技术领域technical field
本发明涉及湿法冶炼渣处理领域，具体涉及一种湿法冶炼渣玻璃化配方及玻璃化无害化处理工艺。The invention relates to the field of wet smelting slag treatment, in particular to a formula for vitrification of wet smelting slag and a vitrification harmless treatment process.
背景技术Background technique
随着工业的发展，大量的含金属废物不断产生，回收其中的有价金属已成为发展循环经济、开发“城市矿产”的重要途径。湿法冶炼因其提取金属的效率较高被普遍使用，但其提取金属后留下的湿法冶炼渣仍不能直接作为资源进行回收利用，部分湿法冶炼渣还具有一定的危险特性。目前常用的湿法冶炼渣后续处理处置工艺，主要包括固化、稳定化和水泥窑协同处置，固化、稳定化后的湿法冶炼渣的去处通常为危险废物填埋场，但危险废物填埋场容积有限不能持续接收；水泥窑协同处置为了保证水泥的品质，对入窑物料的特性和协同处置废物的量有严格要求，这使得水泥窑协同处置也不能满足湿法冶炼渣处置的需求。With the development of industry, a large amount of metal-containing waste is continuously produced, and the recovery of valuable metals has become an important way to develop circular economy and develop "urban minerals". Hydrosmelting is widely used because of its high efficiency in extracting metals, but the hydrosmelting slag left after extracting metals cannot be directly recycled as resources, and some hydrosmelting slags have certain dangerous characteristics. At present, the commonly used follow-up treatment and disposal processes of hydrometallurgy slag mainly include solidification, stabilization and co-processing in cement kilns. The limited volume cannot be continuously received; in order to ensure the quality of cement, cement kiln co-processing has strict requirements on the characteristics of materials entering the kiln and the amount of co-processing waste, which makes cement kiln co-processing unable to meet the needs of hydrometallurgy slag disposal.
因此，亟待开发一种简单高效、适用条件灵活的湿法冶炼渣处理处置工艺。《国家危险废物名录》定义“HW18焚烧处置残渣772-004-18危险废物等离子体、高温熔融等处置过程产生的非玻璃态物质和飞灰”为危险废物，危险废物等离子体、高温熔融等处置过程产生的玻璃态物质被普遍认为不属于危险废物。Therefore, it is urgent to develop a simple, efficient and flexible hydrometallurgy slag treatment and disposal process. The "National Hazardous Waste List" defines "HW18 Incineration Disposal Residue 772-004-18 Hazardous Waste Plasma, High-Temperature Melting and Other Disposal Processes to Produce Non-Glass Matter and Fly Ash" as Hazardous Waste, Hazardous Waste Plasma, High-Temperature Melting and Other Disposals The glassy material produced by the process is generally not considered hazardous waste.
发明内容Contents of the invention
本发明的目的在于解决湿法冶炼渣处理处置过程中的短板，从而使得湿法冶炼成为一种更合理的含金属废物处理工艺，而提供一种湿法冶炼渣玻璃化无害化工艺。The purpose of the present invention is to solve the shortcomings in the treatment and disposal process of hydrosmelting slag, thereby making hydrosmelting a more reasonable metal-containing waste treatment process, and providing a vitrification and harmless process of hydrosmelting slag.
一种湿法冶炼渣玻璃化配方，以质量百分比计组成如下：A vitrification formula of wet smelting slag is composed as follows in terms of mass percentage:
进一步优选地，以质量百分比计组成如下：Further preferably, the composition is as follows in terms of mass percentage:
更进一步优选，以质量百分比计组成如下：More preferably, composition is as follows in mass percent:
本发明还提供一种湿法冶炼渣玻璃化无害化处理工艺，包括如下步骤：The present invention also provides a vitrification and harmless treatment process for hydrometallurgy slag, comprising the following steps:
(1)对湿法冶炼渣进行脱水和初步干化；对含钙矿物、含硅矿物、含钠矿物和废玻璃分别进行破碎和过筛；(1) Dehydration and preliminary drying of hydrometallurgy slag; crushing and screening of calcium-containing minerals, silicon-containing minerals, sodium-containing minerals and waste glass;
(2)将过筛后的含钙矿物、含硅矿物、含钠矿物和废玻璃中的至少一种与初步干化后的湿法冶炼渣以及废活性炭按配比混合，得混合物；(2) mixing at least one of the sieved calcium-containing minerals, silicon-containing minerals, sodium-containing minerals and waste glass with the preliminary dried hydrosmelting slag and waste activated carbon according to the proportion to obtain a mixture;
(3)将所得混合物二次干化后进行高温煅烧，得玻璃化产物。(3) Calcining the obtained mixture at a high temperature after secondary drying to obtain a vitrified product.
本发明所述湿法冶炼渣为含金属废物通过湿法冶炼金属后的残余物。The hydrometallurgy slag in the present invention is the residue after the metal-containing waste is hydrometallurged.
所述含金属废物为《国家危险废物名录》中的表面处理废物、焚烧处置残渣、含铍废物、含铬废物、含铜废物、含锌废物、含砷废物、含硒废物、含镉废物、含锑废物、含碲废物、含汞废物、含铊废物、含铅废物、含镍废物、含钡废物、有色金属冶炼废物、废催化剂。The metal-containing wastes are surface treatment wastes, incineration disposal residues, beryllium-containing wastes, chromium-containing wastes, copper-containing wastes, zinc-containing wastes, arsenic-containing wastes, selenium-containing wastes, cadmium-containing wastes, Antimony-containing waste, tellurium-containing waste, mercury-containing waste, thallium-containing waste, lead-containing waste, nickel-containing waste, barium-containing waste, non-ferrous metal smelting waste, waste catalyst.
所述湿法冶炼为含金属废物在酸性介质水溶液、碱性介质水溶液、有机溶剂中进行化学处理、萃取、分离杂质、提取金属及其化合物的过程。The hydrometallurgy is a process in which metal-containing wastes are chemically treated, extracted, separated from impurities, and metals and their compounds are extracted in aqueous acidic media, aqueous alkaline media, or organic solvents.
步骤(1)中过筛后物料的粒径小于0.5mm。The particle size of the material after sieving in step (1) is less than 0.5 mm.
优选地，步骤(1)中脱水后的湿法冶炼渣含水率低于75％；初步干化后的湿法冶炼渣含水率低于20％。Preferably, the moisture content of the hydrosmelting slag after dehydration in step (1) is lower than 75%; the moisture content of the hydrosmelting slag after preliminary drying is lower than 20%.
优选地，步骤(2)的混合物中废活性炭的质量百分比为0.2～2.5％，湿法冶炼渣的质量百分比为50％～95％，其余为含钙矿物、含硅矿物、含钠矿物和废玻璃中的至少一种，总量为100％。含钙矿物、含硅矿物、含钠矿物、废玻璃的质量百分比根据实际情况而定。Preferably, the mass percentage of waste activated carbon in the mixture of step (2) is 0.2-2.5%, the mass percentage of hydrometallurgy slag is 50%-95%, and the rest are calcium-containing minerals, silicon-containing minerals, sodium-containing minerals and waste At least one kind of glass, the total amount is 100%. The mass percentages of calcium-containing minerals, silicon-containing minerals, sodium-containing minerals, and waste glass are determined according to actual conditions.
进一步优选，步骤(2)的混合物中以质量百分比计，组成如下：Further preferably, in the mixture of step (2), by mass percentage, the composition is as follows:
更进一步优选地，以质量百分比计组成如下：More preferably, composition is as follows in mass percent:
更进一步优选，步骤(2)的混合物中以质量百分比计，组成如下：More preferably, in the mixture of step (2), by mass percentage, composition is as follows:
在上述优选配方下得到的玻璃化处产物中玻璃体的质量百分比在85％左右。The mass percentage of vitreous body in the vitrification product obtained under the above preferred formula is about 85%.
最优选地，步骤(2)的混合物中以质量百分比计，组成如下：Most preferably, in the mixture of step (2), by mass percentage, composition is as follows:
在上述优选配方下得到的玻璃化处产物中玻璃体的质量百分比在95％以上。The mass percentage of vitreous body in the vitrification product obtained under the above preferred formula is above 95%.
所述重量百分比以灰分为计算基础；The weight percentage is calculated based on ash;
进一步优选地，所述含钙矿物为生石灰；所述含硅矿物为石英砂；所述含钠矿物为芒硝。废玻璃进一步优选为玻璃生产过程中的废品或玻璃体含量不低于85％的熔融化产物。Further preferably, the calcium-containing mineral is quicklime; the silicon-containing mineral is quartz sand; and the sodium-containing mineral is Glauber's salt. The waste glass is further preferably a waste product in the glass production process or a melted product with a vitreous body content of not less than 85%.
优选地，步骤(3)中二次干化后的混合物含水率低于10％；高温煅烧的温度不低于1200℃，进一步优选为1200～1400℃。Preferably, the moisture content of the mixture after secondary drying in step (3) is lower than 10%; the temperature for high-temperature calcination is not lower than 1200°C, more preferably 1200-1400°C.
进一步优化脱水过程为调质和压滤脱水，初步干化和二次干化利用煅烧废气中的余热实现干化。The further optimization of the dehydration process is tempering and filter press dehydration, and the primary drying and secondary drying use the waste heat in the calcination exhaust gas to achieve drying.
优选地，高温煅烧时间为1.5～5小时。Preferably, the high-temperature calcination time is 1.5-5 hours.
进一步优选地，所述高温煅烧为在1200～1300℃下煅烧2～2.5小时。Further preferably, the high-temperature calcination is calcination at 1200-1300° C. for 2-2.5 hours.
煅烧过程中废活性炭起到还原作用，将湿法冶炼渣中的离子态金属进一步还原为单质金属；所有物料变成熔融物，熔融物中形成大量中间体氧化物和网络生成体氧化物，熔融物冷却后形成玻璃体。煅烧温度及煅烧时间均由大量实践探索确定，在上述煅烧温度及煅烧时间下能更好的实现本发明的目的。During the calcination process, the waste activated carbon acts as a reducing agent, further reducing the ionic metals in the hydrometallurgy slag to elemental metals; all the materials become melts, and a large number of intermediate oxides and network-forming oxides are formed in the melts, melting After cooling, the material forms a glass body. Both the calcination temperature and the calcination time are determined by a large number of practical explorations, and the purpose of the present invention can be better achieved under the above-mentioned calcination temperature and calcination time.
本发明所得玻璃化产物中玻璃体含量不低于85％，满足湿法冶炼渣无害化的要求。The content of vitreous body in the vitrified product obtained by the invention is not less than 85%, which meets the requirement of harmless slag from hydrometallurgy.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明通过熔融玻璃化的方式实现湿法冶炼渣的无害化。本发明从简单易行、普适性的角度出发，利用湿法冶炼渣、含硅矿物、含钙矿物、含钠矿物、废玻璃以及废活性炭，通过玻璃化的方式实现湿法冶炼渣的无害化。The invention realizes the harmlessness of wet smelting slag through melting vitrification. From the perspective of simplicity and universality, the present invention utilizes hydro-smelting slag, silicon-containing minerals, calcium-containing minerals, sodium-containing minerals, waste glass and waste activated carbon to realize the non-toxic treatment of hydro-smelting slag through vitrification. detrimental.
具体实施方式detailed description
实施例1Example 1
选取3种含金属废物湿法冶炼渣，分别为含镍废物湿法冶炼渣、含铜废物湿法冶炼渣和含锌废物湿法冶炼渣，以下所有描述均以灰分为计算基础的质量百分比进行。Three kinds of metal-containing waste hydrosmelting slags are selected, namely nickel-containing waste hydrosmelting slag, copper-containing waste hydrosmelting slag and zinc-containing waste hydrosmelting slag. All the following descriptions are based on the mass percentage of the ash content calculation basis. .
含镍废物湿法冶炼渣机械脱水后含水率为72.3％，初步干化后含水率为17.5％；将初步干化后的含镍废物湿法冶炼渣、废活性炭和破碎、过筛后的石英砂、生石灰、芒硝、废玻璃进行混合，混合物中废活性炭的含量为1.0％，其余物料的质量百分比为：86％含镍废物湿法冶炼渣、3％石英砂、4％生石灰、1％芒硝、5％废玻璃；该混合物二次干化，二次干化后混合物的含水率为4.3％；二次干化后的混合物在1250～1300℃的条件下煅烧2h。The moisture content of nickel-containing waste hydro-smelting slag after mechanical dehydration is 72.3%, and the moisture content after preliminary drying is 17.5%; the nickel-containing waste hydro-smelting slag, waste activated carbon and crushed and sieved quartz Sand, quicklime, Glauber's salt, and waste glass are mixed, the content of waste activated carbon in the mixture is 1.0%, and the mass percentage of the remaining materials is: 86% nickel-containing waste hydrometallurgy slag, 3% quartz sand, 4% quicklime, 1% Glauber's salt , 5% waste glass; the mixture is dried for the second time, and the moisture content of the mixture after the second drying is 4.3%; the mixture after the second drying is calcined at 1250-1300° C. for 2 hours.
含铜废物湿法冶炼渣机械脱水后含水率为68.7％，初步干化后含水率为14.9％；将初步干化后的含铜废物湿法冶炼渣、废活性炭和破碎、过筛后的石英砂、生石灰、芒硝、废玻璃进行混合，混合物中废活性炭的含量为1.0％，其余物料的质量百分比为：84％含铜废物湿法冶炼渣、4％石英砂、6％生石灰、1％芒硝、4％废玻璃；该混合物二次干化，二次干化后混合物的含水率为5.7％；二次干化后的混合物在1200～1250℃的条件下煅烧2.5h。The moisture content of copper-containing waste hydro-smelting slag after mechanical dehydration is 68.7%, and the moisture content after preliminary drying is 14.9%; the copper-containing waste hydro-smelting slag, waste activated carbon and crushed and sieved quartz Sand, quicklime, Glauber's salt, and waste glass are mixed, the content of waste activated carbon in the mixture is 1.0%, and the mass percentages of the remaining materials are: 84% copper-containing waste hydrometallurgy slag, 4% quartz sand, 6% quicklime, 1% Glauber's salt , 4% waste glass; the mixture is dried for the second time, and the moisture content of the mixture after the second drying is 5.7%; the mixture after the second drying is calcined at 1200-1250° C. for 2.5 hours.
含锌废物湿法冶炼渣机械脱水后含水率为72.6％，初步干化后含水率为17.3％；将初步干化后的含锌废物湿法冶炼渣、废活性炭和破碎、过筛后的石英砂、生石灰、芒硝、废玻璃进行混合，混合物中废活性炭的含量为1.0％，其余物料为94％含锌废物湿法冶炼渣、3％石英砂、2％生石灰、0％芒硝、0％废玻璃；该混合物二次干化，二次干化后混合物的含水率为4.9％；二次干化后的混合物在1250～1300℃的条件下煅烧2h。The moisture content of zinc-containing waste hydro-smelting slag after mechanical dehydration is 72.6%, and the moisture content after preliminary drying is 17.3%; the zinc-containing waste hydro-smelting slag, waste activated carbon and crushed and sieved quartz Sand, quicklime, Glauber's salt, and waste glass are mixed. The content of waste activated carbon in the mixture is 1.0%, and the remaining materials are 94% zinc-containing waste hydrometallurgy slag, 3% quartz sand, 2% quicklime, 0% Glauber's salt, and 0% waste Glass; the mixture is dried for the second time, and the moisture content of the mixture after the second drying is 4.9%; the mixture after the second drying is calcined at 1250-1300° C. for 2 hours.
含镍废物湿法冶炼渣、含铜废物湿法冶炼渣和含锌废物湿法冶炼渣玻璃化产物中玻璃体质量百分比分别为88.6％、95.8％和93.3％(检测方法为XRD)。The mass percentages of vitreous bodies in the vitrification products of nickel-containing waste hydro-smelting slag, copper-containing waste hydro-smelting slag and zinc-containing waste hydro-smelting slag were 88.6%, 95.8% and 93.3% respectively (the detection method was XRD).
以上所述仅为本发明专利的具体实施案例，但本发明专利的技术特征并不局限于此，任何相关领域的技术人员在本发明的领域内，所作的变化或修饰皆涵盖在本发明的专利范围之中。The above is only a specific implementation case of the patent of the present invention, but the technical characteristics of the patent of the present invention are not limited thereto, and any changes or modifications made by those skilled in the relevant fields within the scope of the present invention are covered by the patent of the present invention. within the scope of the patent.
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| CN114275996A (en)* | 2021-12-29 | 2022-04-05 | 新中天环保股份有限公司 | Resourceful treatment method for incinerator slag |
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| CN105483387A (en)* | 2015-12-09 | 2016-04-13 | 中南大学 | Iron-containing metallurgical waste harmless treatment and valuable metal recycling method |
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| CN105392739A (en)* | 2013-06-17 | 2016-03-09 | 住友金属矿山株式会社 | Hematite manufacturing method and hematite manufactured by same |
| CN105441683A (en)* | 2015-11-13 | 2016-03-30 | 湖南中大联合创新科技发展有限公司 | Comprehensive treatment method for mixed waste residues |
| CN105483387A (en)* | 2015-12-09 | 2016-04-13 | 中南大学 | Iron-containing metallurgical waste harmless treatment and valuable metal recycling method |
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| CN109622563A (en)* | 2018-12-17 | 2019-04-16 | 北京高能时代环境技术股份有限公司 | A method of arsenic-containing waste residue is carried out using flotation tailing vitrification solidifying |
| CN114275996A (en)* | 2021-12-29 | 2022-04-05 | 新中天环保股份有限公司 | Resourceful treatment method for incinerator slag |
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