WO2021057010A1 - 一种去除水体中重金属Cd的组合物及其制备方法与应用 - Google Patents

一种去除水体中重金属Cd的组合物及其制备方法与应用 Download PDF

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WO2021057010A1
WO2021057010A1 PCT/CN2020/083180 CN2020083180W WO2021057010A1 WO 2021057010 A1 WO2021057010 A1 WO 2021057010A1 CN 2020083180 W CN2020083180 W CN 2020083180W WO 2021057010 A1 WO2021057010 A1 WO 2021057010A1
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water
composition
heavy metal
cadmium
removing heavy
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French (fr)
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马基琴科夫·弗拉基米尔
博卡尼科娃·埃琳娜
张瑞萍
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江苏爱佳福如土壤修复有限公司
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds

Definitions

  • the invention belongs to the technical field of purifying industrial or natural water polluted by cadmium, and in particular relates to a composition for removing heavy metal Cd in water bodies and a preparation method and application thereof.
  • the final product is highly active in removing soluble cadmium from natural water and wastewater. influences.
  • Cadmium Cd is a highly toxic substance, which has toxic biological effects when the concentration is almost lower than that of any common mineral.
  • the mechanism of cadmium toxicity may be multi-factorial.
  • Cd directly or indirectly affects the functions of various systems and tissue cells, such as bones, respiratory tract and urinary, cardiovascular, gastrointestinal and nervous systems. These toxic effects can cause cell degradation or even deformation.
  • Cadmium can be used as a nutrient, but at high concentrations, they can interact with proteins, can change the structure and enzyme activity in aquatic organisms cells, and show its toxic effects at the level of the entire organism.
  • Fatty acids and fatty acid products are recognized as very promising organic drug transport agents or surfactants.
  • the results show that fatty acids can be used to transport micronutrients.
  • raw fatty acids usually have a high viscosity, which brings difficulties to practical applications.
  • the fatty acid ethyl ester FA has the same viscosity as water, which makes it easier to operate in terms of experimental research and practical applications.
  • the production of FA can be achieved by using natural resources, and the literature reports useful information as a drug delivery agent. This provides the possibility that FA can absorb cadmium from water. Therefore, FA can be used to remove cadmium from water.
  • This application mainly proposes a composition for removing heavy metal Cd in water and a preparation method and application thereof, so as to solve the technical problems of high fatty acid viscosity and difficulty in practical application in the prior art.
  • a preparation method of a composition for removing heavy metal Cd in water body including the following steps:
  • Step 1 Take the aqueous fatty acid ethyl ester suspoemulsion and the silicon-rich solution in a volume ratio of 1:100 to 100:1;
  • Step 2 Put the measured aqueous fatty acid ethyl ester suspoemulsion and silicon-rich solution into a reactor with a stirrer, and stir at 50-100r/min for 30min-14 days at room temperature to remove heavy metals in the water. Cd composition.
  • the silicon-rich solution is a mixed solution of one or more Si-rich solutions.
  • the effective ingredients of the aqueous fatty acid ethyl ester suspoemulsion are saturated fatty acids and unsaturated fatty acids, and the concentration of the effective ingredients in the aqueous fatty acid ethyl ester suspoemulsion is 0.1% to 99.9%.
  • the concentration of the silicon-rich solution is 5-500000 mg Si/L.
  • the Si-rich solution is one or a mixed solution of potassium silicate solution and sodium silicate solution.
  • the present invention also provides a composition for removing heavy metal Cd in water prepared by the above preparation method.
  • the present invention also provides the application of the composition for removing heavy metal Cd in water in the treatment of cadmium-containing sewage.
  • the application of the composition for removing heavy metal Cd from water in the treatment of cadmium-containing sewage includes the following steps:
  • the first step add the composition for removing heavy metal Cd from the water body to the cadmium-containing sewage, mix it evenly and let it stand for 1 minute to 2 weeks;
  • the second step after the completion of standing, separate the treated composition for removing heavy metal Cd from the water from the water;
  • the third step use the separated and treated composition for removing heavy metal Cd from the water body as diesel fuel or combustion to prepare silicon-cadmium-rich ash;
  • the fourth step the ash content rich in silicon-cadmium is used as a raw material for the production of heavy metal cadmium to produce cadmium.
  • the addition ratio of the composition for cadmium-containing sewage and heavy metal Cd removal from the water body is: add 100 ml to 100 liters to 1m 3 of cadmium-containing sewage water to remove heavy metals from the water body The ratio of the composition of Cd.
  • the second step is to separate the treated composition for removing heavy metal Cd from the water.
  • the separation method is to use a pump to extract the upper suspension, or to use a large centrifugal device to centrifuge, after centrifugation Use a pump to remove the upper suspension.
  • composition for removing heavy metal Cd from water bodies as described in the present application and its preparation method and application adopt the above technical scheme, compared with the prior art, and have the following technical effects:
  • An efficient, environmentally friendly and safe method for preparing a composition for removing heavy metal Cd from water bodies is provided, which is used to purify cadmium-contaminated water.
  • the final product can be used to purify natural and industrial polluted water.
  • the final product can be separated from the water surface and used for combustion or as diesel fuel.
  • the ash produced by this process contains a high content of cadmium, so it can be used as a raw material for the production of heavy metal cadmium, and it is an environmentally friendly method to realize recycling industry.
  • the method solves the problem of waste utilization after Cd treatment in sewage, and can be burned as an energy source to provide energy.
  • the resulting ash is also a source of Cd production in industry, which can be described as recycled and environmentally friendly.
  • This method has high removal rate and fast speed for cadmium concentration in sewage.
  • the Cd adsorption capacity of the composition mixture for removing heavy metal Cd in water is much higher than that of unsaturated fatty acid ethyl esters.
  • different silicon-rich materials have different effects on Cd removal.
  • the composition for removing heavy metal Cd in water prepared by sodium silicate solution A has the largest removal rate of Cd, and the composition for removing heavy metal Cd in water: the volume ratio of polluted water is At 1:1000, the content is reduced by 87.2-98.5%, and the composition for removing heavy metal Cd from the water body: when the volume ratio of polluted water is 1:100, the content is reduced by 93.3-99.4%.
  • the composition for removing heavy metal Cd in water prepared by sodium silicate solution B has a moderate effect on the removal rate of Cd, and the composition for removing heavy metal Cd in water: when the volume ratio of polluted water is 1:1000, the content is reduced by 84.6-95%.
  • the composition for removing heavy metal Cd in water the volume ratio of polluted water is 1:100, the content is reduced by 92-98.6%.
  • the composition made of liquid glass for removing heavy metal Cd in water has the smallest Cd removal rate, and the composition for removing heavy metal Cd in water: when the volume ratio of polluted water is 1:1000, the content is reduced by 39.4%-74.8%, and heavy metals are removed from the water.
  • the Cd composition: polluted water volume ratio is 1:100, the content is reduced by 80.3-90.5%. This shows that the higher the silicon content and the higher the pH of the silicon-rich material, the better the removal rate of Cd in sewage.
  • aqueous fatty acid ethyl ester suspoemulsion mentioned in this application was purchased from Agraforum South Africa (Pty) Ltd; liquid glass: purchased from Russia Ivdis Co., Ltd., company address prospektkomsomolsky, cheliabinsk, Russia.
  • a preparation method of a composition for removing heavy metal Cd in water body including the following steps:
  • the first step the effective ingredients of the water-based fatty acid ethyl ester suspoemulsion are saturated fatty acids and unsaturated fatty acids.
  • the concentration of the effective ingredients in the water-based fatty acid ethyl ester suspoemulsion is 0.1%-99.9%, from Agra Forum, South Africa. Purchased by South Africa (Pty) Ltd;
  • Step 2 Take the aqueous fatty acid ethyl ester suspoemulsion and the silicon-rich solution in a volume ratio of 1:100 to 100:1, and put them into a reactor with a stirrer, at room temperature, press 50-100r/min Stir for 30 min-14 days to prepare a composition for removing heavy metal Cd in water.
  • the silicon-rich solution is a mixed solution of one or two of potassium silicate solution and sodium silicate solution, and the concentration of the silicon-rich solution is 5- 500000mg Si/L.
  • composition for removing heavy metal Cd from water bodies in the treatment of cadmium-containing sewage includes the following steps:
  • Step 1 Add the composition for removing heavy metal Cd from the water at the ratio of 100 ml to 100 liters of cadmium-containing sewage in 1m 3 of water, add the composition for removing heavy metal Cd from the water to the cadmium-containing sewage, mix well and then stand still Processing 1 minute to 2 weeks;
  • Step 2 After the completion of standing, the fatty acid ethyl ester will be concentrated on the top of the liquid surface in the form of suspension, and the upper suspension liquid will be pumped out by a pump, or centrifuged by a large centrifugal device. After centrifugation, the upper suspension liquid will be pumped out from the water. Separation of the treated composition for removing heavy metal Cd from the water body;
  • the third step use the separated and treated composition for removing heavy metal Cd from the water body as diesel fuel or combustion to prepare silicon-cadmium-rich ash;
  • the fourth step the ash content rich in silicon-cadmium is used as a raw material for the production of heavy metal cadmium to produce cadmium.
  • the first laboratory experiment was carried out at the Institute of Basic Biology of the Russian Academy of Sciences.
  • the main purpose of this test is to determine the effect of treated and untreated aqueous fatty acid ethyl ester suspoemulsions on the concentration of cadmium in polluted water.
  • silicon-rich solutions were used in the experiment; the chemical properties of these substances are shown in Table 1.
  • Sodium silicate solution A Procured by Jiangsu Aijiafuru Soil Remediation Co., Ltd. according to the data configuration in Table 1;
  • Sodium silicate solution B Procured from the Russian Ekksi company according to the data in Table 1.
  • aqueous fatty acid ethyl ester suspoemulsion FA is used, and the effective ingredients of the suspoemulsion are saturated fatty acids and unsaturated fatty acids.
  • Each liter of aqueous fatty acid ethyl ester suspoemulsion contains 25 grams of active ingredients.
  • aqueous fatty acid ethyl ester suspoemulsion and the silicon-rich solution are mixed in a volume ratio of 1:1 and 10:1 to prepare a composition for removing heavy metal Cd in water.
  • a composition for removing heavy metal Cd from the water body was added to the water contaminated with cadmium at a ratio of 0.1 liter and 1 liter per cubic meter of contaminated water.
  • the polluted water contains 80 ppm of cadmium in the form of Cd(NO 3 ) 2 and its pH is about 7.
  • the solution was stirred at a speed of 100 rpm for 1 hour, mixed evenly and then allowed to stand for 1 hour, 24 hours, and 48 hours, and then water samples were collected.
  • the composition for removing heavy metal Cd in the water body is separated by centrifugation.
  • the cleaning solution was analyzed for cadmium by ICP-MS I Cap-Q (USA).
  • the obtained results show (see Table 2) that the use of the composition mixture for removing heavy metal Cd in water significantly reduces the cadmium content in sewage.
  • the Cd adsorption capacity of the composition mixture for removing heavy metal Cd in water is much higher than that of unsaturated fatty acid ethyl esters.
  • different silicon-rich materials have different effects on Cd removal.
  • the composition for removing heavy metal Cd in water prepared by sodium silicate solution A has the largest removal rate of Cd, and the composition for removing heavy metal Cd in water: the volume ratio of polluted water is At 1:1000, the content is reduced by 87.2-98.5%, and the composition for removing heavy metal Cd from the water body: the volume ratio of polluted water is 1:100, the content is reduced by 93.3-99.4%.
  • the composition for removing heavy metal Cd from the water made by the silicon-rich solution B has a moderate effect on the removal rate of Cd, and the composition for removing heavy metal Cd from the water: when the volume ratio of polluted water is 1:1000, the content is reduced by 84.6-95%, and the water is removed.
  • the content is reduced by 92-98.6%.
  • the Cd removal rate of the composition for removing heavy metal Cd in the water body made with liquid glass is the smallest, and the composition for removing heavy metal Cd in the water body: when the volume ratio of polluted water is 1:1000, the content is reduced by 39.4%-74.8%, removing heavy metals from the water body
  • the volume ratio of Cd composition: polluted water is 1:100, the content is reduced by 80.3-90.5%. . This shows that the higher the silicon content and the higher the pH of the silicon-rich material, the better the removal rate of Cd in sewage.
  • a preparation method of a composition for removing heavy metal Cd in water body including the following steps:
  • the first step the aqueous fatty acid ethyl ester suspoemulsion and the silicon-rich solution are measured in a volume ratio of 1:100 to 100:1.
  • the effective ingredients of the aqueous fatty acid ethyl ester suspoemulsion are saturated fatty acids and unsaturated fatty acids.
  • the concentration of the active ingredient in the fatty acid ethyl ester suspoemulsion is 0.1%-99.9%
  • the Si-rich solution is a mixed solution of one or two of potassium silicate solution and sodium silicate solution, and the concentration of the silicon-rich solution is 5-500000mg Si/L;
  • Step 2 Put the measured aqueous fatty acid ethyl ester suspoemulsion and silicon-rich solution into a reactor with a stirrer, and stir at 50-100r/min for 30min-14 days at room temperature to remove heavy metals in the water. Cd composition.
  • composition for removing heavy metal Cd from water bodies in the treatment of cadmium-containing sewage includes the following steps:
  • Step 1 Add the composition for removing heavy metal Cd from the water at the ratio of 100 ml to 100 liters of cadmium-containing sewage in 1m 3 of water, add the composition for removing heavy metal Cd from the water to the cadmium-containing sewage, mix well and then stand still Processing 1 minute to 2 weeks;
  • Step 2 The fatty acid ethyl ester will be concentrated on the top of the liquid surface in the form of a suspension, and the upper suspension will be pumped out with a pump, or centrifuged with a large centrifugal device. After centrifugation, the upper suspension will be pumped out with a pump, and the treated water will be removed from the water. The composition of the heavy metal Cd is separated.
  • the third step use the separated and treated composition for removing heavy metal Cd from the water body as diesel fuel or combustion to prepare silicon-cadmium-rich ash;
  • the fourth step the ash content rich in silicon-cadmium is used as a raw material for the production of heavy metal cadmium to produce cadmium.
  • the second experiment was carried out at the Institute of Basic Biology of the Russian Academy of Sciences.
  • the main purpose of this test is to purify the concentration of cadmium in polluted water with a composition mixture that removes heavy metal Cd in water.
  • the silicon-rich solution used sodium silicate solution A (China) and sodium silicate solution B (Russia).
  • the chemical properties of these substances are shown in Table 1.
  • An aqueous fatty acid ethyl ester suspoemulsion FA is used, and the effective ingredients of the suspoemulsion are saturated fatty acids and unsaturated fatty acids.
  • the composition for removing heavy metal Cd in the water body is added to the water contaminated by cadmium at a rate of 5 liters per cubic meter of contaminated water.
  • Contaminated water contains 140 ppm of cadmium in the form of Cd(NO3)2, and its pH is about 7.
  • the solution was stirred at a speed of 100 rpm for 1 hour, mixed evenly and then allowed to stand for 24 hours, and then water samples were collected.
  • the composition for removing heavy metal Cd in the water body is separated by centrifugation.
  • the cleaning solution was analyzed for cadmium by ICP-MS I Cap-Q (USA).
  • the concentrated and treated composition for removing heavy metal Cd in the water was burned, and the resulting ash was collected, and the total cadmium content was determined by microwave digestion of HNO3-H2O2-HFMedia, and analyzed by ICP-MS I Cap-Q (USA) .
  • the data obtained in Table 3 shows that both the original aqueous fatty acid ethyl ester suspoemulsion and the composition for removing heavy metal Cd in the water can remove cadmium in the solution and the effect is significant.
  • the aqueous fatty acid ethyl ester suspoemulsion reduces the cadmium concentration by 87.7-95.9%
  • the composition that removes the heavy metal Cd in the water body reduces the cadmium concentration by 95.1-99.7%.
  • the method has high removal rate and fast speed for the concentration of cadmium in the sewage, and the sodium silicate solution A with high silicon content of the silicon-rich material is more effective than the sodium silicate solution B with low content.
  • the total cadmium content in the aqueous fatty acid ethyl ester suspoemulsion is as high as 83.4-85.8%, while the total cadmium content in the composition for removing heavy metal Cd from the water body is 49.5-57.6%.
  • both ashes can be used as raw materials for the production of Cd.
  • the third experiment was carried out at the Institute of Basic Biology of the Russian Academy of Sciences.
  • the main purpose of this experiment is to prove that it is feasible to remove cadmium from industrial wastewater with a composition that removes heavy metal Cd in water.
  • This experiment was carried out using sodium silicate solution A (China) and liquid glass (Ivdis Co., Ltd., Russia). Waste water is taken from Kursk Battery Enterprise (Kursk, Russia).
  • the chemical composition of the wastewater is shown in Table 4.
  • the characteristics of the silicon-rich solution are shown in Table 1. Two concentrations of FA are used: 50g/L and 200g/L.
  • FA and the silicon-rich solution are mixed, and a composition mixture for removing heavy metal Cd in water is prepared after 1 day.
  • composition mixture for removing heavy metal Cd in the water body was added to the contaminated wastewater at a rate of 5 liters and 10 liters per cubic meter. The mixture was stirred periodically during 24 hours. The composition for removing heavy metal Cd in the water body is separated by centrifugation. Use icp-ms-i-cap-q (USA) to analyze the Cd content in the cleaning solution.
  • the treated composition for removing heavy metal Cd in the water body was fired and the ash was collected , and the total Cd content was measured after microwave digestion (HNO 3 -H 2 O 2 -HF medium), and Icp-Ms-I-Cap- Q (United States) for analysis.
  • the data obtained are shown in Table 5.
  • the concentration of Cd in raw water is very high.
  • the single use of FA can significantly reduce the concentration of Cd in the solution by 27-60%.
  • the higher the FA content the better the effect.
  • the composition for removing heavy metal Cd in water bodies can significantly increase the reduction rate of Cd in wastewater.
  • the use effect of sodium silicate solution A is better than that of liquid glass. The maximum effect is 99.5%.
  • the FA is 200 g/L and the application rate is 10 liters/m3.
  • the Cd content in the ash after FA treatment is higher (59.3-60.3%), and the Cd content in the composition for removing heavy metal Cd in the water after treatment is between 35.4-48.5%. All of these ash can be used in the production of Cd.
  • Table 5 The Cd content in the solution after the experiment and the total Cd content in the ash of the composition for removing heavy metal Cd from the water after combustion.

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

本申请公开一种去除水体中重金属Cd的组合物及其制备方法与应用，将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:100至100:1的比例量取，将量取的水性脂肪酸乙酯悬乳剂和富硅溶液投入带有搅拌器的反应釜中，常温下，按50--100r/min搅拌30min-14天，制得去除水体中重金属Cd的组合物，提供了高效、环保、安全的去除水体中重金属Cd的组合物的制备方法，用于净化镉污染水。最终产品可用于净化天然和工业污染水。最终产品可与水面分离，用于燃烧或用作柴油机燃料。该工艺产生的灰分含有高含量的镉，因此可作为一种生产重金属镉的原料，实现循环产业，是环境友好型的方法。

Description

一种去除水体中重金属Cd的组合物及其制备方法与应用 技术领域
本发明属于净化受镉污染的工业或天然水技术领域，特别涉及一种去除水体中重金属Cd的组合物及其制备方法与应用，最终产品对天然水和废水中去除可溶性镉具有很高的积极影响。
背景技术
镉Cd是一种剧毒物质，在浓度几乎比任何常见矿物的浓度都小的情况下具有毒性生物效应。镉致毒性的机制可能是多因素的。Cd通过直接或间接影响各种系统和组织细胞的功能，如骨骼、呼吸道和泌尿、心血管、胃肠和神经系统等而产生毒性。这些毒性效应会导致细胞退化甚至变形。
镉因存在普遍，易在水中溶解和转运成为造成环境污染的重要原因。它很容易被水生生物吸收。镉可以作为一种营养物质，但在高浓度下，它们可以与蛋白质相互作用，可以改变水生生物细胞内的结构和酶活性，并在整个生物体水平上显示其毒性作用。
中国和其他国家的许多河流、湖泊和河口都受到镉污染，这给水中的生物和使用鱼和其他水产养殖产品的人类带来了严重的问题。
污染水的净化是一个困难且非常昂贵的过程，通常使用不同的过滤系统。现在也有一些新的技术，例如使用特殊微生物从水中去除镉。但这些技术都是无效的，而且还没有解决饱和微藻利用的问题。
脂肪酸和脂肪酸产品，如脂肪酸乙酯，被公认为非常有前景的有机药物运输剂或表面活性剂。结果表明，脂肪酸可用于输送微量营养元素。
然而，原始脂肪酸通常具有高粘度，这给实际应用带来了困难。但是，脂肪酸乙酯FA与水具有相同的粘度，这使得在实验研究和实际应用方面更容易操作。此外，FA的生产可以通过使用自然资源来实现，而文献报道了作为药物递送剂的有用信息。这为FA可以从水中吸收镉提供了可能性。因此，FA可用于从水中去除镉。
发明内容
解决的技术问题：本申请主要是提出一种去除水体中重金属Cd的组合物及其制备方法与应用，解决现有技术中存在的脂肪酸粘度高、实际应用困难等技术问题。
技术方案：
一种去除水体中重金属Cd的组合物的制备方法，包括如下步骤：
第一步：将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:100至100:1的比例量取；
第二步：将量取的水性脂肪酸乙酯悬乳剂和富硅溶液投入带有搅拌器的反应釜中，常温下，按50--100r/min搅拌30min-14天，制得去除水体中重金属Cd的组合物。
作为本发明的一种优选技术方案：所述富硅溶液为一种或多种富Si溶液的混合溶液。
作为本发明的一种优选技术方案：所述水性脂肪酸乙酯悬乳剂的有效成分为饱和脂肪酸和不饱和脂肪酸，水性脂肪酸乙酯悬乳剂中有效成分的浓度为0.1％-99.9％。
作为本发明的一种优选技术方案：所述富硅溶液的浓度为5-500000mg Si/L。
作为本发明的一种优选技术方案：所述富Si溶液为硅酸钾溶液和硅酸钠溶液中的一种或两种溶液的混合溶液。
本发明还提出一种由上述制备方法制备所得的去除水体中重金属Cd的组合物。
另外，本发明还提供了所述去除水体中重金属Cd的组合物在含镉污水处理中的应用。
作为本发明的一种优选技术方案：所述去除水体中重金属Cd的组合物在含镉污水处理中的应用，包括如下步骤：
第一步：将去除水体中重金属Cd的组合物添加到含镉污水中，混合均匀后静置处理1分钟到2周；
第二步：静置完成后，从水中将处理后的去除水体中重金属Cd的组合物分离；
第三步：将分离出的处理后的去除水体中重金属Cd的组合物作为柴油机燃料或燃烧，制备成富硅-镉的灰分；
第四步：将富硅-镉的灰分作为一种生产重金属镉的原料生产镉。
作为本发明的一种优选技术方案：所述第一步中含镉污水与去除水体中重金属Cd的组合物添加比例为：按照1m 3的含镉污水中添加100毫升到100升去除水体中重金属Cd的组合物的比例。
作为本发明的一种优选技术方案：所述第二步从水中将处理后的去除水体中重金属Cd的组合物分离，分离方法为用泵抽出上层悬浮液，或者采用大型离心装置离心，离心后用泵抽走上层悬浮液。
有益效果：本申请所述一种去除水体中重金属Cd的组合物及其制备方法与应用采用以上技术方案与现有技术相比，具有以下技术效果：
1、提供了高效、环保、安全的去除水体中重金属Cd的组合物的制备方法，用于净化镉污染水。最终产品可用于净化天然和工业污染水。最终产品可与水面分离，用于燃烧或用作柴油机燃料。该工艺产生的灰分含有高含量的镉，因此可作为一种生产重金属镉的原料，实现循环产业，是环境友好型的方法。
2、利用去除水体中重金属Cd的组合物去除天然水和工业水中镉，以脂肪酸乙酯对镉的吸附为基础，采用可溶性硅饱和的方法去除水中的镉。
3、该方法解决了污水中Cd处理后的废物利用问题，可以作为能源原料进行燃烧，提供能量，所得灰分还是工业中生产Cd的一种来源，可谓循环利用，环境友好。
4、去除水体中重金属Cd的组合物的使用显著降低了污水中的镉含量，原始脂肪酸乙酯混合物使得镉浓度下降87.7-95.9％，去除水体中重金属Cd的组合物使得镉浓度下降95.1-99.7％。
5、该方法对污水中镉浓度的去除率高、速度快。
6、去除水体中重金属Cd的组合物混合物对Cd的吸附量远高于不饱和的脂肪酸乙酯。且不同的富硅材料对Cd去除的效果不同，经硅酸钠溶液A制得去除水体中重金属Cd的组合物对Cd的去除率最大，去除水体中重金属Cd的组合物:污染水体积比例为1:1000时，含量 减少87.2-98.5％，去除水体中重金属Cd的组合物:污染水体积比例为1:100时，含量减少93.3-99.4％。经硅酸钠溶液B制得去除水体中重金属Cd的组合物对Cd的去除率效果居中，去除水体中重金属Cd的组合物:污染水体积比例为1:1000时，含量减少84.6-95％，去除水体中重金属Cd的组合物:污染水体积比例为1:100时，含量减少92-98.6％。用液态玻璃制得去除水体中重金属Cd的组合物的Cd去除率最小，去除水体中重金属Cd的组合物:污染水体积比例为1:1000时，含量减少39.4％-74.8％，去除水体中重金属Cd的组合物:污染水体积比例为1:100时，含量减少80.3-90.5％。这说明，硅含量越高且pH高的富硅材料对污水中Cd的去除率效果越好。
具体实施方式
本申请中提及的水性脂肪酸乙酯悬乳剂从南非阿格福莱有限公司Agraforum South Africa(Pty)Ltd采购获得；液态玻璃：从俄罗斯Ivdis有限公司采购、公司地址prospektkomsomolsky、cheliabinsk、俄罗斯。
实施例1
一种去除水体中重金属Cd的组合物的制备方法，包括如下步骤：
第一步：准备水性脂肪酸乙酯悬乳剂的有效成分为饱和脂肪酸和不饱和脂肪酸，该水性脂肪酸乙酯悬乳剂中有效成分的浓度为0.1％-99.9％，从南非阿格福莱有限公司Agraforum South Africa(Pty)Ltd采购获得；
第二步：将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:100至100:1的比例量取，投入带有搅拌器的反应釜中，常温下，按50--100r/min搅拌30min-14天，制得去除水体中重金属Cd的组合物，富硅溶液为硅酸钾溶液和硅酸钠溶液中的一种或两种溶液的混合溶液，富硅溶液的浓度为5-500000mg Si/L。
去除水体中重金属Cd的组合物在含镉污水处理中的应用，包括如下步骤：
第一步：按照1m 3的含镉污水中添加100毫升到100升去除水体中重金属Cd的组合物的比例，将去除水体中重金属Cd的组合物添加到含镉污水中，混合均匀后静置处理1分钟到2周；
第二步：静置完成后，脂肪酸乙酯会以悬浮液形式集中在液面顶部，用泵抽出上层悬浮液，或者采用大型离心装置离心，离心后用泵抽走上层悬浮液，从水中将处理后的去除水体中重金属Cd的组合物分离；
第三步：将分离出的处理后的去除水体中重金属Cd的组合物作为柴油机燃料或燃烧，制备成富硅-镉的灰分；
第四步：将富硅-镉的灰分作为一种生产重金属镉的原料生产镉。
试验1
第一次实验室实验是在俄罗斯科学院基础生物研究所进行的。本试验的主要目的是测定经处理和未经处理的水性脂肪酸乙酯悬乳剂对污染水中镉浓度的影响。实验中使用了几种不同的富硅溶液；这些物质的化学特性见表1。
表1.测试富硅溶液的化学性质。
Figure PCTCN2020083180-appb-000001
硅酸钠溶液A：由江苏爱佳福如土壤修复有限公司按照表1数据配置采购；硅酸钠溶液B：按照表1数据从俄罗斯Ekksi公司采购。
采用水性脂肪酸乙酯悬乳剂FA，该悬乳剂有效成分为饱和脂肪酸和不饱和脂肪酸。每升水性脂肪酸乙酯悬乳剂含有25克有效成分。
将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:1和10:1的比例混合，制备去除水体中重金属Cd的组合物。
以每立方米污染水添加0.1升和1升的比例向受镉污染的水中添加去除水体中重金属Cd的组合物。受污染的水中含有80ppm以Cd(NO 3) 2形式存在的镉，其pH值约为7。以100rpm的速度搅拌溶液1小时，混合均匀后静置处理1小时、24小时和48小时后采集水样。用离心法分离处理后的去除水体中重金属Cd的组合物。用ICP-MS I Cap-Q(美国)对清洗液进行了镉分析。
所得结果显示(见表2)，去除水体中重金属Cd的组合物混合物的使用显著降低了污水中的镉含量。去除水体中重金属Cd的组合物混合物对Cd的吸附量远高于不饱和的脂肪酸乙酯。且不同的富硅材料对Cd去除的效果不同，经硅酸钠溶液A制得去除水体中重金属Cd的组合物对Cd的去除率最大，去除水体中重金属Cd的组合物:污染水体积比为1:1000时，含量减少87.2-98.5％，去除水体中重金属Cd的组合物:污染水体积比为1:100时，含量减少93.3-99.4％。富硅溶液B制得去除水体中重金属Cd的组合物对Cd的去除率效果居中，去除水体中重金属Cd的组合物:污染水体积比为1:1000时，含量减少84.6-95％，去除水体中重金属Cd的组合物:污染水体积比为1:100时，含量减少92-98.6％。用液态玻璃制得去除水体中重金属Cd的组合物的Cd去除率最小，去除水体中重金属Cd的组合物:污染水体积比为1:1000时，含量减少39.4％-74.8％，去除水体中重金属Cd的组合物:污染水体积比为1:100时，含量减少80.3-90.5％。。这说明，硅含量越高且pH高的富硅材料对污水中Cd的去除率效果越好。
表2纯化液中镉的含量
Figure PCTCN2020083180-appb-000002
Figure PCTCN2020083180-appb-000003
实施例2
一种去除水体中重金属Cd的组合物的制备方法，包括如下步骤：
第一步：将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:100至100:1的比例量取，所述水性脂肪酸乙酯悬乳剂的有效成分为饱和脂肪酸和不饱和脂肪酸，水性脂肪酸乙 酯悬乳剂中有效成分的浓度为0.1％-99.9％，所述富Si溶液为硅酸钾溶液和硅酸钠溶液中的一种或两种溶液的混合溶液，富硅溶液的浓度为5-500000mg Si/L；
第二步：将量取的水性脂肪酸乙酯悬乳剂和富硅溶液投入带有搅拌器的反应釜中，常温下，按50--100r/min搅拌30min-14天，制得去除水体中重金属Cd的组合物。
去除水体中重金属Cd的组合物在含镉污水处理中的应用，包括如下步骤：
第一步：按照1m 3的含镉污水中添加100毫升到100升去除水体中重金属Cd的组合物的比例，将去除水体中重金属Cd的组合物添加到含镉污水中，混合均匀后静置处理1分钟到2周；
第二步：脂肪酸乙酯会以悬浮液形式集中在液面顶部，用泵抽出上层悬浮液，或者采用大型离心装置离心，离心后用泵抽走上层悬浮液，从水中将处理后的去除水体中重金属Cd的组合物分离。
第三步：将分离出的处理后的去除水体中重金属Cd的组合物作为柴油机燃料或燃烧，制备成富硅-镉的灰分；
第四步：将富硅-镉的灰分作为一种生产重金属镉的原料生产镉。
第二个实验是在俄罗斯科学院基础生物研究所进行的。本试验的主要目的是用去除水体中重金属Cd的组合物混合物对污染水中镉的浓度进行净化。本实验富硅溶液采用了硅酸钠溶液A(中国)和硅酸钠溶液B(俄罗斯)。这些物质的化学性质见表1。
采用水性脂肪酸乙酯悬乳剂FA，该悬乳剂有效成分为饱和脂肪酸和不饱和脂肪酸。使用两种水性脂肪酸乙酯悬乳剂中饱和脂肪酸和不饱和脂肪酸浓度的FA，25g/L和100g/L。
按照体积比5:1的比例，将FA与富硅溶液混合，经过2天和1周的时间制备去除水体中重金属Cd的组合物混合物。
将去除水体中重金属Cd的组合物以每立方米污染水添加5升的比例添加到受镉污染的水中。受污染的水含有140ppm以Cd(NO3)2的形式存在的镉，其pH值约为7。以100rpm的速度搅拌溶液1小时，混合均匀后静置处理24小时后采集水样。用离心法分离处理后的去除水体中重金属Cd的组合物。用ICP-MS I Cap-Q(美国)对清洗液进行镉分析。
将实验后的浓缩的处理后的去除水体中重金属Cd的组合物燃烧，收集所得灰份，经微波消解HNO3-H2O2-HFMedia测定总镉含量，并用ICP-MS I Cap-Q(美国)进行分析。
表3.试验后溶液中的镉含量和燃烧后FA的灰份中的总镉含量
Figure PCTCN2020083180-appb-000004
所得数据如表3显示，在原始水性脂肪酸乙酯悬乳剂和去除水体中重金属Cd的组合物均能去除溶液中的镉且效果显著，其中水性脂肪酸乙酯悬乳剂使得镉浓度下降87.7-95.9％，去除水体中重金属Cd的组合物物使得镉浓度下降95.1-99.7％。该方法对污水中镉浓度的去除率高、速度快，使用富硅材料硅含量高的硅酸钠溶液A比含量低的硅酸钠溶液B更有效。
水性脂肪酸乙酯悬乳剂中的总镉含量高达83.4-85.8％，而去除水体中重金属Cd的组合物中的总镉含量为49.5-57.6％。然而，这两种灰烬都可以作为生产Cd的原料。
实施例3
第三个实验在俄罗斯科学院基础生物研究所进行。本试验的主要目的是证明用去除水体中重金属Cd的组合物从工业废水中去除镉是可行的。本实验采用硅酸钠溶液A(中国)和液体玻璃(Ivdis有限公司，俄罗斯)进行。废水取自库尔斯克蓄电池企业(俄罗斯库尔斯克)。该废水的化学成分见表4。富硅溶液的特性见表1。使用两种浓度的FA：50g/L和200g/L。
按照体积比10:1的比例，将FA与富硅溶液混合，经过1天的时间制备去除水体中重金属Cd的组合物混合物。
将去除水体中重金属Cd的组合物混合物以每立方米5升和10升的速率添加到受污染废水中。混合物在24小时内定期搅拌。用离心法分离处理后的去除水体中重金属Cd的组合物。用icp-ms-i-cap-q(美国)分析清洗液中的Cd含量。
将实验后的处理后的去除水体中重金属Cd的组合物烧制后收集灰分，微波消解(HNO 3–H 2O 2–HF介质)后测定总Cd含量，并用Icp-Ms-I-Cap-Q(美国)进行分析。
所得数据见表5。与其它污染物相比，原水中Cd的浓度很高。单用FA可显著降低溶液中Cd的浓度，降低幅度为27-60％。FA含量越高，效果越好。去除水体中重金属Cd的组合物可显著提高废水中Cd的还原率。硅酸钠溶液A的使用效果优于液体玻璃。最大效应为99.5％，对于经硅酸钠溶液A处理的FA，FA为200g/L，施用量为10升/m3。
FA处理后的灰分中Cd含量较高(59.3-60.3％)，而处理后的去除水体中重金属Cd的组合物中Cd含量在35.4-48.5％之间。所有这些灰分都可用于Cd的生产。
表4工业废水的化学特性(库尔斯克蓄电池企业)。
Figure PCTCN2020083180-appb-000005
表5实验后的溶液中Cd含量和燃烧后的去除水体中重金属Cd的组合物灰分中总Cd含量。
Figure PCTCN2020083180-appb-000006

Claims (10)

  1. 一种去除水体中重金属Cd的组合物的制备方法，其特征在于包括如下步骤：
    第一步：将水性脂肪酸乙酯悬乳剂与富硅溶液按体积比1:100至100:1的比例量取；
    第二步：将量取的水性脂肪酸乙酯悬乳剂和富硅溶液投入带有搅拌器的反应釜中，常温下，按50--100r/min搅拌30min-14天，制得去除水体中重金属Cd的组合物。
  2. 根据权利要求1所述去除水体中重金属Cd的组合物的制备方法，其特征在于：所述富硅溶液为一种或多种富Si溶液的混合溶液。
  3. 根据权利要求1所述去除水体中重金属Cd的组合物的制备方法，其特征在于：所述水性脂肪酸乙酯悬乳剂的有效成分为饱和脂肪酸和不饱和脂肪酸，水性脂肪酸乙酯悬乳剂中有效成分的浓度为0.1％-99.9％。
  4. 根据权利要求2所述去除水体中重金属Cd的组合物的制备方法，其特征在于：所述富硅溶液的浓度为5-500000mg Si/L。
  5. 根据权利要求2所述去除水体中重金属Cd的组合物的制备方法，其特征在于：所述富Si溶液为硅酸钾溶液和硅酸钠溶液中的一种或两种溶液的混合溶液。
  6. 一种去除水体中重金属Cd的组合物，其特征在于：通过权利要求1～5任一项所述的制备方法制备得到。
  7. 一种权利要求6所述去除水体中重金属Cd的组合物在含镉污水处理中的应用。
  8. 根据权利要求7所述去除水体中重金属Cd的组合物在含镉污水处理中的应用，其特征在于，包括如下步骤：
    第一步：将去除水体中重金属Cd的组合物添加到含镉污水中，混合均匀后静置处理1分钟到2周；
    第二步：静置完成后，从水中将处理后的去除水体中重金属Cd的组合物分离；
    第三步：将分离出的处理后的去除水体中重金属Cd的组合物作为柴油机燃料或燃烧，制备成富硅-镉的灰分；
    第四步：将富硅-镉的灰分作为一种生产重金属镉的原料生产镉。
  9. 根据权利要求8所述去除水体中重金属Cd的组合物在含镉污水处理中的应用，其特征在于，所述第一步中含镉污水与去除水体中重金属Cd的组合物添加比例为：按照1m 3的含镉污水中添加100毫升到100升去除水体中重金属Cd的组合物的比例。
  10. 根据权利要求9所述去除水体中重金属Cd的组合物在含镉污水处理中的应用，其特征在于：所述第二步从水中将处理后的去除水体中重金属Cd的组合物分离，分离方法为用泵抽出上层悬浮液，或者采用大型离心装置离心，离心后用泵抽走上层悬浮液。
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