CN104438285B - A method for the harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as an additive - Google Patents

A method for the harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as an additive Download PDF

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CN104438285B
CN104438285B CN201410641749.4A CN201410641749A CN104438285B CN 104438285 B CN104438285 B CN 104438285B CN 201410641749 A CN201410641749 A CN 201410641749A CN 104438285 B CN104438285 B CN 104438285B
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朱建新
任亚峰
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Research Center for Eco Environmental Sciences of CAS
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Abstract

本发明为一种以硫为添加剂机械球磨无害化处理废汞触媒的方法,属于含汞废物无害化处置技术领域,具体包括以下步骤:第一步,将废汞触媒和升华硫按质量比为1:8均匀混合,其中汞触媒中氯化汞(HgCl2)的含量为4.0~7.0%;第二步,将第一步中混合均匀的废汞触媒和升华硫加入到球磨机的不锈钢密闭球磨罐中进行球磨反应,使用球料比为40:1,球磨转速为550r/min,反应时间为2小时,汞的毒性浸出值低于美国环保部的危险废物标准限值(0.2mg/L)以及中国国家危险废物鉴别标准限值(0.1mg/L),可以实现废汞触媒固化和稳定化。本方法可以解决电石法PVC生产过程中产生的大量废汞触媒的环境污染问题,具有处理速度快、过程简单、操作安全和高效环保的特点。

The invention relates to a method for harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as an additive, which belongs to the technical field of harmless disposal of mercury-containing waste, and specifically comprises the following steps: the first step is to mix waste mercury catalyst and sublimated sulfur by mass The ratio is 1:8, and the content of mercury chloride (HgCl 2 ) in the mercury catalyst is 4.0-7.0%. In the second step, the waste mercury catalyst and sublimated sulfur mixed uniformly in the first step are added to the stainless steel surface of the ball mill. Carry out ball mill reaction in airtight ball mill jar, use ball material ratio is 40:1, and ball mill rotating speed is 550r/min, and reaction time is 2 hours, and the toxic leaching value of mercury is lower than the hazardous waste standard limit value (0.2mg/ L) and the Chinese National Hazardous Waste Identification Standard Limit (0.1mg/L), which can realize solidification and stabilization of waste mercury catalyst. The method can solve the problem of environmental pollution caused by a large amount of waste mercury catalysts produced in the calcium carbide method PVC production process, and has the characteristics of fast processing speed, simple process, safe operation, high efficiency and environmental protection.

Description

一种以硫为添加剂机械球磨无害化处理废汞触媒的方法A method for the harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as an additive

技术领域technical field

本发明属于含汞危险废物管理与安全处置领域,涉及机械化学法高效无害化处理电石法生产聚氯乙烯(PVC)过程中产生的废汞触媒,具体涉及一种以硫为添加剂机械球磨无害化处理废汞触媒的方法。The invention belongs to the field of mercury-containing hazardous waste management and safe disposal, and relates to the efficient and harmless treatment of waste mercury catalyst produced in the process of producing polyvinyl chloride (PVC) by the calcium carbide method by mechanochemical method, and specifically relates to a mechanical ball milling non-toxic catalyst with sulfur as an additive. A method for detoxifying waste mercury catalysts.

背景技术Background technique

氯化汞触媒是电石法生产聚氯乙烯工业中乙炔和氯化氢反应的催化剂。其产生的废汞触媒具有浸出毒性和腐蚀性,其浸出的汞浓度超过《有色金属工业固体废物污染标准》中的固定。我国是世界上最大的电石法PVC生产国,资料显示在2013年电石法PVC产能为1512万t,约占全国总的PVC产能的82%。而其用到的氯化汞触媒是工行业中生产量最大的产品也是消耗汞量最多的产品。电石法PVC生产占中国总用汞量的60%,占世界汞消耗量的30%。每年产生的废汞触媒在1.1万吨左右,并且产生量在以每年10%-15%的速度递增。此外,目前电石法PVC行业中废汞触媒回收再利用体系不完善,汞的回收量不到1/3。Mercury chloride catalyst is a catalyst for the reaction of acetylene and hydrogen chloride in the production of polyvinyl chloride by calcium carbide method. The waste mercury catalyst produced by it has leaching toxicity and corrosiveness, and its leached mercury concentration exceeds the fixed value set in the "Pollution Standards for Non-ferrous Metal Industry Solid Wastes". my country is the largest producer of calcium carbide-based PVC in the world. Statistics show that in 2013, the production capacity of calcium carbide-based PVC was 15.12 million tons, accounting for about 82% of the country's total PVC production capacity. The mercuric chloride catalyst it uses is the product with the largest production volume in the industry and also the product that consumes the most mercury. Calcium carbide PVC production accounts for 60% of the total mercury consumption in China and 30% of the world's mercury consumption. The waste mercury catalyst produced every year is about 11,000 tons, and the production volume is increasing at an annual rate of 10%-15%. In addition, the current waste mercury catalyst recycling system in the calcium carbide PVC industry is not perfect, and the amount of mercury recovered is less than 1/3.

《氯碱行业化解产能过剩加快结构调整的对策建议》中指出高工触媒(氯化汞质量分数6.5%以上)和使用高工触媒的电石法PVC生产装置将在2015年被限制。随着煤制烯烃、甲醇制烯烃的发展,乙烯的来源更加广泛,会对电石法PVC生产工业造成冲击。此外,无汞触媒的研发也将逐步替代氯化汞触媒。届时,产生大量的废汞触媒造成巨大的环境压力,对人们的健康以及生态安全构成巨大威胁。"Countermeasures and Suggestions for Resolving Overcapacity and Accelerating Structural Adjustment in the Chlor-Alkali Industry" pointed out that high-tech catalysts (mercury chloride mass fraction above 6.5%) and calcium carbide PVC production devices using high-tech catalysts will be restricted in 2015. With the development of coal-to-olefins and methanol-to-olefins, the sources of ethylene are more extensive, which will have an impact on the calcium carbide process PVC production industry. In addition, the research and development of mercury-free catalysts will gradually replace mercury chloride catalysts. At that time, a large amount of waste mercury catalysts will be produced, causing huge environmental pressure and posing a huge threat to people's health and ecological security.

废弃后的汞触媒的大量堆放会在周过环境中大量释放汞污染物,这些污染物主要以三种形式存在:元素汞化合物、无机汞化合物和有机汞化合物。汞是毒性最强的几种化合物之一,其毒性主要取决于汞在环境中的存在形式。金属汞具有较高蒸汽压,极易被吸入人体进入血管系统快速分布于人体内部,然后被氧化成活性很高的二价汞(Hg2+)。暴露于高剂量的无机汞会损伤人的胃肠道、神经系统以及肾脏系统。汞污染物还会在特定环境下与有机物形成稳定的有机汞化合物。相对于无机汞,有机汞流动性、生物累积性、毒性更强。尤其是形成的甲基汞,可以快速通过细胞膜,Clarkson和Lacerda等人的研究表明,汞及及其化合物会损害婴幼儿的神经系统的发育以及成人的综述神经系统。The mass accumulation of discarded mercury catalysts will release a large amount of mercury pollutants in the surrounding environment. These pollutants mainly exist in three forms: elemental mercury compounds, inorganic mercury compounds and organic mercury compounds. Mercury is one of the most toxic compounds and its toxicity mainly depends on the form of mercury in the environment. Metallic mercury has a relatively high vapor pressure, so it is easily inhaled into the human body, enters the vascular system and quickly distributes in the human body, and then is oxidized into highly active divalent mercury (Hg 2+ ). Exposure to high doses of inorganic mercury can damage the human gastrointestinal tract, nervous system, and renal system. Mercury pollutants can also form stable organic mercury compounds with organic matter under certain circumstances. Compared with inorganic mercury, organic mercury is more fluid, bioaccumulative, and more toxic. In particular, the formed methylmercury can quickly pass through the cell membrane. The studies of Clarkson and Lacerda et al. have shown that mercury and its compounds can damage the development of the nervous system of infants and the nervous system of adults.

由于汞对人类健康和环境造成了不利影响,国内外制定了法律法规以限制汞的供应和应用。因此,大量的过量的汞以及含汞废物需要安全处置。我国国家环境保护部也要求涉汞企业无害化处理其废弃物,避免污染周边的大气、水和土壤。目前,含汞废物主要处理方法包括:汞齐化法、热处理法、玻璃固化法、土壤洗脱法、硫聚合物稳定固化法、形成硫化汞法、磷陶瓷化学结合法以及其他封存工艺。目前,稳定固化法是处理含汞废物所推荐的方法,具有良好的处置效果。这些技术存在的问题成本高、技术复杂、含汞废物中的汞不能完全固定以及可能产生二次污染等。Due to the adverse effects of mercury on human health and the environment, laws and regulations have been formulated at home and abroad to limit the supply and application of mercury. Therefore, large amounts of excess mercury as well as mercury-containing wastes require safe disposal. The Ministry of Environmental Protection of my country also requires mercury-related enterprises to dispose of their waste in a harmless manner to avoid polluting the surrounding air, water and soil. At present, the main treatment methods for mercury-containing waste include: amalgamation, heat treatment, vitrification, soil elution, sulfur polymer stabilization and solidification, mercury sulfide formation, phosphorus ceramic chemical bonding and other storage processes. At present, the stable solidification method is the recommended method for treating mercury-containing wastes, and it has a good disposal effect. The problems of these technologies are high cost, complex technology, incomplete fixation of mercury in mercury-containing waste, and possible secondary pollution.

球磨法又称机械化学法,是通过机械力引起的物质的物理化学性质及其结构的转变,通过剪切、磨擦、冲击、挤压等手段,使固体、液体等凝聚态物质产生活性表面、促进传质,并诱发化学反应。与普通热化学反应不同,机械化学反应的动力是机械能而非热能,因而反应无须高温、高压等苛刻条件即可完成,同时机械化学法还有操作简单、灵活、降解速率快等优点。西班牙的科学家F.ALopez等人初步运用机械球磨法将金属汞转化为硫化汞,实现了汞废物的无害化。文献调研表明,目前还未有关于氯化汞及废汞触媒无害化处理技术方面的报道。鉴于我国废汞触媒产生量巨大,回收再生利用率较低,二次污染严重,目前急需开发环保高效的废汞触媒固化稳定化无害化处置技术和工艺。The ball milling method, also known as the mechanochemical method, is the transformation of the physical and chemical properties and structure of the substance caused by mechanical force, through shearing, friction, impact, extrusion and other means, so that solid, liquid and other condensed substances produce active surfaces, Facilitate mass transfer and induce chemical reactions. Different from ordinary thermochemical reactions, the driving force of mechanochemical reactions is mechanical energy rather than thermal energy, so the reaction can be completed without harsh conditions such as high temperature and high pressure. At the same time, mechanochemical methods have the advantages of simple operation, flexibility, and fast degradation rate. Spanish scientist F.A Lopez and others initially used mechanical ball milling to convert metallic mercury into mercury sulfide, realizing the harmlessness of mercury waste. The literature survey shows that there is no report on the harmless treatment technology of mercuric chloride and waste mercury catalyst. In view of the huge amount of waste mercury catalysts produced in my country, the low recycling rate and serious secondary pollution, there is an urgent need to develop environmentally friendly and efficient waste mercury catalyst solidification, stabilization and harmless disposal technologies and processes.

发明内容Contents of the invention

基于机械化学法的优点,本发明创造性地提出一种以硫为添加剂机械球磨无害化处理废汞触媒的方法,处理完成后废汞触媒中汞的毒性浸出值低于美国环保部的危险废物标准(0.2mg/L)以及中国国家危险废物鉴别标准(0.1mg/L),具有操作简单、安全、灵活等特点。Based on the advantages of the mechanochemical method, the present invention creatively proposes a method for the harmless treatment of waste mercury catalyst by mechanical ball milling with sulfur as an additive. After the treatment, the toxic leaching value of mercury in the waste mercury catalyst is lower than the hazardous waste of the US Department of Environmental Protection Standard (0.2mg/L) and China National Hazardous Waste Identification Standard (0.1mg/L), it has the characteristics of simple operation, safety and flexibility.

本发明的采用的技术方案是::The technical scheme adopted in the present invention is:

第一步,将废汞触媒和升华硫以质量比1:8混合均匀The first step is to mix the spent mercury catalyst and sublimated sulfur evenly with a mass ratio of 1:8

第二步,将第一步混合均匀的废汞触媒和升华硫加入到球磨机的不锈钢密闭球磨罐中进行球磨反应,使用球料比为40:1,球磨转速为550r/min,反应时间为2小时。In the second step, the waste mercury catalyst and sublimated sulfur mixed uniformly in the first step are added to the stainless steel airtight ball mill tank of the ball mill for ball milling reaction. Hour.

所述升华硫与汞触媒以质量比8:1,球料比为40:1,球磨转速为550r/min,在空气氛下密闭不锈钢球磨罐内常温常压条件下进行。The mass ratio of the sublimated sulfur and the mercury catalyst is 8:1, the ball-to-material ratio is 40:1, and the ball milling speed is 550r/min, and it is carried out under the conditions of normal temperature and pressure in a closed stainless steel ball milling tank under an air atmosphere.

所述球磨反应结束后,可以直接在空气中打开球磨罐,换下一批处理样。After the ball milling reaction is finished, the ball milling tank can be opened directly in the air, and a batch of treated samples can be replaced.

本发明具有如下优点:The present invention has the following advantages:

1)反应时间短,处理效率高,汞的固定率达到99.9%以上;1) The reaction time is short, the treatment efficiency is high, and the fixation rate of mercury reaches more than 99.9%;

2)废汞触媒经过机械球磨法处理之后,汞的毒性浸出值低于美国环保部的危险废物鉴别标准(0.2mg/L)以及中国国家危险废物鉴别标准(0.1mg/L),废汞触媒可以由危险废物转为普通废物;2) After the waste mercury catalyst is treated by mechanical ball milling, the toxic leaching value of mercury is lower than the hazardous waste identification standard (0.2mg/L) of the US Department of Environmental Protection and the national hazardous waste identification standard of China (0.1mg/L). Can be converted from hazardous waste to general waste;

2)汞触媒的汞在处理之后转为为硫化汞,自然界最稳定的形态汞2) The mercury in the mercury catalyst is converted into mercury sulfide after treatment, the most stable form of mercury in nature

3)所用的升华硫易得,成本低,来源广泛;3) The sublimated sulfur used is easy to get, low in cost and wide in source;

4)操作简单,反应条件温和,不需要高温加热,降低了处理能耗。4) The operation is simple, the reaction conditions are mild, no high-temperature heating is required, and the processing energy consumption is reduced.

附图说明Description of drawings

图1是在不同的汞触媒与升华硫质量比情况下,机械球磨后汞的毒性浸出值的对比,其中球磨时间为12小时,纵坐标为毒性浸出测试之后汞的浸出值,横坐标表示不同的汞触媒与升华硫质量比,图中分别给出了1:1、1:2、1:4、1:8、1:20、1:40等6不同质量比情况汞的毒性浸出值。其中:球磨时间为12小时,球料比为40:1,转速为550r/min,空气气氛,磨罐磨球材质均为不锈钢。Figure 1 is a comparison of mercury toxicity leaching values after mechanical ball milling under different mass ratios of mercury catalysts and sublimated sulfur. The ball milling time is 12 hours. The mass ratio of mercury catalyst to sublimated sulfur is shown in the figure, and the toxic leaching values of mercury in six different mass ratios of 1:1, 1:2, 1:4, 1:8, 1:20, and 1:40 are respectively given. Among them: the ball milling time is 12 hours, the ball-to-material ratio is 40:1, the rotation speed is 550r/min, the air atmosphere, and the material of the grinding pot and the balls are all stainless steel.

图2是实施例一中以汞触媒与升华硫的质量比为1:8时,不同球磨反应时间汞的毒性浸出值的影响,其中横坐标为球磨时间,单位为分钟,纵坐标为经过毒性浸出测试后球磨样品中汞的浸出值。其中:汞触媒与升华硫的质量比为1:8,球料比为40:1,转速为550r/min,空气气氛,磨罐磨球材质均为不锈钢。Fig. 2 is when the mass ratio of mercury catalyst and sublimated sulfur is 1:8 in embodiment 1, the influence of the toxicity leaching value of mercury of different ball milling reaction time, and wherein abscissa is ball milling time, and the unit is minute, and ordinate is through toxicity Leaching values of mercury from ball-milled samples after leaching tests. Among them: the mass ratio of mercury catalyst to sublimated sulfur is 1:8, the ball-to-material ratio is 40:1, the rotation speed is 550r/min, the air atmosphere, and the material of the grinding pot and grinding balls are all stainless steel.

图3是实施例一中以汞触媒与升华硫的质量比为1:8时,基于不同球磨反应时间汞的毒性浸出值根据公式计算出的汞固定效率,其中横坐标为球磨时间,单位为分钟,纵坐标为汞的固定率。其中:汞触媒与升华硫的质量比为1:8,球料比为40:1,转速为550r/min,空气气氛,磨罐磨球材质均为不锈钢。Fig. 3 is when the mass ratio of mercury catalyst and sublimated sulfur is 1:8 in embodiment 1, based on the toxicity leaching value of mercury of different ball milling reaction times, the mercury immobilization efficiency calculated according to the formula, wherein the abscissa is ball milling time, unit is minutes, and the ordinate is the fixation rate of mercury. Among them: the mass ratio of mercury catalyst to sublimated sulfur is 1:8, the ball-to-material ratio is 40:1, the rotation speed is 550r/min, the air atmosphere, and the material of the grinding pot and grinding balls are all stainless steel.

SR为固定效率;Vu为没有经过球磨处理的样品的毒性浸出值;Vt经过不同球磨时间处理过的样品的毒性浸出值。S R is the fixing efficiency; V u is the toxicity leaching value of the sample without ball milling treatment; V t is the toxicity leaching value of the sample treated by different ball milling time.

图4是实施例一中在不同的汞触媒与升华硫质量比情况下,球磨12小时后混合粉体的XRD衍射分析图。当汞触媒与升华硫的质量比为1:2,有硫化汞出现。在其他的球磨样品中,由于硫磺过量,主要是硫磺的衍射峰。球磨之后负载氯化汞的活性结构被破坏转化为无定型碳,所以在XRD衍射谱图上没有相应的峰出现。Fig. 4 is an XRD diffraction analysis diagram of the mixed powder after ball milling for 12 hours under different mass ratios of mercury catalyst and sublimed sulfur in Example 1. When the mass ratio of mercury catalyst to sublimated sulfur is 1:2, mercury sulfide appears. In other milled samples, the diffraction peaks of sulfur are mainly due to the excess of sulfur. After ball milling, the active structure of mercuric chloride loaded is destroyed and transformed into amorphous carbon, so there is no corresponding peak in the XRD diffraction pattern.

具体实施方式Detailed ways

下面结合附图和实施例对本发明做进一步详细说明.Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail.

实施例一Embodiment one

将汞触媒与升华硫的质量比分别按1:1、1:2、1:4、1:8、1:20、1:40混合作为球磨反应物,向每个不锈钢球磨罐中添加6g球磨反应物及14个直径为15mm,重量为15g的不锈钢小球和球磨罐有效容积为250ml,球磨罐与球磨盖之间用弹性O型圈密封。设定球磨机转速为550r/min,球磨时间12h。The mass ratio of mercury catalyst and sublimated sulfur is mixed according to 1:1, 1:2, 1:4, 1:8, 1:20, 1:40 respectively as ball mill reactant, and 6g ball mill is added to each stainless steel ball mill jar The reactant and 14 diameters are 15mm, and the stainless steel balls with a weight of 15g and the effective volume of the ball mill jar are 250ml, and the ball mill jar and the ball mill cover are sealed with an elastic O-ring. Set the rotational speed of the ball mill to 550r/min, and the ball milling time to 12h.

按汞触媒与升华硫的质量比为1:8将其混合作为球磨反应物,向每个不锈钢球磨罐中添加6g球磨反应物及14个直径为15mm,重量为15g的不锈钢小球和球磨罐有效容积为250ml,球磨罐与球磨盖之间用弹性O型圈密封。设定球磨机转速为550r/min,球磨时间为分别为15min,30min,45min,60min,90min,105min、120min、240min。According to the mass ratio of mercury catalyst and sublimated sulfur as 1:8, mix it as the ball milling reactant, add 6g of ball milling reactant and 14 stainless steel balls and ball milling jars with a diameter of 15mm and a weight of 15g to each stainless steel ball milling jar The effective volume is 250ml, and the elastic O-ring is used to seal the ball mill jar and the ball mill cover. Set the rotational speed of the ball mill to 550r/min, and the ball milling time to be 15min, 30min, 45min, 60min, 90min, 105min, 120min, and 240min, respectively.

在不同的球磨时间后取出球磨粉体,根据美国环保局制定的毒性浸出特性步骤(TCLP)进行分析。称取1.0g球磨后粉体,加入TCLP#1号提取液,在常温下搅拌18h,过滤定容至100ml,然后用ICP-OES测定提取液中的汞。球磨2h后。汞的浸出值低于0.1mg/L,汞的固定率大于99%。After different milling times, the milled powders were taken out and analyzed according to the Toxic Leaching Characteristic Procedure (TCLP) formulated by the US Environmental Protection Agency. Weigh 1.0g of ball-milled powder, add TCLP#1 extract, stir at room temperature for 18h, filter to 100ml, and then use ICP-OES to measure mercury in the extract. After ball milling for 2h. The leaching value of mercury is lower than 0.1mg/L, and the fixing rate of mercury is greater than 99%.

综上所述,使用本发明之后,汞触媒中的汞转化为硫化汞,是一种处理速度快,操作过程简单安全,过程环保的方法。In summary, after using the present invention, the mercury in the mercury catalyst is converted into mercury sulfide, which is a method with fast processing speed, simple and safe operation process, and environmentally friendly process.

Claims (2)

1.一种以硫为添加剂机械球磨无害化处理废汞触媒的方法,包括以下步骤:1. A method for the harmless treatment of spent mercury catalysts by mechanical ball milling with sulfur as an additive, comprising the following steps: 第一步,将废汞触媒与升华硫以质量比为不高于1:8均匀混合,其中废汞触媒中汞的含量为4.0%~7.0%;In the first step, the waste mercury catalyst and sublimated sulfur are evenly mixed at a mass ratio of not higher than 1:8, wherein the mercury content in the waste mercury catalyst is 4.0% to 7.0%; 第二步,将第一步混合均匀的废汞触媒与升华硫加入到球磨机的不锈钢密闭球磨罐中进行机械化学反应,使用球料比为40:1,球磨转速为550r/min,反应时间为2小时。In the second step, the waste mercury catalyst and sublimated sulfur mixed uniformly in the first step are added to the stainless steel airtight ball mill tank of the ball mill to carry out the mechanochemical reaction. The ball-to-material ratio is 40:1, the ball mill speed is 550r/min, and the reaction time is 2 hours. 2.根据权利要求1所述的一种以硫为添加剂机械球磨无害化处理废汞触媒的方法,其特征在于:所述球磨使用球料比为40:1,球磨转速为550r/min,在空气气氛下密闭不锈钢球磨罐内常温常压条件下进行。2. a kind of method according to claim 1 with sulfur as additive mechanical ball mill harmless treatment waste mercury catalyst, it is characterized in that: described ball mill uses ball material ratio to be 40:1, ball mill rotating speed is 550r/min, It is carried out under normal temperature and pressure conditions in a closed stainless steel ball mill jar under an air atmosphere.
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