技术领域Technical Field
本发明涉及铀污染地下水修复领域，尤其指一种注射型HAP及其制备方法和应用。The invention relates to the field of uranium contaminated groundwater remediation, and in particular to an injection type HAP and a preparation method and application thereof.
背景技术Background technique
目前地浸采铀生产主要以酸法和“CO2＋O2”中性浸出法为主导。酸法地浸采用的浸出剂H2SO4在注入地下后，不仅将铀浸出，同时也会浸出其他非放射性组分。而中性浸出法相较于酸法地浸对地下水影响较小，但浸出剂的注入也会导致地下水中铀与其他组分的含量升高，造成地下水污染。因此为了避免地浸采区终采后周围地下水被污染，消除环境隐患，需要对地浸采区终采后的地下水进行修复。At present, the production of in-situ uranium leaching is mainly dominated by the acid method and the "CO2 + O2 " neutral leaching method. The leaching agent H2 SO4 used in the acid in-situ leaching will not only leach uranium but also other non-radioactive components after being injected into the ground. Compared with the acid in-situ leaching, the neutral leaching method has less impact on groundwater, but the injection of the leaching agent will also increase the content of uranium and other components in the groundwater, causing groundwater pollution. Therefore, in order to avoid the pollution of the surrounding groundwater after the in-situ leaching area is finally mined and eliminate environmental risks, it is necessary to repair the groundwater after the in-situ leaching area is finally mined.
常用的地浸铀矿山地下水修复技术包括自然衰减技术、微生物修复技术和抽出—处理技术等。自然衰减技术无需人工干预，环境友好但修复周期长，长期监测所需成本较高。微生物修复技术修复成本低，受环境影响较小，操作简单。但在实际应用中，微生物修复技术周期长、碳源供给不足、修复效果稳定性差。抽出—处理技术需定期对地下水进行水质检测、提供能量供给和设备维护等，这使得修复成本大大提高。因此，研发一种高效、低廉的铀污染地下水修复方法十分有必要。Commonly used in-situ leaching uranium mine groundwater remediation technologies include natural attenuation technology, microbial remediation technology, and extraction-treatment technology. Natural attenuation technology does not require human intervention and is environmentally friendly, but the remediation cycle is long and the cost of long-term monitoring is high. Microbial remediation technology has low remediation costs, is less affected by the environment, and is simple to operate. However, in actual applications, microbial remediation technology has a long cycle, insufficient carbon source supply, and poor stability of remediation effects. Extraction-treatment technology requires regular water quality testing of groundwater, energy supply, and equipment maintenance, which greatly increases the cost of remediation. Therefore, it is very necessary to develop an efficient and low-cost method for remediating uranium-contaminated groundwater.
纳米羟基磷灰石（hydroxyapatite，简称HAP），是动物与人体中重要的无机成分，具有良好的生物活性和生物相容性。作为表面具有大量空隙的纳米材料，其为吸附重金属离子提供了大量的吸附点位，可通过吸附沉淀和离子交换的方式去除铀污染物，在铀污染地下水修复领域受到广泛关注。但在实际时，纳米羟基磷灰石在铀污染地下水修复过程中存在着溶解性、分散性较低的局限。Nanohydroxyapatite (HAP) is an important inorganic component in animals and humans, with good bioactivity and biocompatibility. As a nanomaterial with a large number of voids on the surface, it provides a large number of adsorption sites for heavy metal ions, and can remove uranium pollutants through adsorption precipitation and ion exchange. It has received extensive attention in the field of uranium-contaminated groundwater remediation. However, in practice, nanohydroxyapatite has the limitations of low solubility and dispersibility in the remediation of uranium-contaminated groundwater.
发明内容Summary of the invention
本发明的目的之一在于提供一种注射型HAP的制备方法，以制备出具有高溶解性、高分散性的注射型HAP。One of the objectives of the present invention is to provide a method for preparing an injectable HAP, so as to prepare an injectable HAP with high solubility and high dispersibility.
为了解决上述技术问题，本发明采用如下技术方案：一种注射型HAP的制备方法，包括以下步骤：In order to solve the above technical problems, the present invention adopts the following technical solution: a method for preparing an injectable HAP, comprising the following steps:
步骤一、取钙盐溶于水中，得到溶液A；Step 1: dissolving calcium salt in water to obtain solution A;
步骤二、取磷酸盐和柠檬酸盐溶于水中，得溶液B；Step 2: dissolving phosphate and citrate in water to obtain solution B;
步骤三、将溶液A滴加到溶液B中得到混合溶液，再将混合溶液进行水浴加热；Step 3, adding solution A dropwise to solution B to obtain a mixed solution, and then heating the mixed solution in a water bath;
步骤四、对水浴加热后的混合溶液静置从而得到胶体溶液状的注射型HAP。Step 4: The mixed solution heated in a water bath is allowed to stand to obtain an injectable HAP in the form of a colloidal solution.
优选地，步骤一中，所述钙盐为氯化钙、硝酸钙、硫酸钙、氢氧化钙中的一种。Preferably, in step 1, the calcium salt is one of calcium chloride, calcium nitrate, calcium sulfate and calcium hydroxide.
更优选地，步骤二中，所述柠檬酸盐为柠檬酸钙、柠檬酸铵、柠檬酸钾中的一种。More preferably, in step 2, the citrate is one of calcium citrate, ammonium citrate and potassium citrate.
更优选地，步骤二中，所述磷酸盐为磷酸氢铵、磷酸二氢钠、磷酸钠、磷酸中的一种。More preferably, in step 2, the phosphate is one of ammonium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, and phosphoric acid.
更优选地，所述钙盐与磷酸盐的摩尔比为1.67:1。More preferably, the molar ratio of the calcium salt to the phosphate is 1.67:1.
更优选地，步骤三中，静置时的温度为常温。More preferably, in step three, the temperature during standing is room temperature.
另外，本发明还提供一种上述方法制备得到的注射型HAP的应用方法：将所述注射型HAP加入经过酸法或中性浸出法采铀后的铀污染地下水中，在铀污染地下水的pH值发生变化后，然后对pH值进行调节以使其复原。In addition, the present invention also provides an application method of the injectable HAP prepared by the above method: adding the injectable HAP into uranium-contaminated groundwater after uranium is mined by acid or neutral leaching, and after the pH value of the uranium-contaminated groundwater changes, the pH value is adjusted to restore it.
优选地，用缓冲剂对pH值进行调节，所述缓冲剂包括柠檬酸、蔗渣木质素、离子活化剂、络合剂。Preferably, the pH value is adjusted with a buffer, which includes citric acid, bagasse lignin, an ion activator, and a complexing agent.
其中，所述离子活化剂为EDTA、DTPA、海藻粉、塔姆MN盐中的一种或多种的混合；所述络合剂为氨基三乙酸、葡萄酸钠、植酸中的一种或多种的混合物。The ion activator is a mixture of one or more of EDTA, DTPA, seaweed powder and Tam's MN salt; the complexing agent is a mixture of one or more of aminotriacetic acid, sodium gluconate and phytic acid.
与现有技术相比，本发明制备得到的注射型HAP材料对酸法地浸采区的铀污染地下水的铀去除率可达到97.74%，对“CO2＋O2”中性浸出法的铀污染地下水的铀去除率可达到96.04%。另一方面还可改善纳米羟基磷灰石在铀污染地下水中的的溶解性、分散性，并增加其化学稳定性，使其在除铀过程中更加稳定可靠。Compared with the prior art, the injection type HAP material prepared by the present invention can achieve a uranium removal rate of 97.74% for uranium contaminated groundwater in acid in-situ leaching areas, and a uranium removal rate of 96.04% for uranium contaminated groundwater in "CO2 +O2 " neutral leaching method. On the other hand, it can also improve the solubility and dispersibility of nano-hydroxyapatite in uranium contaminated groundwater, and increase its chemical stability, making it more stable and reliable in the uranium removal process.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明制备得到的注射型HAP的XRD照片；FIG1 is an XRD photograph of the injection type HAP prepared by the present invention;
图2为本发明制备得到的注射型HAP的SEM图谱。FIG. 2 is a SEM image of the injectable HAP prepared in the present invention.
具体实施方式Detailed ways
为了便于本领域技术人员的理解，下面结合实施例与附图对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments and drawings. The contents mentioned in the implementation modes are not intended to limit the present invention.
制备胶体溶液状的注射型HAP：Preparation of injectable HAP in colloidal solution form:
（1）称取1.482g氢氧化钙粉末溶于40mL去离子水中，放入超声波清洗器中超声5min，得到分散均匀的溶液A。(1) Weigh 1.482 g of calcium hydroxide powder and dissolve it in 40 mL of deionized water. Place the powder in an ultrasonic cleaner and ultrasonicate for 5 min to obtain a uniformly dispersed solution A.
（2）称取3.510g柠檬酸钠粉末溶于20mL去离子水中，加入0.63mL浓磷酸，放入磁子，放到磁力搅拌器上持续搅拌得到均一透明的溶液B。(2) Weigh 3.510 g of sodium citrate powder and dissolve it in 20 mL of deionized water. Add 0.63 mL of concentrated phosphoric acid, place a magnetic bar in the solution, and place it on a magnetic stirrer and stir continuously to obtain a uniform and transparent solution B.
（3）将步骤（1）中的A溶液边滴边搅拌加入步骤（2）中的B溶液，滴加完之后，持续搅拌10min，将其用保鲜膜封口放入超声波清洗器中超声处理10min，然后将其放入85℃的水浴锅中，边搅拌边水浴加热反应6h，反应结束后将混合溶液放入超声波清洗器中超声处理15min。(3) Add solution A in step (1) to solution B in step (2) dropwise while stirring. After the addition is complete, continue stirring for 10 minutes. Seal the mixture with plastic wrap and place it in an ultrasonic cleaner for ultrasonic treatment for 10 minutes. Then place it in a water bath at 85°C and heat it in a water bath for reaction for 6 hours while stirring. After the reaction is complete, place the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15 minutes.
（4）将步骤（3）所得混合溶液在常温下静置得到胶体溶液状的注射型HAP。(4) The mixed solution obtained in step (3) is allowed to stand at room temperature to obtain an injectable HAP in the form of a colloidal solution.
制备得到的注射型HAP的XRD照片以及SEM图谱分别如图1和图2所示。The XRD image and SEM spectrum of the prepared injection-type HAP are shown in FIG1 and FIG2 , respectively.
制备粉末状的柠檬酸钠改性纳米羟基磷灰石：Preparation of powdered sodium citrate-modified nano-hydroxyapatite:
（1）称取1.482g氢氧化钙粉末溶于40mL去离子水中，放入超声波清洗器中超声5min，得到分散均匀的溶液A。(1) Weigh 1.482 g of calcium hydroxide powder and dissolve it in 40 mL of deionized water. Place the powder in an ultrasonic cleaner and ultrasonicate for 5 min to obtain a uniformly dispersed solution A.
（2）称取3.510g柠檬酸钠粉末溶于20mL去离子水中，加入0.63mL浓磷酸，放入磁子，放到磁力搅拌器上持续搅拌得到均一透明的溶液B。(2) Weigh 3.510 g of sodium citrate powder and dissolve it in 20 mL of deionized water. Add 0.63 mL of concentrated phosphoric acid, place a magnetic bar in the solution, and place it on a magnetic stirrer and stir continuously to obtain a uniform and transparent solution B.
（3）将步骤（1）中的A溶液边滴边搅拌加入步骤（2）中的B溶液，滴加完之后，持续搅拌10min，将其用保鲜膜封口放入超声波清洗器中超声处理10min，将其放入85℃的水浴锅中，边搅拌边水浴加热反应6h。反应结束后将混合溶液放入超声波清洗器中超声处理15min。(3) Add the solution A in step (1) to the solution B in step (2) while stirring. After the addition is complete, continue stirring for 10 minutes. Seal the mixture with plastic wrap and place it in an ultrasonic cleaner for ultrasonic treatment for 10 minutes. Place it in an 85°C water bath and heat it in the water bath for 6 hours while stirring. After the reaction is complete, place the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15 minutes.
（4）将步骤（3）所得溶液静置取上层溶液采用高速离心机离心分离，离心转速11000rmp/min，离心20min，用无水乙醇洗涤数次将其固体放入真空干燥箱中干燥24h，研磨至无颗粒感，得到粉末状的柠檬酸钠改性纳米羟基磷灰石。(4) The solution obtained in step (3) was allowed to stand, and the upper layer of the solution was centrifuged in a high-speed centrifuge at a speed of 11000 rpm for 20 min. The solid was washed several times with anhydrous ethanol, dried in a vacuum drying oven for 24 h, and ground until there was no particle feeling, thereby obtaining powdered sodium citrate-modified nano-hydroxyapatite.
下面通过将上述两种材料分别应用于酸法或中性浸出法采铀后的铀污染地下水中进行除铀，并以各实施例和对比例的具体操作来探究对应材料的铀去除率的效果。The following is the process of removing uranium by applying the above two materials to uranium-contaminated groundwater after uranium mining by acid or neutral leaching, and exploring the effect of uranium removal rate of the corresponding materials through the specific operations of each embodiment and comparative example.
实施例1Example 1
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到3.05±0.2。反应30min后，测定剩余铀浓度，铀的去除率达85.78%。50 mL of uranium solution with a uranium concentration of 10 mg/L was added to a 150 mL conical flask. The pH of the uranium solution was 3.05 ± 0.2. Then 1 ml of colloidal solution injection-type HAP was added and stirred evenly. The pH of the uranium solution was measured to be 11.24. 1 mol/L sodium hydroxide and 1 mol/L hydrochloric acid were used to adjust the pH of the uranium solution to 3.05 ± 0.2. After 30 minutes of reaction, the remaining uranium concentration was measured, and the uranium removal rate reached 85.78%.
实施例2Example 2
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到3.05±0.2。反应60min后，测定剩余铀浓度，铀的去除率达91.78%。50 mL of uranium solution with a uranium concentration of 10 mg/L was added to a 150 mL conical flask. The pH of the uranium solution was 3.05 ± 0.2. Then 1 ml of colloidal solution injection-type HAP was added and stirred evenly. The pH of the uranium solution was measured to be 11.24. 1 mol/L sodium hydroxide and 1 mol/L hydrochloric acid were used to adjust the pH of the uranium solution to 3.05 ± 0.2. After 60 minutes of reaction, the remaining uranium concentration was measured, and the uranium removal rate reached 91.78%.
实施例3Example 3
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到3.05±0.2。反应90min后，测定剩余铀浓度，铀的去除率达97.74%。Add 50mL of uranium solution with a uranium concentration of 10mg/L into a 150mL conical flask, and the pH of the uranium solution is 3.05±0.2. Then add 1ml of colloidal solution injection type HAP and stir evenly. The pH of the uranium solution is measured to be 11.24. Use 1mol/L sodium hydroxide and 1mol/L hydrochloric acid to adjust the pH of the uranium solution to 3.05±0.2. After 90 minutes of reaction, the remaining uranium concentration is measured, and the uranium removal rate reaches 97.74%.
实施例4Example 4
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到7.2±0.1。反应240min后，测定剩余铀浓度，铀的去除率达86.29%。50 mL of uranium solution with a uranium concentration of 10 mg/L was added to a 150 mL conical flask. The pH of the uranium solution was 7.2 ± 0.1. Then 1 ml of colloidal solution injection-type HAP was added and stirred evenly. The pH of the uranium solution was measured to be 11.24. 1 mol/L sodium hydroxide and 1 mol/L hydrochloric acid were used to adjust the pH of the uranium solution to 7.2 ± 0.1. After 240 minutes of reaction, the remaining uranium concentration was measured, and the uranium removal rate reached 86.29%.
实施例5Example 5
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到7.2±0.1。反应300min后，测定剩余铀浓度，铀的去除率达92.48%。Add 50mL of uranium solution with a uranium concentration of 10mg/L into a 150mL conical flask, and the pH of the uranium solution is 7.2±0.1. Then add 1ml of colloidal solution injection type HAP and stir evenly. The pH of the uranium solution is measured to be 11.24. Use 1mol/L sodium hydroxide and 1mol/L hydrochloric acid to adjust the pH of the uranium solution to 7.2±0.1. After reacting for 300min, measure the residual uranium concentration, and the uranium removal rate reaches 92.48%.
实施例6Example 6
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用1mol/L氢氧化钠和1mol/L盐酸调节铀溶液pH值恢复到7.2±0.1。反应360min后，测定剩余铀浓度，铀的去除率达96.04%。50 mL of uranium solution with a uranium concentration of 10 mg/L was added to a 150 mL conical flask. The pH of the uranium solution was 7.2 ± 0.1. Then 1 ml of colloidal solution injection-type HAP was added and stirred evenly. The pH of the uranium solution was measured to be 11.24. 1 mol/L sodium hydroxide and 1 mol/L hydrochloric acid were used to adjust the pH of the uranium solution to 7.2 ± 0.1. After 360 minutes of reaction, the residual uranium concentration was measured, and the uranium removal rate reached 96.04%.
对比例1Comparative Example 1
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应30min后，测定剩余铀浓度，铀的去除率达80.16%。In a 150mL conical flask, add 50mL of uranium solution with a uranium concentration of 10mg/L, the pH of the uranium solution is 3.05±0.2, then add 0.012g of powdered sodium citrate modified nanohydroxyapatite and mix evenly, and the pH value of the solution is measured to have no significant change. After 30 minutes of reaction, the remaining uranium concentration is measured, and the uranium removal rate reaches 80.16%.
对比例2Comparative Example 2
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应60min后，测定剩余铀浓度，铀的去除率达85.37%。In a 150mL conical flask, 50mL of uranium solution with a uranium concentration of 10mg/L was added, and the pH of the uranium solution was 3.05±0.2. Then 0.012g of powdered sodium citrate-modified nanohydroxyapatite was added and mixed evenly. The pH value of the solution was measured to have no significant change. After 60 minutes of reaction, the residual uranium concentration was measured, and the uranium removal rate reached 85.37%.
对比例3Comparative Example 3
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应90min后，测定剩余铀浓度，铀的去除率达88.79%。In a 150mL conical flask, 50mL of uranium solution with a uranium concentration of 10mg/L was added, and the pH of the uranium solution was 3.05±0.2. Then 0.012g of powdered sodium citrate-modified nanohydroxyapatite was added and mixed evenly. The pH value of the solution was measured to have no significant change. After 90 minutes of reaction, the residual uranium concentration was measured, and the uranium removal rate reached 88.79%.
对比例4Comparative Example 4
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应240min后，测定剩余铀浓度，铀的去除率达82.41%。In a 150mL conical flask, 50mL of uranium solution with a uranium concentration of 10mg/L was added, and the pH of the uranium solution was 7.2±0.1. Then 0.012g of powdered sodium citrate-modified nanohydroxyapatite was added and mixed evenly. The pH value of the solution was measured to have no significant change. After 240min of reaction, the remaining uranium concentration was measured, and the uranium removal rate reached 82.41%.
对比例5Comparative Example 5
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应300min后，测定剩余铀浓度，铀的去除率达88.38%。In a 150mL conical flask, 50mL of uranium solution with a uranium concentration of 10mg/L was added, and the pH of the uranium solution was 7.2±0.1. Then 0.012g of powdered sodium citrate-modified nanohydroxyapatite was added and mixed evenly. The pH value of the solution was measured to have no significant change. After 300min of reaction, the residual uranium concentration was measured, and the uranium removal rate reached 88.38%.
对比例6Comparative Example 6
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为7.2±0.1，然后添加0.012g粉末状的柠檬酸钠改性纳米羟基磷灰石混合均匀，测得溶液pH值无明显变化。反应360min后，测定剩余铀浓度，铀的去除率达90.29%。In a 150mL conical flask, 50mL of uranium solution with a uranium concentration of 10mg/L was added, and the pH of the uranium solution was 7.2±0.1. Then 0.012g of powdered sodium citrate-modified nanohydroxyapatite was added and mixed evenly. The pH value of the solution was measured to have no significant change. After 360min of reaction, the residual uranium concentration was measured, and the uranium removal rate reached 90.29%.
实施例7Example 7
在150mL的锥形瓶中加入50mL铀浓度为10mg/L的铀溶液，铀溶液pH为3.05±0.2，然后添加1ml胶体溶液状的注射型HAP搅拌均匀，测得铀溶液pH为11.24，采用缓冲剂将铀溶液pH值恢复到3.05±0.2。反应30min后，测定剩余铀浓度，铀的去除率达97.25%。50 mL of uranium solution with a uranium concentration of 10 mg/L was added to a 150 mL conical flask. The pH of the uranium solution was 3.05 ± 0.2. Then 1 ml of colloidal solution injection-type HAP was added and stirred evenly. The pH of the uranium solution was measured to be 11.24. The buffer was used to restore the pH of the uranium solution to 3.05 ± 0.2. After 30 minutes of reaction, the remaining uranium concentration was measured, and the uranium removal rate reached 97.25%.
其中，缓冲剂包括柠檬酸、蔗渣木质素、离子活化剂、络合剂，而离子活化剂选用EDTA，络合剂选用氨基三乙酸。The buffer comprises citric acid, bagasse lignin, an ion activator and a complexing agent, wherein the ion activator is EDTA and the complexing agent is aminotriacetic acid.
通过实施例1-3和实施例4-6可知，投加相同量的注射型HAP时，对pH为3.05±0.2的铀溶液和pH为7.2±0.1的铀溶液的铀去除率都能达到97%左右，这表明使用本发明的注射型HAP加入经过酸法或中性浸出法采铀后的铀污染地下水中能够实现很好的除铀效果。其中，铀溶液pH值为3.05±0.2的反应平衡时间比铀溶液pH值为7.2±0.1的更短。It can be seen from Examples 1-3 and Examples 4-6 that when the same amount of injectable HAP is added, the uranium removal rate of the uranium solution with a pH of 3.05±0.2 and the uranium solution with a pH of 7.2±0.1 can reach about 97%, which indicates that the use of the injectable HAP of the present invention added to the uranium contaminated groundwater after uranium mining by acid or neutral leaching can achieve a good uranium removal effect. Among them, the reaction equilibrium time of the uranium solution with a pH of 3.05±0.2 is shorter than that of the uranium solution with a pH of 7.2±0.1.
通过实施例4-6和对比例4-6之间的比较可知，在相同条件下，使用本发明的胶体溶液状的注射型HAP的铀去除率要明显高于使用粉末状的柠檬酸钠改性纳米羟基磷灰石。而且加入胶体溶液状的注射型HAP的铀溶液pH值发生明显变化，但加入粉末状的柠檬酸钠改性纳米羟基磷灰石的铀溶液pH值基本不变，证明了本发明制备的注射型HAP材料在铀溶液中溶解性、分散性要高于纳米羟基磷灰石粉末材料。By comparing Examples 4-6 with Comparative Examples 4-6, it can be seen that under the same conditions, the uranium removal rate of the injectable HAP in the form of a colloidal solution of the present invention is significantly higher than that of the nano-hydroxyapatite modified with sodium citrate in powder form. Moreover, the pH value of the uranium solution to which the injectable HAP in the form of a colloidal solution is added changes significantly, but the pH value of the uranium solution to which the nano-hydroxyapatite modified with sodium citrate in powder form remains substantially unchanged, which proves that the injectable HAP material prepared by the present invention has higher solubility and dispersibility in the uranium solution than the nano-hydroxyapatite powder material.
通过实施例3和实施例7的比较可以看出，在相同条件下，采用特定的缓冲剂调节pH，能够显著缩短反应平衡时间，这是由于缓冲剂中，柠檬酸作为天然有机酸，具有很好的缓冲能力，它可以在调节pH的同时，通过其酸性官能团与金属离子形成络合物，从而有助于稳定铀离子，提高其与HAP的反应效率；而蔗渣木质素具有吸附作用，有助于固定铀离子，减少铀离子在溶液中的自由移动，这促进了铀与HAP的接触和反应；EDTA可以增加溶液中铀离子的有效浓度，因为它们可以与铀离子形成可溶性络合物，减少了沉淀或吸附在HAP表面的铀离子，从而提高了铀离子与HAP的反应速率；此外，氨基三乙酸能与铀离子形成稳定的络合物，这有助于提高铀的溶解度，从而加速了铀与注射型HAP的反应。因此，通过本发明特定的缓冲剂来调节pH，实现了显著缩短反应平衡时间的效果，这具有重要的实际意义。By comparing Example 3 and Example 7, it can be seen that under the same conditions, the reaction equilibrium time can be significantly shortened by adjusting the pH with a specific buffer. This is because in the buffer, citric acid, as a natural organic acid, has a good buffering capacity. It can form a complex with metal ions through its acidic functional group while adjusting the pH, thereby helping to stabilize uranium ions and improve their reaction efficiency with HAP; while bagasse lignin has an adsorption effect, which helps to fix uranium ions and reduce the free movement of uranium ions in the solution, which promotes the contact and reaction between uranium and HAP; EDTA can increase the effective concentration of uranium ions in the solution because they can form soluble complexes with uranium ions, reducing uranium ions precipitated or adsorbed on the surface of HAP, thereby increasing the reaction rate of uranium ions with HAP; in addition, aminotriacetic acid can form a stable complex with uranium ions, which helps to increase the solubility of uranium, thereby accelerating the reaction of uranium with injectable HAP. Therefore, by adjusting the pH with a specific buffer of the present invention, the effect of significantly shortening the reaction equilibrium time is achieved, which has important practical significance.
本发明所制备得到的胶体溶液状的注射型HAP，由于其纳米级或微米级的粒径，通常具有比粉末状的羟基磷灰石更高的比表面积。这意味着有更多的表面可用于与铀离子发生吸附或反应，从而提高了去除效率。而且胶体溶液中的HAP颗粒在溶液中分散得更均匀，这有助于提高其与铀离子的接触机会，增加了反应的可能性，同时，胶体溶液状的HAP由于其胶体性质，通常具有较好的悬浮稳定性，这有助于保持HAP颗粒在溶液中均匀分布，避免颗粒聚集和沉淀，从而维持其高反应活性。况且，胶体溶液状的HAP更适合于注射应用，因为它们可以更容易地通过注射器或其他设备进行输送。因此，由于其独特的物理和化学特性，本发明制备得到的胶体溶液状的注射型HAP在酸性和中性铀溶液中都能达到较高的除铀率。The colloidal solution-like injectable HAP prepared by the present invention generally has a higher specific surface area than powdered hydroxyapatite due to its nanometer or micrometer particle size. This means that there are more surfaces available for adsorption or reaction with uranium ions, thereby improving the removal efficiency. Moreover, the HAP particles in the colloidal solution are more evenly dispersed in the solution, which helps to increase the contact opportunities with uranium ions and increase the possibility of reaction. At the same time, the colloidal solution-like HAP generally has good suspension stability due to its colloidal properties, which helps to keep the HAP particles evenly distributed in the solution, avoid particle aggregation and precipitation, and thus maintain its high reactivity. Moreover, the colloidal solution-like HAP is more suitable for injection applications because they can be more easily delivered through a syringe or other equipment. Therefore, due to its unique physical and chemical properties, the colloidal solution-like injectable HAP prepared by the present invention can achieve a high uranium removal rate in both acidic and neutral uranium solutions.
为了让本领域普通技术人员更方便地理解本发明相对于现有技术的改进之处，本发明的一些附图和描述已经被简化，并且上述实施例为本发明较佳的实现方案，除此之外，本发明还可以其它方式实现，在不脱离本技术方案构思的前提下任何显而易见的替换均在本发明的保护范围之内。In order to make it easier for ordinary technicians in the field to understand the improvements of the present invention over the prior art, some drawings and descriptions of the present invention have been simplified, and the above-mentioned embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present technical solution is within the protection scope of the present invention.
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| CN202410522762.1ACN118343709A (en) | 2024-04-28 | 2024-04-28 | Injection HAP and preparation method and application thereof |
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| CN202410522762.1ACN118343709A (en) | 2024-04-28 | 2024-04-28 | Injection HAP and preparation method and application thereof |
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