CN114735845A - A method for recycling modified manganese slag to treat heavy metal ions - Google Patents

Abstract

Translated fromChinese

本发明公开了一种改性锰矿渣循环利用处理重金属离子的方法，属于重金属离子处理技术领域，所述步骤如下：(1)将待处理的重金属废水用碱性溶液调节pH＝9‑10；(2)将重金属废水与改性锰矿渣混合，搅拌20‑40min后静置；(3)静置12‑24h后过滤，分离后的废水进行后续处理，本发明的目的是开发一种利用锰矿渣去除废水中重金属离子的方法，同时解决目前废弃锰矿渣活性低，去除重金属离子效果差的问题。The invention discloses a method for treating heavy metal ions by recycling modified manganese slag, and belongs to the technical field of heavy metal ion treatment. (2) mixing heavy metal waste water with modified manganese slag, stirring for 20-40min and then leaving standstill; (3) filtering after standing for 12-24h, and the separated waste water is subjected to follow-up treatment, and the purpose of the present invention is to develop a kind of manganese ore utilizing manganese ore. The method for removing heavy metal ions in wastewater by slag simultaneously solves the problems of low activity of current waste manganese slag and poor removal effect of heavy metal ions.

Description

Translated fromChinese

一种改性锰矿渣循环利用处理重金属离子的方法A method for recycling modified manganese slag to treat heavy metal ions

技术领域technical field

本发明涉及重金属离子处理技术领域，尤其涉及一种改性锰矿渣循环利用处理重金属离子的方法。The invention relates to the technical field of heavy metal ion treatment, in particular to a method for treating heavy metal ions by recycling modified manganese slag.

背景技术Background technique

重金属对环境及人体的危害主要是由于含重金属废水被排入水体，使水体中的重金属含量急剧升高，进而浸染土壤并通过食物链富集危害人体健康。重金属元素具有难降解、毒性大、处理后不易回收等特点，严重危害人类的安全，如Cr⁶⁺、Cd²⁺等重金属元素具有致癌、致畸、致突变等危害，如日本富士山县神通川流域发生“痛痛病”就是典型的Cd²⁺中毒事件。而这主要是由于电解、电镀、金属矿山、冶炼、化工、电子、制革等行业的重金属废水的不合理排放导致的。为了兼顾环境和经济发展效益，因此对于处理水中的重金属污染研究已成为一种必然趋势。The harm of heavy metals to the environment and human body is mainly because the wastewater containing heavy metals is discharged into the water body, so that the heavy metal content in the water body rises sharply, which infects the soil and harms human health through the enrichment of the food chain. Heavy metal elements have the characteristics of refractory degradation, high toxicity, and difficult recycling after treatment, which seriously endanger human safety. For example, heavy metal elements such as Cr⁶⁺ and Cd²⁺ are carcinogenic, teratogenic, and mutagenic. The occurrence of "Ititai disease" in the basin is a typical Cd²⁺ poisoning event. This is mainly due to the unreasonable discharge of heavy metal wastewater from industries such as electrolysis, electroplating, metal mining, smelting, chemical industry, electronics, and tanning. In order to take into account the benefits of environmental and economic development, research on heavy metal pollution in treated water has become an inevitable trend.

锰矿是自然界中分布十分广泛的一类矿物，但是长久以来锰矿的开发利用主要在其资源属性方面，如电池、冶金、化工、玻璃等领域。而锰矿渣是天然锰矿经过电解或还原后剩余的废料，目前锰矿渣主要用于制造锰肥、混凝土、微晶玻璃等，其主要含有铁、铝、硅、钙、硫等成分。锰矿渣表面致密，少孔、颗粒较大，其主要由结晶矿渣和部分玻璃相组成，化学性质较稳定，活性发挥速度缓慢，因此，实现锰矿渣的再利用，使其变废为宝，循环利用处理废水中的重金属离子一条可持续发展的道路。因此激活锰矿渣活性后开发一条锰矿渣循环利用去除废水中的重金属离子的方法是亟不可待的。Manganese ore is a class of minerals widely distributed in nature, but the development and utilization of manganese ore has been mainly in its resource attributes for a long time, such as batteries, metallurgy, chemical industry, glass and other fields. Manganese slag is the remaining waste after electrolysis or reduction of natural manganese ore. At present, manganese slag is mainly used to manufacture manganese fertilizer, concrete, glass-ceramic, etc. It mainly contains iron, aluminum, silicon, calcium, sulfur and other components. The surface of manganese slag is dense, with few pores and large particles. It is mainly composed of crystalline slag and part of glass phase. Its chemical properties are relatively stable and its activity is slow. Therefore, the reuse of manganese slag is realized, turning waste into treasure and recycling A sustainable way to treat heavy metal ions in wastewater. Therefore, it is urgent to develop a method of recycling manganese slag to remove heavy metal ions in wastewater after activating the activity of manganese slag.

发明内容SUMMARY OF THE INVENTION

有鉴于此，本发明的目的是开发一种利用锰矿渣去除废水中重金属离子的方法，同时解决目前废弃锰矿渣活性低，去除重金属离子效果差的问题。In view of this, the purpose of the present invention is to develop a method for utilizing manganese slag to remove heavy metal ions in waste water, and simultaneously solve the problems of low activity of current waste manganese slag and poor removal of heavy metal ions.

一种改性锰矿渣循环利用处理重金属离子的方法，所述步骤如下：A method for recycling modified manganese slag for processing heavy metal ions, the steps are as follows:

(1)将待处理的重金属废水用碱性溶液调节pH＝9-10；(1) the heavy metal wastewater to be treated is adjusted to pH=9-10 with an alkaline solution;

(2)将重金属废水与改性锰矿渣混合，搅拌20-40min后静置；(2) mixing heavy metal waste water with modified manganese slag, stirring for 20-40min and leaving it to stand;

(3)静置12-24h后过滤，分离后的废水进行后续处理。(3) filter after standing for 12-24h, and the separated waste water is subjected to subsequent treatment.

工业重金属废水中废水的酸性较强，为了便于改性锰矿渣捕捉和絮集重金属离子因此需要调节pH值呈碱性，最佳的范围为pH＝9-10。调节pH时可以采用石灰水调节pH。The acidity of wastewater in industrial heavy metal wastewater is strong. In order to facilitate the capture and flocculation of heavy metal ions by modified manganese slag, it is necessary to adjust the pH value to be alkaline, and the optimal range is pH=9-10. When adjusting the pH, lime water can be used to adjust the pH.

同时为了更好的去除废水中的其他污染物，还可以与格栅、筛网、曝气池、生化池、沉淀池等其他处理手段结合使用。At the same time, in order to better remove other pollutants in wastewater, it can also be used in combination with other treatment methods such as grids, screens, aeration tanks, biochemical tanks, and sedimentation tanks.

进一步，所述改性锰矿渣的用量为1-1000g/L，改性锰矿渣主要去除废水中的铜离子、铅离子、汞离子、镉离子，重金属含量越高改性锰矿渣的使用量越多。Further, the amount of the modified manganese slag is 1-1000g/L, and the modified manganese slag mainly removes copper ions, lead ions, mercury ions, and cadmium ions in the wastewater. The higher the heavy metal content, the more the modified manganese slag is used. many.

进一步，所述改性锰矿渣的制备方法包括以下步骤：Further, the preparation method of the modified manganese slag comprises the following steps:

a.将锰矿渣粉碎后置于70-80℃的热水中静置24h，捞出后用三乙醇胺溶液于室温下浸泡搅拌处理24-36h，捞出用清水冲洗，晾干，研磨成锰矿粉；a. Pulverize the manganese slag and place it in hot water at 70-80°C for 24 hours, then take it out and soak it in triethanolamine solution for 24-36 hours at room temperature, rinse it with water, dry it, and grind it into manganese ore pink;

b.将处理后的锰矿粉加入Tris-盐酸缓冲液中，再加入多巴胺、月桂磺酸钠，调节pH＝9-10，搅拌3-4h后静置12h，静置完成后过滤，在室温下加入柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液制成的混合溶液，反应4h取出，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，搅拌24h后得到改性后的锰矿渣。b. Add the treated manganese ore powder to Tris-hydrochloric acid buffer, then add dopamine and sodium lauryl sulfonate, adjust pH=9-10, stir for 3-4h, then let stand for 12h, filter after standing, and filter at room temperature A mixed solution made of sodium citrate solution, sodium nitrate solution and potassium fluoride solution was added, reacted for 4 hours and taken out, then mixed with phthalate and polylactic acid-glycolic acid copolymer, and stirred for 24 hours to obtain a modified Manganese slag.

锰矿渣主要由结构致密的结晶矿物、玻璃体、可溶性盐以及杂质等物质组成，粉碎后锰矿渣颗粒和结晶矿物细化，锰矿渣内部结构发生改变，用热水浸泡后可去除大部分可溶性盐和杂质，避免后续操作的原料与可溶性盐反应。三乙醇胺溶液呈弱碱性，对锰矿渣粉具有局部腐蚀溶解作用，促使锰矿渣的晶格进一步变化，形成具有孔隙的颗粒，初步激活锰矿渣活性，而后通过研磨，在机械力的作用下锰矿渣的晶型转变、晶粒细化，比表面积增大。锰矿渣通过热水和三乙醇胺溶液处理后晶型发生变化，随后与多巴胺、月桂磺酸钠在碱性条件下生成具有亲水作用的聚多巴胺，使锰矿渣表面具有较高的可修饰性。再经过柠檬酸钠、硝酸钠和氟化钾对锰矿渣进行改性处理，使锰矿渣表面的聚多巴胺与金属氧化物以及改性物稳定螯合，进一步提高锰矿渣的活性。废水处理过程中在碱性条件下锰矿渣水化生成凝胶吸附重金属离子。邻苯二甲酸酯和聚乳酸-羟基乙酸共聚物混合于锰矿渣粉表面生成薄膜，将具有吸附性和高活性的锰矿渣粉包裹在内，与碱性废水搅拌接触后薄膜降解，锰矿渣粉吸附重金属离子，达到处理废水的目的，也便于平时保存。Manganese slag is mainly composed of densely structured crystalline minerals, glass bodies, soluble salts and impurities. After crushing, manganese slag particles and crystalline minerals are refined, and the internal structure of manganese slag is changed. After soaking in hot water, most soluble salts and minerals can be removed. impurities, to avoid the reaction of raw materials for subsequent operations with soluble salts. The triethanolamine solution is weakly alkaline, which has a local corrosion and dissolution effect on the manganese slag powder, which promotes the further change of the lattice of the manganese slag to form particles with pores, and initially activates the activity of the manganese slag. The crystal form of the slag is transformed, the grains are refined, and the specific surface area is increased. The crystal form of manganese slag was changed after being treated with hot water and triethanolamine solution, and then polydopamine with hydrophilic effect was formed with dopamine and sodium lauryl sulfonate under alkaline conditions, which made the surface of manganese slag highly modifiable. Then, the manganese slag is modified by sodium citrate, sodium nitrate and potassium fluoride, so that the polydopamine on the surface of the manganese slag can be stably chelated with metal oxides and modified substances, and the activity of the manganese slag is further improved. In the wastewater treatment process, the manganese slag is hydrated under alkaline conditions to form a gel to adsorb heavy metal ions. Phthalates and polylactic acid-glycolic acid copolymers are mixed on the surface of manganese slag powder to form a film, and the manganese slag powder with adsorption and high activity is wrapped in it. After stirring and contacting with alkaline wastewater, the film is degraded and the manganese slag The powder adsorbs heavy metal ions to achieve the purpose of treating wastewater, and it is also convenient for normal storage.

进一步，所述锰矿渣中的氧化铁含量≤3％，锰矿渣中含有性质不稳定的氧化铁，极易导致在活化过程中与原料发生反应，对锰矿渣改性时需要控制铁含量。Further, the iron oxide content in the manganese slag is less than or equal to 3%, and the manganese slag contains unstable iron oxide, which can easily cause a reaction with the raw materials during the activation process, and the iron content needs to be controlled when modifying the manganese slag.

进一步，所述三乙醇胺溶液的浓度为5-10wt％。Further, the concentration of the triethanolamine solution is 5-10 wt%.

进一步，所述锰矿渣与多巴胺、月桂磺酸钠质量比为10：(0.5-1)：0.01。Further, the mass ratio of the manganese slag to dopamine and sodium lauryl sulfonate is 10:(0.5-1):0.01.

进一步，所述锰矿渣与柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的质量比为1：0.6：1：1。Further, the mass ratio of the manganese slag to sodium citrate solution, sodium nitrate solution and potassium fluoride solution is 1:0.6:1:1.

进一步，所述柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的浓度分别为0.2mol/L、1mol/L、0.1mol/L。Further, the concentrations of the sodium citrate solution, sodium nitrate solution and potassium fluoride solution are respectively 0.2 mol/L, 1 mol/L and 0.1 mol/L.

进一步，所述邻苯二甲酸酯与聚乳酸-羟基乙酸共聚物的质量比为1：0.4。Further, the mass ratio of the phthalate to the polylactic acid-glycolic acid copolymer is 1:0.4.

有益效果：Beneficial effects:

1、本发明对废弃锰矿渣进行改性利用，改性后提高了锰矿渣的活性，可以处理含有铜离子、铅离子、汞离子、镉离子的工业重金属废水，去除率达到了95％以上，而对汞离子和镉离子的去除率达到了99％以上。1. The present invention modifies and utilizes waste manganese slag. After modification, the activity of manganese slag is improved, and industrial heavy metal wastewater containing copper ions, lead ions, mercury ions and cadmium ions can be treated, and the removal rate reaches more than 95%. The removal rate of mercury ions and cadmium ions reached more than 99%.

2、本发明扩大了锰矿渣的使用场景，提高资源利用率，实现了绿色循环发展，减少和避免污染物的产生。2. The present invention expands the use scene of manganese slag, improves resource utilization rate, realizes green circular development, and reduces and avoids the generation of pollutants.

3、本发明的处理方法简单方便，适合在工厂中大规模推广使用。3. The processing method of the present invention is simple and convenient, and is suitable for large-scale promotion and use in factories.

具体实施方式Detailed ways

以下将结合实施例对本发明进行详细说明：Below in conjunction with embodiment, the present invention will be described in detail:

实施例1：改性锰矿渣制备一Embodiment 1: Modified manganese slag preparation one

本实施例制备锰矿渣先称取原料：The present embodiment prepares manganese slag by weighing raw materials first:

200g锰矿渣、10g多巴胺、0.2g月桂磺酸钠、0.2mol/L 120g柠檬酸钠溶液、1mol/L200g硝酸钠溶液、0.1mol/L 200g氟化钾溶液、200g邻苯二甲酸酯、80g聚乳酸-羟基乙酸共聚物，本实施的锰矿渣来源于重庆秀山某矿业公司，其中，锰矿渣中氧化铁的含量约为2.1％。200g manganese slag, 10g dopamine, 0.2g sodium lauryl sulfonate, 0.2mol/L 120g sodium citrate solution, 1mol/L 200g sodium nitrate solution, 0.1mol/L 200g potassium fluoride solution, 200g phthalate, 80g The polylactic acid-glycolic acid copolymer, the manganese slag used in this implementation comes from a mining company in Xiushan, Chongqing, wherein the content of iron oxide in the manganese slag is about 2.1%.

制备步骤如下：The preparation steps are as follows:

a.将锰矿渣粉碎成2-3mm左右的细渣后置于80℃的热水中静置24h，捞出，用5wt％的三乙醇胺溶液于室温下浸泡搅拌处理24h，三乙醇胺溶液没过锰矿渣即可，随后捞出用清水冲洗，晾干，研磨成锰矿粉，粒径约为0.05mm左右；a. Pulverize the manganese slag into fine slag of about 2-3mm, put it in hot water at 80°C for 24 hours, take it out, soak it with 5wt% triethanolamine solution at room temperature and stir it for 24 hours, the triethanolamine solution does not pass the Manganese slag is enough, then take it out, rinse it with water, dry it, and grind it into manganese ore powder with a particle size of about 0.05mm;

b.将处理后的锰矿粉加入0.05mmol/L Tris-盐酸缓冲液中，没过即可，再加入多巴胺、月桂磺酸钠，调节pH＝9，搅拌3h后静置12h，静置完成后过滤，在室温下将锰矿粉加入柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的混合溶液中，反应4h取出，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，常温下搅拌24h后得到改性后的锰矿渣。b. Add the processed manganese ore powder to 0.05mmol/L Tris-hydrochloric acid buffer solution, and then add dopamine and sodium lauryl sulfonate, adjust pH=9, stir for 3h and let stand for 12h. Filter, add manganese ore powder to the mixed solution of sodium citrate solution, sodium nitrate solution and potassium fluoride solution at room temperature, take out after reaction for 4 hours, and then mix with phthalate and polylactic acid-glycolic acid copolymer, at room temperature After stirring for 24h, the modified manganese slag was obtained.

实施例2：改性锰矿渣制备二Embodiment 2: Modified manganese slag preparation two

本实施例制备锰矿渣先称取原料：The present embodiment prepares manganese slag by weighing raw materials first:

100g锰矿渣、10g多巴胺、0.1g月桂磺酸钠、0.2mol/L 60g柠檬酸钠溶液、1mol/L100g硝酸钠溶液、0.1mol/L 100g氟化钾溶液、100g邻苯二甲酸酯、40g聚乳酸-羟基乙酸共聚物，本实施的锰矿渣来源于重庆秀山某矿业公司，其中，锰矿渣中氧化铁的含量约为2.1％。100g manganese slag, 10g dopamine, 0.1g sodium lauryl sulfonate, 0.2mol/L 60g sodium citrate solution, 1mol/L 100g sodium nitrate solution, 0.1mol/L 100g potassium fluoride solution, 100g phthalate, 40g The polylactic acid-glycolic acid copolymer, the manganese slag used in this implementation comes from a mining company in Xiushan, Chongqing, wherein the content of iron oxide in the manganese slag is about 2.1%.

制备步骤如下：The preparation steps are as follows:

a.将锰矿渣粉碎成2-5mm左右的细渣后置于70℃的热水中静置24h，捞出，用8wt％的三乙醇胺溶液于室温下浸泡搅拌处理36h，三乙醇胺溶液没过锰矿渣即可，随后捞出用清水冲洗，晾干，研磨成锰矿粉，粒径约为0.05mm左右；a. Pulverize the manganese slag into fine slag of about 2-5mm, put it in hot water at 70°C for 24 hours, take it out, soak it with 8wt% triethanolamine solution at room temperature and stir for 36 hours, the triethanolamine solution does not pass Manganese slag is enough, then take it out, rinse it with water, dry it, and grind it into manganese ore powder with a particle size of about 0.05mm;

b.将处理后的锰矿粉加入0.05mmol/L Tris-盐酸缓冲液中，没过即可，再加入多巴胺、月桂磺酸钠，调节pH＝10，搅拌4h后静置12h，静置完成后过滤，在室温下将锰矿粉加入柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的混合溶液中，反应4h取出，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，常温下搅拌24h后得到改性后的锰矿渣。b. Add the treated manganese ore powder to 0.05mmol/L Tris-hydrochloric acid buffer solution, and then add dopamine and sodium lauryl sulfonate, adjust pH=10, stir for 4h and then let stand for 12h. Filter, add manganese ore powder to the mixed solution of sodium citrate solution, sodium nitrate solution and potassium fluoride solution at room temperature, take out after reaction for 4 hours, and then mix with phthalate and polylactic acid-glycolic acid copolymer, at room temperature After stirring for 24h, the modified manganese slag was obtained.

实施例3：改性锰矿渣制备三Embodiment 3: Modified manganese slag preparation three

本实施例制备锰矿渣先称取原料：The present embodiment prepares manganese slag by weighing raw materials first:

50g锰矿渣、3.5g多巴胺、0.05g月桂磺酸钠、0.2mol/L 30g柠檬酸钠溶液、1mol/L50g硝酸钠溶液、0.1mol/L 50g氟化钾溶液、50g邻苯二甲酸酯、20g聚乳酸-羟基乙酸共聚物，本实施的锰矿渣来源于重庆秀山某矿业公司，其中，锰矿渣中氧化铁的含量约为2.1％。50g manganese slag, 3.5g dopamine, 0.05g sodium lauryl sulfonate, 0.2mol/L 30g sodium citrate solution, 1mol/L 50g sodium nitrate solution, 0.1mol/L 50g potassium fluoride solution, 50g phthalate, 20 g of polylactic acid-glycolic acid copolymer, the manganese slag used in this implementation is from a mining company in Xiushan, Chongqing, and the content of iron oxide in the manganese slag is about 2.1%.

制备步骤如下：The preparation steps are as follows:

a.将锰矿渣粉碎成2-5mm左右的细渣后置于75℃的热水中静置24h，捞出，用10wt％的三乙醇胺溶液于室温下浸泡搅拌处理25h，三乙醇胺溶液没过锰矿渣即可，随后捞出用清水冲洗，晾干，研磨成锰矿粉，粒径约为0.05mm左右；a. Pulverize the manganese slag into fine slag of about 2-5mm, then place it in hot water at 75°C for 24 hours, remove it, and soak it in a 10wt% triethanolamine solution at room temperature for 25 hours. Manganese slag is enough, then take it out, rinse it with water, dry it, and grind it into manganese ore powder with a particle size of about 0.05mm;

b.将处理后的锰矿粉加入0.05mmol/L Tris-盐酸缓冲液中没过即可，再加入多巴胺、月桂磺酸钠，调节pH＝9.5，搅拌3.5h后静置12h，静置完成后过滤，在室温下将锰矿粉加入柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的混合溶液中，反应4h取出，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，常温下搅拌24h后得到改性后的锰矿渣。b. Add the treated manganese ore powder to 0.05mmol/L Tris-hydrochloric acid buffer solution, then add dopamine and sodium lauryl sulfonate to adjust pH=9.5, stir for 3.5h and then let stand for 12h, after the standstill is completed Filter, add manganese ore powder to the mixed solution of sodium citrate solution, sodium nitrate solution and potassium fluoride solution at room temperature, take out after reaction for 4 hours, and then mix with phthalate and polylactic acid-glycolic acid copolymer, at room temperature After stirring for 24h, the modified manganese slag was obtained.

实施例4：Example 4:

用实施例1-3制备的改性锰矿渣处理重金属废水的方法如下：The method for treating heavy metal waste water with the modified manganese slag prepared by Example 1-3 is as follows:

(1)将待处理的重金属废水用碱性溶液调节pH＝9-10，优选石灰水溶液调节pH；(1) the heavy metal waste water to be treated is adjusted pH=9-10 with alkaline solution, preferably lime aqueous solution is adjusted pH;

(2)将重金属废水与改性锰矿渣混合，搅拌20-40min后静置；(2) mixing heavy metal waste water with modified manganese slag, stirring for 20-40min and leaving it to stand;

(3)静置12-24h后过滤，分离后的废水进行后续处理。(3) filter after standing for 12-24h, and the separated waste water is subjected to subsequent treatment.

对比例1：Comparative Example 1:

本对比例与实施例1形成对比。将相同的锰矿渣直接粉碎成0.05mm左右的细粉后用于废水处理。This comparative example is in contrast to Example 1. The same manganese slag is directly pulverized into fine powder of about 0.05mm for wastewater treatment.

对比例2：Comparative Example 2:

本对比例与实施例1形成对比，与实施例1的区别仅在于步骤a中未用热水浸泡，直接用三乙醇胺溶液在室温下浸泡搅拌后进行后续处理。This comparative example is in contrast with Example 1, and the difference from Example 1 is only that in step a, it is not soaked in hot water, but is directly soaked in triethanolamine solution at room temperature and stirred for subsequent treatment.

对比例3：Comparative Example 3:

本对比例与实施例1形成对比，与实施例1的区别仅在于将锰矿渣直接进行步骤b处理。This comparative example is in contrast with Example 1, and the difference from Example 1 is only that the manganese slag is directly processed in step b.

对比例4：Comparative Example 4:

本对比例与实施例1形成对比，与实施例1的区别仅在于步骤b中未使用多巴胺和月桂磺酸钠，其具体的制备步骤如下：This comparative example is contrasted with Example 1, and the difference from Example 1 is only that dopamine and sodium lauryl sulfonate are not used in step b, and the specific preparation steps are as follows:

a.将锰矿渣粉碎成2-5mm左右的细渣后置于80℃的热水中静置24h，捞出，用5wt％的三乙醇胺溶液于室温下浸泡搅拌处理24h，三乙醇胺溶液没过锰矿渣即可，随后捞出用清水冲洗，晾干，研磨成锰矿粉，粒径约为0.05mm左右；a. Pulverize the manganese slag into fine slag of about 2-5mm, put it in hot water at 80°C for 24 hours, take it out, soak it with 5wt% triethanolamine solution at room temperature and stir for 24 hours, the triethanolamine solution has not passed the Manganese slag is enough, then take it out, rinse it with water, dry it, and grind it into manganese ore powder with a particle size of about 0.05mm;

b.将处理后的锰矿粉在室温下加入柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液的混合溶液中，反应4h取出，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，常温下搅拌24h后得到改性后的锰矿渣。b. Add the processed manganese ore powder to the mixed solution of sodium citrate solution, sodium nitrate solution and potassium fluoride solution at room temperature, take out after reaction for 4 hours, and then mix with phthalate, polylactic acid-glycolic acid copolymer After mixing and stirring at room temperature for 24 hours, the modified manganese slag was obtained.

对比例5：Comparative Example 5:

本对比例与实施例1形成对比，与实施例1的区别仅在于步骤b中未使用柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液处理锰矿粉，其具体的制备步骤如下：This comparative example forms a contrast with Example 1, and the difference from Example 1 is only that in step b, sodium citrate solution, sodium nitrate solution, potassium fluoride solution are not used to treat manganese ore powder, and its specific preparation steps are as follows:

a.将锰矿渣粉碎成2-5mm左右的细渣后置于80℃的热水中静置24h，捞出，用5wt％的三乙醇胺溶液于室温下浸泡搅拌处理24h，三乙醇胺溶液没过锰矿渣即可，随后捞出用清水冲洗，晾干，研磨成锰矿粉，粒径约为0.05mm左右；a. Pulverize the manganese slag into fine slag of about 2-5mm, put it in hot water at 80°C for 24 hours, take it out, soak it with 5wt% triethanolamine solution at room temperature and stir for 24 hours, the triethanolamine solution has not passed the Manganese slag is enough, then take it out, rinse it with water, dry it, and grind it into manganese ore powder with a particle size of about 0.05mm;

b.将处理后的锰矿粉加入0.05mmol/L Tris-盐酸缓冲液中没过即可，再加入多巴胺、月桂磺酸钠，调节pH＝9，搅拌3h后静置12h，静置完成后过滤，随后与邻苯二甲酸酯、聚乳酸-羟基乙酸共聚物混合，常温下搅拌24h后得到改性后的锰矿渣。b. Add the processed manganese ore powder to 0.05mmol/L Tris-hydrochloric acid buffer solution, then add dopamine and sodium lauryl sulfonate, adjust pH=9, stir for 3h, let stand for 12h, and filter after standing , and then mixed with phthalate and polylactic acid-glycolic acid copolymer, and stirred at room temperature for 24 hours to obtain modified manganese slag.

将实施例1和对比例1-5的制备的改性后的锰矿渣进行废水处理试验：The modified manganese slag prepared in Example 1 and Comparative Examples 1-5 was subjected to a wastewater treatment test:

(1)、将硫酸铜、硝酸铅、氯化汞、氯化镉配置成配制成溶液模拟废水，使水中铜离子、铅离子、汞离子、镉离子浓度均10mg/L；(1), configure copper sulfate, lead nitrate, mercury chloride, and cadmium chloride into a solution to simulate wastewater, so that the concentrations of copper ions, lead ions, mercury ions, and cadmium ions in the water are all 10 mg/L;

(2)、调节废水pH，随后将废水分成每份1L，随后分别以200g/L的量加入实施例1和对比例1-5制备的改性锰矿渣，搅拌40min后静置；(2), adjust waste water pH, waste water is divided into every 1L subsequently, then add the modified manganese slag prepared by embodiment 1 and comparative example 1-5 with the amount of 200g/L respectively, leave standstill after stirring 40min;

(3)、静置24h后过滤掉改性锰矿渣，检测分离后水中的铜离子、铅离子、汞离子、镉离子浓度。(3) After standing for 24 hours, filter out the modified manganese slag, and detect the concentrations of copper ions, lead ions, mercury ions and cadmium ions in the separated water.

一、将上述制备的废水采用石灰水调节pH＝5、9、13，将实施例1制备的改性锰矿渣分别用于上述废水中，得到的结果如表1所示：One, the waste water of above-mentioned preparation adopts lime water to adjust pH=5, 9, 13, the modified manganese slag prepared by embodiment 1 is used in above-mentioned waste water respectively, the result that obtains is as shown in table 1:

表1Table 1

Cu²⁺mg/LCu²⁺mg/LPb²⁺mg/LPb²⁺mg/LHg²⁺mg/LHg²⁺mg/LCd²⁺mg/LCd²⁺mg/LpH＝5pH=52.102.103.203.201.701.701.501.50pH＝9pH=90.110.110.230.230.020.020.040.04pH＝13pH=130.730.730.520.520.250.250.180.18

根据表1的结果可知，本发明制备的改性锰矿渣在pH＝9的时候去除效果最佳，当pH过低，废水呈酸性时，改性锰矿渣难以捕捉和絮集重金属，而当pH过高、碱性较强时，改性锰矿渣捕捉和絮集后出现反溶现象，导致聚集在改性锰矿渣周围的重金属离子重新溶解在溶液中，导致去除效果下降。According to the results in Table 1, the modified manganese slag prepared by the present invention has the best removal effect when pH=9. When the pH is too low and the wastewater is acidic, the modified manganese slag is difficult to capture and flocculate heavy metals, and when the pH is too low, the wastewater is acidic. When it is too high and the alkalinity is strong, the modified manganese slag will be reverse-dissolved after being captured and flocculated, resulting in the heavy metal ions gathered around the modified manganese slag being redissolved in the solution, resulting in a decrease in the removal effect.

二、将废水用石灰水调节至pH＝9的条件下，分别用实施例1和对比例1-5制备的改性锰矿渣按照上述方法处理废水，得到的数据如表2所示。2. Under the condition that the wastewater is adjusted to pH=9 with lime water, the modified manganese slag prepared in Example 1 and Comparative Examples 1-5 is used to treat the wastewater according to the above method, and the obtained data are shown in Table 2.

表2Table 2

根据表2的结果可知，实施例1制备的改性锰矿渣重金属去除率较高，均达到了95％以上，尤其是汞离子和镉离子去除效果最佳。而对比例1是直接将原料锰矿渣粉碎后使用未作其他处理，仅靠内部较少的孔隙吸附重金属，其去除重金属的效果较差。对比例2与实施例1相比未在改性处理前用热水处理，导致锰矿渣中的部分可溶性盐溶解后与原料反应附着于锰矿渣表面导致去除效果降低。对比例3未进行步骤a处理，未将锰矿渣颗粒和结晶矿物细化，同时也未进行三乙醇胺改性和热水除杂处理，导致锰矿渣的整体颗粒较大、比表面积小，锰矿渣内部结构和晶型未发生变化，后期仅能对锰矿渣表面进行处理，去除的重金属离子量显著降低。对比例4和对比例5是分别未添加多巴胺、月桂磺酸钠和柠檬酸钠溶液、硝酸钠溶液、氟化钾溶液对锰矿渣进行改性激活，导致其制备的改性锰矿渣去除率较低，对比例4的锰矿渣表面未生成亲水作用的聚多巴胺，降低了锰矿渣的可修饰性，而对比例5虽然表面生成了聚多巴胺，但未进行二次修饰显著降低吸附性。因此，实施例1结合步骤a和步骤b协同作用于锰矿渣对其进行改性，显著提高重金属离子的去除率。According to the results in Table 2, the modified manganese slag prepared in Example 1 has a high removal rate of heavy metals, all reaching more than 95%, especially the removal effect of mercury ions and cadmium ions is the best. In Comparative Example 1, the raw manganese slag was directly pulverized and used without other treatment, and the heavy metals were adsorbed only by the few pores inside, and the effect of removing heavy metals was poor. Compared with Example 1, Comparative Example 2 was not treated with hot water before the modification treatment, which resulted in partial soluble salts in the manganese slag being dissolved and reacted with the raw materials to adhere to the surface of the manganese slag, resulting in a reduced removal effect. Comparative example 3 does not carry out step a treatment, does not refine manganese slag particles and crystalline minerals, and also does not carry out triethanolamine modification and hot water impurity removal treatment, resulting in larger overall particles of manganese slag, small specific surface area, and manganese slag. The internal structure and crystal form have not changed, and only the surface of manganese slag can be treated in the later stage, and the amount of heavy metal ions removed is significantly reduced. In Comparative Example 4 and Comparative Example 5, the manganese slag was modified and activated without adding dopamine, sodium lauryl sulfonate and sodium citrate solution, sodium nitrate solution, and potassium fluoride solution, respectively, resulting in a higher removal rate of the modified manganese slag prepared. The surface of the manganese slag in Comparative Example 4 did not generate hydrophilic polydopamine, which reduced the modifiability of the manganese slag, while in Comparative Example 5, although polydopamine was generated on the surface, no secondary modification was carried out to significantly reduce the adsorption. Therefore, Example 1 combines steps a and b to act synergistically on manganese slag to modify it, significantly improving the removal rate of heavy metal ions.

以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。本发明未详细描述的技术、形状、构造部分均为公知技术。The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced. Without departing from the spirit and scope of the technical solutions of the present invention, all of them should be included in the scope of the claims of the present invention. The technology, shape, and configuration part that are not described in detail in the present invention are all well-known technologies.

Claims (9)

1. A method for treating heavy metal ions by recycling modified manganese slag is characterized by comprising the following steps:

(1) adjusting the pH value of the heavy metal wastewater to be treated to 9-10 by using an alkaline solution;

(2) mixing the heavy metal wastewater with the modified manganese slag, stirring for 20-40min, and standing;

(3) standing for 12-24h, filtering, and performing subsequent treatment on the separated wastewater.

2. The method for recycling heavy metal ions from modified manganese slag according to claim 1, wherein the preparation method of the modified manganese slag comprises the following steps:

a. crushing manganese slag, placing the crushed manganese slag in hot water at 70-80 ℃ for standing for 24h, taking out the manganese slag, soaking and stirring the manganese slag with triethanolamine solution at room temperature for 24-36h, taking out the manganese slag, washing the manganese slag with clear water, drying the manganese slag in the air, and grinding the manganese slag into manganese ore powder;

b. adding the processed manganese ore powder into Tris-hydrochloric acid buffer solution, adding dopamine and sodium laurylsulfate, adjusting the pH value to 9-10, stirring for 3-4h, standing for 12h, filtering after standing, adding a mixed solution prepared from a sodium citrate solution, a sodium nitrate solution and a potassium fluoride solution at room temperature, reacting for 4h, taking out, then mixing with phthalic acid ester and polylactic acid-glycolic acid copolymer, and stirring for 24h to obtain modified manganese ore slag.

3. The method for recycling heavy metal ions by using the modified manganese slag as claimed in claim 2, wherein the content of iron oxide in the manganese slag is less than or equal to 3%.

4. The method for recycling the modified manganese slag to treat the heavy metal ions as claimed in claim 3, wherein the manganese slag in the step a is crushed into 2-5mm fine slag, and the particle size of the manganese ore powder is 0.03-0.06 mm.

5. The method for recycling heavy metal ions by using the modified manganese slag according to claim 3, wherein the concentration of the triethanolamine solution is 5-10 wt%.

6. The method for treating heavy metal ions by recycling modified manganese slag according to claim 5, wherein the mass ratio of the manganese slag to dopamine to sodium lauryl sulfate is 10: (0.5-1): 0.01.

7. the method for treating heavy metal ions by recycling modified manganese slag according to claim 6, wherein the mass ratio of the manganese slag to the sodium citrate solution, the sodium nitrate solution and the potassium fluoride solution is 1: 0.6: 1: 1.

8. the method for treating heavy metal ions by recycling modified manganese slag according to claim 7, wherein the concentrations of the sodium citrate solution, the sodium nitrate solution and the potassium fluoride solution are respectively 0.2mol/L, 1mol/L and 0.1 mol/L.

9. The method for treating heavy metal ions by recycling modified manganese slag according to claim 8, wherein the mass ratio of the phthalate to the polylactic acid-glycolic acid copolymer is 1: 0.4.