CN106693980B - 一种烟气汞氧化催化剂及其应用 - Google Patents
一种烟气汞氧化催化剂及其应用 Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 49
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Abstract
本发明公开了一种烟气汞氧化催化剂及其应用。本发明的催化剂是基于铜冶炼或镍冶炼的金属冶炼水淬渣;本发明的烟气汞氧化催化剂,对燃煤烟气中单质汞具有极强的催化氧化能力,即使在烟气中氯化氢浓度较低的情况下,也具有很高的单质汞氧化率,并且可利用自身的磁性进行回收和重复利用,进入飞灰后也不影响飞灰的后续利用。本发明催化剂通过颗粒喷射、流化床或固定床等方式与烟气进行接触,能实现烟气中单质汞的高效氧化。本发明具有简单易行、投资少、无二次污染等优势,具有广阔的市场应用前景。
Description
技术领域
本发明属于烟气净化技术领域,具体的说,涉及一种烟气汞氧化催化剂及其应用。
背景技术
汞因其剧毒性、挥发性、持久性以及生物富集效应已被联合国环境规划署(UNEP)认定为全球性环境污染物,受到了国际社会的广泛关注。人为排放的汞在进入大气后,通过干湿沉降重新返回到地面,污染土壤和水体,并在食物链中富集,严重危害动植物及人类的健康。
中国作为全球最大的人为汞排放国,与发达国家相比我国汞排放的控制及立法状况相对较为落后。近年来,随着经济和社会可持续发展的必然要求,我国政府高度重视燃煤电厂烟气汞的排放控制。环境保护部在2011年 7月 29日颁布的最新《火电厂大气污染物排放标准(GB 13223-2011)》明确要求燃煤锅炉从2015年 1月 1日起将汞及其化合物的排放量严格限制在0.03 mg·m-3以下。因此,加强燃煤烟气汞排放的控制研究刻不容缓,寻求经济、高效的汞排放控制方法已成为国内外研究的热点。
煤烟气中的汞通常以单质汞(Hg0)、二价汞(Hg2+)以及颗粒态汞(Hgp)三种形式存在。二价汞(Hg2+)和颗粒态汞(Hgp)可以在现有污染物控制设备中得到脱除(可溶性的Hg2+可以在湿法烟气脱硫系统(WFGD)中被脱除,颗粒态汞(Hgp)可以在静电除尘器(ESP)、布袋除尘器(FF)等颗粒物控制设备(PMCD)中被脱除);Hg0极易挥发且不溶于水,很难利用现有的污染物控制设备直接将其去除,故控制燃煤汞排放的关键在于控制 Hg0的排放。由于 Hg2+极易被脱除,所以将燃煤烟气中 Hg0氧化为 Hg2+,继而利用现有的污染物控制设备将 Hg2+脱除被认为是一种极具潜力的汞污染控制技术。商用选择性催化还原(SCR)催化剂对于Hg0的氧化具有催化作用,但现有的商用 SCR催化剂一般为钒基催化剂,毒性较大,生产和使用过程易对环境造成危害,且商用 SCR催化剂对单质汞的氧化效率极大地依赖于烟气中氯化氢的浓度。例如,低阶煤烟气中HCl浓度较低,钒基SCR催化剂对单质汞的氧化效率低于30%。随着煤资源的枯竭,越来越多的低阶煤将被利用,能够在低浓度 HCl条件下促进Hg0的高效氧化的催化剂具有非常广阔的市场前景。
综上所述,为了降低成本以及为了保护环境,如果能开发出具有价格低廉、环境友好型以及在较低的HCl浓度下即可实现Hg0的高效氧化的催化剂已成为各国研究的热点。
发明内容
为了克服现有技术的不足,本发明的目的是提供一种低污染、低成本、环境友好型的新型高效烟气汞氧化催化剂及其应用。本发明的烟气汞氧化催化剂具有高效催化氧化能力,在较低的HCl浓度下,即能将燃煤烟气中的单质汞氧化为易被除尘器和湿法脱硫装置脱除的二价汞,实现燃煤烟气的净化。
本发明的技术方案具体介绍如下。
本发明提供一种烟气汞氧化催化剂,其是铜冶炼或者镍冶炼的水淬渣。也可是经过热处理、酸处理或者掺杂处理的铜冶炼或者镍冶炼的水淬渣。
上述烟气汞氧化催化剂,热处理时,温度在 350-550℃之间;酸处理时用10%的稀盐酸或者10%的稀硫酸浸泡1-2h;掺杂处理时,将金属水淬渣和CuCl2或者CeO2进行掺杂处理,金属水淬渣和CuCl2的质量比为100:1~20:1、金属水淬渣和CeO2的质量比为300:1~100:1。
进一步的,本发明提供一种上述的烟气汞氧化催化剂在燃煤烟气中单质汞的催化氧化方面的应用。应用方法如下:在180 ℃至 350 ℃条件下,烟气汞氧化催化剂以颗粒喷射、流化床、固定床方式与燃煤烟气发生接触,脱除燃煤烟气中的单质汞。
本发明中,采用颗粒喷射方式,利用烟气汞氧化催化剂对燃煤烟气中单质汞催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥并碾碎至粒度为10-600 μm后,采用压缩空气将烟气汞氧化催化剂喷入颗粒物控制设备前的烟道中,喷射的烟气汞氧化催化剂的质量与燃煤烟气中汞的质量比在5000:1-100000:1之间。本发明中,采用流化床方式,利用烟气汞氧化催化剂对燃煤烟气中单质汞催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥并碾碎至粒度为10-1000 μm后,在流化床中与烟气中的汞发生接触,流化床布置于任意除尘设备或脱硫设备之前,流化床的温度180-350 ℃之间,压力在-100Pa 到100 Pa之间。
本发明中,采用固定床方式,利用烟气汞氧化催化剂对燃煤烟气中单质汞催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥并以蜂窝状或蜂球状形式在固定床中与烟气中的汞发生接触,固定床内温度在180-350℃,气体流速为0.1-2 m/s,压力降小于 5000Pa。
本发明中的烟气汞氧化催化剂是基于铜冶炼、镍冶炼的水淬渣,这些金属冶炼水淬渣中除了含有对单质汞具有较强的催化氧化作用的氧化铁和氧化铜等金属氧化物外,还富集大量的锰、钼、铬、钴、钼等过渡金属元素,其中,锰、铬、钼等元素及其金属氧化物已被证明具有极强催化氧化汞能力,炼铜水淬渣中还含有微量的金、银等贵金属元素可以与烟气中痕量的汞反应形成汞齐,从而脱除烟气中的汞。
本发明中,经过热处理、酸处理或者掺杂处理的铜冶炼或者镍冶炼的水淬渣可以更好的用作烟气汞氧化催化剂,原因可能在于,热处理(350-550℃)使得水淬渣中的晶粒细化,消除了些晶体缺陷,进而提高了催化剂的催化氧化性能;酸处理有助于催化剂表孔隙的打开或形成,同时使用稀盐酸酸洗使得催化剂表面负载了一定的氯离子,有利于催化剂表面形成跟多的活性氯,从而增强了冶炼水淬渣对汞的氧化能力;而掺杂处理主要是利用用CeO2或CuCl2自身较强的催化氧化作用,从而进一步增强了金属冶炼水淬渣对汞的氧化作用。
本发明与现有技术相比具有以下优点:
(1)铜冶炼、镍冶炼等金属冶炼水淬渣对单质汞具有较好的催化氧化作用,制备工艺简单,利用其脱除烟气中的单质汞时,能够高效的将单质汞氧化为易被除尘器和湿法脱硫装置脱除的二价汞,无需复杂的预处理,操作简单,无需复杂的设备,投资较少。
(2)铜冶炼、镍冶炼等金属冶炼水淬渣本身可用于水泥、建材等领域,其在燃煤电厂使用时无二次污染,对后续设备脱汞无任何影响,进入飞灰后也不影响飞灰的后续利用。
(3)铜冶炼、镍冶炼等金属冶炼水淬渣,具有脱汞效率高(脱汞效率在85%以上)、反应温度区间广,在较低HCl浓度下即可实现对单质汞的高效脱除。
(4)选用铜冶炼、镍冶炼等金属冶炼水淬渣脱除燃煤烟气中零价汞具有价格低廉、投资少等优势外,而且在实现燃煤烟气中单质汞高效脱除的同时实现炼铜水淬渣的高附加值资源化利用,避免铜渣大量堆存引起的占地及污染问题。
具体实施方式
以下通过具体实施例对本发明的技术方案做进一步描述。实施例并非对保护范围的限制。
实施例中,铜冶炼水淬渣来自河南省某铜冶炼厂,由x射线荧光光谱仪定量分析,其主要元素如表1所示:
表1
元素 | Fe | Ca | Zn | Mg | Al | Na | K | Cu | Si |
含量 | 34.1 | 5.51 | 2.04 | 1.39 | 1.96 | 1.02 | 0.79 | 0.55 | 15.89 |
镍冶炼水淬渣来自广西某镍冶炼厂,由x射线荧光光谱仪定量分析,其主要元素如表2所示:
表2
元素 | Fe | Mg | Zn | Ca | Al | Ni | K | Cu | Si |
含量 | 38.9 | 4.8 | 1.89 | 2.39 | 2.04 | 0.39 | 0.99 | 0.39 | 17.69 |
实施例1
选取少量的未经预处理的铜冶炼水淬渣,将其干燥后研磨至 60-100目筛,称取研磨后的铜冶炼水淬渣 0.3g,将其置于长为 500 mm,内径为10 mm的圆柱形石英玻璃固定床反应器中。采用管式炉控制反应温度,通过质量流量计模拟烟气成分以及浓度,其中烟气成分为20 ppm HCl,75µg/m3 Hg0。模拟烟气流速为 0.15 m/s,使用测汞仪监测反应器进出口单质汞浓度,在250 ℃反应时,对单质汞的氧化率高达90%以上。
实施例2
选取少量的经过10%的稀硫酸浸泡1.5h的铜冶炼水淬渣,将其干燥后研磨60-100目筛,称取研磨后的铜冶炼水淬渣0.3 g,将其置于长为500 mm,内径为10 mm的圆柱形石英玻璃固定床反应器中。采用管式炉控制反应温度,通过质量流量计模拟烟气成分以及浓度,在模拟烟气气氛为300 ppm NO、400 ppm SO2、20 ppm HCl、8% H2O,75µg/m3 Hg0下,烟气流速为0.15 m/s,使用测汞仪监测反应器进出口单质汞浓度,在250 ℃反应温度时对单质汞的脱除率高达95%以上。
实施例3
选取少量掺杂质量分数为1%的CuCl2镍冶炼水淬渣,将掺杂的镍冶炼水淬渣干燥并磨细至粒度为200-300 μm后,采用压缩空气将金属冶炼水淬渣喷入颗粒物控制设备前的烟道中,喷射的镍冶炼水淬渣的质量与燃煤烟气中汞的质量比在80000:1-100000:1之间,在模拟燃煤烟气成分,75µg/m3 Hg0初始汞浓度下,使用测汞仪监测反应器进出口单质汞浓度,在180-300 ℃反应温度模拟烟气成分下对单质汞的脱除率均高达85%以上。
实施例4
实际燃煤烟气流量约为1000 m3/h,烟气温度约为250 ℃,烟气中单质汞的浓度约为20 µg/m3。选取干燥后的500℃热处理5h的铜冶炼水淬渣以流化床的形式与燃煤烟气进行接触,在实际燃煤烟气下铜冶炼水淬渣高效的将单质汞氧化为二价汞,进而被下游的洗涤器捕集脱除,从而实现烟气中单质汞的脱除。烟气出口单质汞的浓度用燃煤烟气测汞仪在线监测。结果表明:烟气出口单质汞浓度可控制在5µg/m3 以下,使用该新型催化剂结合湿式洗涤装置可以实现燃煤烟气中单质汞的高效脱除。
以上实施例是对本发明的说明,不是对本发明的限定,任何对本发明进行简单修改后的方案,都属于本发明的保护范围。
Claims (4)
1.一种烟气汞氧化催化剂在燃煤烟气中单质汞的催化氧化方面的应用,其特征在于,应用方法如下:在180 ℃至 350 ℃的温度下,烟气汞氧化催化剂以颗粒喷射、流化床、固定床方式与燃煤烟气发生接触,氧化、脱除燃煤烟气中的单质汞;其中:烟气汞氧化催化剂是基于铜冶炼或镍冶炼的金属冶炼水淬渣。
2.根据权利要求1所述的应用,其特征在于,采用颗粒喷射方式进行催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥并碾碎至粒度为10-600 μm后,采用压缩空气将烟气汞氧化催化剂喷入颗粒物控制设备前的烟道中,喷射的烟气汞氧化催化剂的质量与燃煤烟气中汞的质量比在5000:1-100000:1之间。
3.根据权利要求1所述的应用,其特征在于,采用流化床方式,利用流化床方式进行催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥并碾碎至粒度为10-1000 μm后,在流化床中与烟气中的汞发生接触,流化床布置于任意除尘设备或脱硫设备之前,流化床的温度180-350 ℃之间,压力在-100Pa 到100 Pa之间。
4.根据权利要求1所述的应用,其特征在于,采用固定床方式进行催化氧化时,具体步骤如下:将烟气汞氧化催化剂干燥,并以蜂窝状或蜂球状形式在固定床中与烟气中的汞发生接触,固定床内温度在180-350℃,气体流速为0.1-2 m/s,压力降小于 5000 Pa。
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