 500mg/kg，重金属镉含量大于500 mg/kg。As a preferred example, the content of soil particles smaller than 0.075 mm in the heavy metal-polluted soil is greater than 60%, wherein the content of heavy metal lead is greater than 2500 mg/kg, the content of heavy metal zinc is greater than 2500 mg/kg, and the content of heavy metal cadmium is greater than 500 mg/kg.
下面通过试验来论证本发明的固化剂具有优良的固化效果。The following test demonstrates that the curing agent of the present invention has an excellent curing effect.
试验对修复后的复合重金属污染土，即使用固化剂对复合重金属污染场地进行处理 后的污染土体的毒性浸出特性、酸碱度进行评定，其中，毒性浸出特性测试通过硫酸硝酸法进行测定；土壤的酸碱度通过固化土的水溶液pH值(固液比为1:1)进行评定。The test evaluates the toxic leaching characteristics and pH of the rehabilitated composite heavy metal-contaminated soil, that is, the contaminated soil after the composite heavy metal-contaminated site is treated with a curing agent. Among them, the toxic leaching characteristics test is determined by the sulfuric acid nitric acid method; The acidity and alkalinity are evaluated by the pH value of the aqueous solution of the solidified soil (solid-liquid ratio is 1:1).
试验材料experiment material
1)污染土：取自某一工业污染场地的铅、锌、镉复合污染土。其它主要理化特性如表1所示。1) Contaminated soil: lead, zinc and cadmium compound polluted soil taken from an industrial polluted site. Other main physical and chemical properties are shown in Table 1.
表1污染土主要物理化学性质Table 1 Main physical and chemical properties of polluted soil
2)钢渣粉：钢渣取自某钢铁厂磁选后的粒化转炉水淬钢渣，取回实验室后进行球磨 后，过200目筛备用。主要化学成分如表2所示。2) Steel slag powder: The steel slag is obtained from the granulated converter water-quenched steel slag after magnetic separation in a steel plant. After being taken back to the laboratory, it is ball milled and passed through a 200-mesh sieve for later use. The main chemical components are shown in Table 2.
表2钢渣主要成分及含量Table 2 Main components and content of steel slag
3)其他材料：3) Other materials:
石灰粉：分析纯。粉煤灰：国家一级粉煤灰，过200目筛。磷酸二氢钾：分析纯。 水玻璃粉：分析纯。硅酸钠：分析纯。氢氧化钠：分析纯。Lime powder: analytically pure. Fly ash: national first-class fly ash, passed through a 200-mesh sieve. Potassium dihydrogen phosphate: analytically pure. Water glass powder: analytically pure. Sodium silicate: analytically pure. Sodium hydroxide: analytically pure.
利用上述原材料，采用本发明实施例的制备方法分别制备石灰粉、粉煤灰、活化钢渣粉、磷酸二氢钾粉及配制相应的固化剂。Using the above-mentioned raw materials, lime powder, fly ash, activated steel slag powder, potassium dihydrogen phosphate powder and corresponding curing agent were prepared respectively by using the preparation method of the embodiment of the present invention.
作为优选例，所述的固化剂按照质量百分比，由以下组分组成：As a preferred example, the curing agent consists of the following components according to mass percentage:
石灰粉：10％～30％Lime powder: 10% to 30%
粉煤灰粉：20％～50％Fly ash powder: 20% to 50%
活化钢渣粉：30％～50％；Activated steel slag powder: 30% to 50%;
磷酸二氢钾粉：0.5％～2％；Potassium dihydrogen phosphate powder: 0.5% to 2%;
实施例1Example 1
将制备好的固化剂分别与试验材料1)中的复合重金属污染土样混合搅拌，其中固化 剂的掺量为5％(占复合金属污染土干重)，控制制备样含水率在20±2％之间，搅拌均匀后 采用静压法制样，制备成直径5cm，高度10cm的柱状样，用保鲜袋裹紧密封，在20℃、 湿度>95％条件下养护28天。Mix and stir the prepared curing agent with the composite heavy metal-contaminated soil sample in test material 1), wherein the dosage of the curing agent is 5% (accounting for the dry weight of the composite metal-contaminated soil), and the moisture content of the prepared sample is controlled at 20 ± 2 %, after stirring evenly, adopt the static pressure method to prepare a columnar sample with a diameter of 5cm and a height of 10cm, wrap it tightly with a fresh-keeping bag, and preserve it for 28 days at 20°C and humidity >95%.
实施例2Example 2
与实施例1的制样过程和养护过程相同，不同点是，固化剂的掺量为10％(固化剂占 重金属及有机物复合污染土干重)。Same as the sample preparation process and curing process of embodiment 1, difference is, the dosage of curing agent is 10% (curing agent accounts for heavy metal and organic matter compound polluted soil dry weight).
实施例3Example 3
与实施例1的制样过程和养护过程相同，不同点是，固化剂的掺量为15％(固化剂占 重金属及有机物复合污染土干重)。Same as the sample preparation process and curing process of embodiment 1, difference is, the dosage of curing agent is 15% (curing agent accounts for heavy metal and organic matter compound polluted soil dry weight).
对比例1Comparative example 1
不添加任何固化剂，仅取试验材料1)中的复合重金属污染土样，即采用素土，采样静压法制样，制备成直径5cm，高度10cm的柱状样，用保鲜袋裹紧密封，在20℃、湿 度>95％条件下养护28天。Without adding any curing agent, only take the composite heavy metal-contaminated soil sample in the test material 1), that is, use plain soil, sample static pressure sample preparation, prepare a columnar sample with a diameter of 5 cm and a height of 10 cm, wrap it tightly with a fresh-keeping bag, and store it in a fresh-keeping bag. Cured for 28 days at 20°C and humidity >95%.
试验中涉及到的具体实验项目为：The specific experimental items involved in the test are:
试验1.毒性浸出试验Test 1. Toxicity leaching test
试验标准：国家环境保护行业标准《固体废物浸出毒性浸出方法硫酸硝酸法》(HJ/T 299-2007)。Test standard: National Environmental Protection Industry Standard "Solid Waste Leaching Toxic Leaching Method Sulfuric Acid Nitric Acid Method" (HJ/T 299-2007).
试验过程：实施例1、实施例2、实施例3和对比例1的各样品的制备和养护过程相同。养护后的固化污染土，称取其中60g样品置于105℃的烘箱中烘干，恒重至两次称量 值的误差小于±1％，计算得到试样含水率。按照含水率计算修复后固化土干重，称取干 基质量为20g的固化土样，并按照《固体废物浸出毒性浸出方法硫酸硝酸法》(HJ/T 299-2007)规定的方法及步骤进行试验。试验结果如表3所示。Test process: the preparation and curing process of each sample of Example 1, Example 2, Example 3 and Comparative Example 1 are the same. For the solidified contaminated soil after curing, weigh 60g of the sample and place it in an oven at 105°C for drying, and keep the weight constant until the error of the two weighing values is less than ±1%, and calculate the moisture content of the sample. Calculate the dry weight of the restored solidified soil according to the moisture content, weigh the solidified soil sample with a dry basis mass of 20g, and carry out the method and steps in accordance with the "Solid Waste Leaching Toxicity Leaching Method Sulfuric Acid Nitric Acid Method" (HJ/T 299-2007) test. The test results are shown in Table 3.
表3毒性浸出试验结果(mg/L)Table 3 Toxicity leaching test results (mg/L)
硫酸硝酸法浸出方法被用来评价固体废物是否为危险废物的标准，也是分析固体废 物在酸性降雨作用下的污染物浸出毒性特征的常用方法。从表3的毒性浸出试验结果可以看出：掺有本发明固化剂的修复后的土壤，其浸出液中铅(Pb)、锌(Zn)和镉(Cd) 的浸出浓度均随着固化剂的掺量增加而减少。通过对比例1可以发现，未处理的污染土 中的重金属迁移性和毒性极强，重金属铅(Pb)、锌(Zn)和镉(Cd)的浸出量远高于 《地下水质量标准》(GB/T 14848-9)中第四类水标准的界限值。与对比例1相比，可以看 出添加药剂可以显著降低污染土壤中重金属铅(Pb)、锌(Zn)和镉(Cd)的浸出浓度， 而且随着固化剂产量的增加，重金属浸出浓度显著降低，尤其是活性较高的镉(Cd)在 10％掺量下就无法检测出，大大提高了重金属污染土壤的环境安全性。从实施例2和3 可以看出，掺加本发明中的固化剂并养护28d后，铅(Pb)、锌(Zn)和镉(Cd)的稳 定性得到极大的提高，其浸出量远低于《地下水质量标准》(GB/T 14848-9)中第四类水标 准的界限值。Sulfuric acid nitric acid leaching method is used as a standard to evaluate whether solid waste is hazardous waste, and it is also a common method to analyze the leaching toxicity characteristics of pollutants in solid waste under the action of acidic rainfall. As can be seen from the toxicity leaching test result of table 3: the soil after being mixed with the remediation of solidifying agent of the present invention, the leaching concentration of lead (Pb), zinc (Zn) and cadmium (Cd) in its leachate all increases with the concentration of solidifying agent. Decrease with increasing dosage. From Comparative Example 1, it can be found that the mobility and toxicity of heavy metals in the untreated contaminated soil are extremely strong, and the leaching amount of heavy metals lead (Pb), zinc (Zn) and cadmium (Cd) is much higher than the "Groundwater Quality Standard" (GB /T 14848-9) the threshold value of the fourth type of water standard. Compared with Comparative Example 1, it can be seen that adding chemicals can significantly reduce the leaching concentration of heavy metals lead (Pb), zinc (Zn) and cadmium (Cd) in polluted soil, and with the increase of curing agent output, the leaching concentration of heavy metals is significantly Reduce, especially cadmium (Cd) with higher activity just can't be detected under 10% dosage, has improved the environmental safety of heavy metal polluted soil greatly. As can be seen from Examples 2 and 3, after adding the curing agent of the present invention and curing for 28d, the stability of lead (Pb), zinc (Zn) and cadmium (Cd) is greatly improved, and its leaching amount is far It is lower than the limit value of the fourth category water standard in the "Groundwater Quality Standard" (GB/T 14848-9).
试验2：修复土酸碱度试验Test 2: pH test of remediation soil
试验标准：ASTM Standard Test methods for pH of Soils D 4972-01。Test standard: ASTM Standard Test methods for pH of Soils D 4972-01.
试验过程：养护后的固化污染土，称取其中50g样品置于105℃下烘干，恒重至两次称量值的误差小于±1％，计算得到样品含水率。按照含水率计算修复土干重，过2mm 筛并称取干基质量为20g的修复土样，与20g蒸馏水搅拌混合，静置1h后取上清液测 试溶液pH值。试验结果如表4所示。Test process: Weigh 50g of the solidified contaminated soil after curing and dry it at 105°C, keep the weight until the error of the two weighing values is less than ±1%, and calculate the moisture content of the sample. Calculate the dry weight of the remediation soil according to the moisture content, pass through a 2mm sieve and weigh 20g of the remediation soil sample on a dry basis, stir and mix with 20g of distilled water, and take the supernatant to test the pH value of the solution after standing for 1h. The test results are shown in Table 4.
表4酸碱度试验结果Table 4 pH test results
固化土体的PH值是评价固化剂固化稳定化重金属效果的一项重要指标，对其修复场地二次开发利用的形式具有重大影响。通过表4酸碱度试验结果，通过对比三个实施 例和一个对比例的试验可得，添加固化剂后，污染土体的PH值增幅明显，修复后的污 染土体的PH均值在10～11之间，偏碱性。The PH value of the solidified soil is an important index to evaluate the effect of the solidification agent on the stabilization of heavy metals, and has a major impact on the form of secondary development and utilization of the restoration site. Through table 4 pH test result, can obtain by comparing three embodiments and a comparative example test, after adding solidifying agent, the PH value increase of polluted soil body is obvious, and the PH average value of the polluted soil body after repairing is between 10～11 Between, slightly alkaline.
以上所述，仅是本发明的较佳实施例而已，并非对本发明的结构做任何形式上的限 制。凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明的技术方案的范围内。The above descriptions are only preferred embodiments of the present invention, and do not limit the structure of the present invention in any form. All simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solutions of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201711114557.8ACN107814544A (en) | 2017-11-13 | 2017-11-13 | A kind of curing agent and methods for making and using same for Compound Heavy Metals soil |
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| CN201711114557.8ACN107814544A (en) | 2017-11-13 | 2017-11-13 | A kind of curing agent and methods for making and using same for Compound Heavy Metals soil |
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| CN201711114557.8APendingCN107814544A (en) | 2017-11-13 | 2017-11-13 | A kind of curing agent and methods for making and using same for Compound Heavy Metals soil |
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