CN115400720B - 一种用于去除有色金属矿区含硫恶臭气体的吸附剂及其制备方法和应用 - Google Patents
一种用于去除有色金属矿区含硫恶臭气体的吸附剂及其制备方法和应用 Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 60
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 21
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- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 description 1
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- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
本发明公开了一种用于去除有色金属矿区含硫恶臭气体的吸附剂,是将铅锌矿尾矿与碱性添加剂混合后煅烧、粉碎得到,所述含硫恶臭气体包含硫化氢;所述碱性添加剂选自碳酸钠、氢氧化钠、氢氧化钾中的一种或多种,碱性添加剂为固体或液体溶液。还公开了其制备方法和在去除恶臭气体中的应用。与传统的H2S去除工艺不同,本发明遵循环保以废治废原则,以铅锌矿选矿后的废弃物为原材料制得了含硫恶臭污染气体的吸附剂,成本低,原料来源广,去除效果显著。与传统的H2S去除工艺相比,大大节约了成本,而且操作非常简单,只需将吸附剂放置于含有H2S气体的环境即可。
Description
技术领域
本发明涉及污染气体处理技术领域,涉及含硫恶臭气体的处理技术,具体涉及一种用于去除有色金属矿区含硫恶臭气体的吸附剂及其制备方法和应用。
背景技术
矿区选矿过程中会投加大量的选矿药剂、硫化物、还进行一系列的加热等,导致这个过程会产生大量的有机硫、有机胺等恶臭物质,这些恶臭物质在生产、储运过程中,以排放、挥发、泄漏等方式进入大气,引起周围环境不同程度的恶臭污染。人的感观对恶臭污染极其敏感,某些恶臭物质的嗅觉阀值低可低至0.0001mg/m3。因此,只要恶臭源排放或泄漏少量这类恶臭物质就能在很大范围内引起恶臭污染。恶臭污染是选矿行业的特征污染之一,作为环境公害已为当今世界所公认。
而铅锌矿选矿药剂如黄药等本身具有较浓烈的气味,其次由于药剂的氧化产生其他刺激性气体如硫化氢(H2S)等,导致浮选厂生产区气味较为浓烈,影响工作环境。H2S是有毒、有恶臭气味的刺激性气体,高浓度的H2S存在于生物气中在运输使用生物气过程中会降低能源热值,腐蚀管路,甚至对人体造成伤害,所以除去H2S是充分发挥生物气效能、达到绿色能源标准的前提。
脱除H2S的方法主要分为湿法脱硫工艺与干法脱硫工艺,湿法脱硫可以处理生产中的高浓度H2S,满足工业高负荷要求,但操作工艺复杂、成本高、易产生二次污染、有些吸收液有剧毒等缺陷,干法脱硫可以用于精细脱硫,但对高浓度H2S不耐受,硫容量低。近年来离子液体由于其蒸汽压低、不易挥发、良好的热稳定性以及化学稳定性、结构性质可设计性,被应用于H2S等酸性气体的吸收中,具有高效吸收性能、吸收剂易再生、能够分离多相酸性气体等特点,尤其是金属基功能化离子液体吸收H2S,利用H2S化学性质吸收效率高,并可循环再生。但由于离子液体价格昂贵、黏稠度过高、较低的气液传质效率导致离子液体工业应用化受阻。所以开发一种成本低且容易操作的改良剂对实现选矿车间恶臭H2S去除具有一定的现实意义。
发明内容
本发明的目的是针对上述问题,提供一种低成本、原料来源广、使用简单方便的用于去除有色金属矿区含硫恶臭气体的吸附剂。
本发明为了实现其目的,采用的技术方案是:
一种用于去除有色金属矿区含硫恶臭气体的吸附剂,是将铅锌矿尾矿与碱性添加剂混合后煅烧、粉碎得到,所述含硫恶臭气体包含硫化氢;所述碱性添加剂选自碳酸钠、氢氧化钠、氢氧化钾中的一种或多种,碱性添加剂为固体或液体溶液。
所述碱性添加剂为固体;
铅锌矿尾矿与碱性添加剂的配比为:干燥后的铅锌矿尾矿与固体碱性添加剂的质量比为1~10:1。
煅烧温度为200~1000℃,优选400~1000℃或600~1000℃或600℃;煅烧时间为30min~7h或30min~6h,优选1~6h或2~6h或2h。
优选地,所述铅锌矿尾矿与碱性添加剂的质量比为1~5:1或1~3:1或1~2.5:1或2.5:1。
优选地,所述吸附剂的粒度为10~200目,优选20~200目或60~200目或80~200目或100~200目或80~120目或100目。
在上述技术方案中,所述铅锌矿尾矿是指铅锌矿经浮选工艺选矿后剩下的废弃物;
所述碱性添加剂为碳酸钠。
本发明还提供上述的吸附剂的制备方法,包括如下步骤:取铅锌矿尾矿,干燥,加入碱性添加剂后煅烧、研磨,即得。
本发明还提供上述的吸附剂在去除恶臭气体中的应用,将所述吸附剂放置于含有含硫恶臭气体的环境中对恶臭气体进行吸附。
在上述应用技术方案中,所述含有含硫恶臭气体的环境为铅锌矿选矿车间。
在上述应用技术方案中,所述吸附剂投放量按照环境中硫化氢浓度为5~20mg/m3,投放80-120克吸附剂,吸附1h以上,优选吸附2h以上;
优选按照环境中硫化氢浓度为8~15mg/m3或10~14mg/m3,投放90-110克吸附剂,吸附1~50h或者1~40h或者1~36h或者1~24h或者2~12h或者2~8h。
本发明的吸附剂将铅锌矿尾矿和碱性添加剂混合后煅烧,首先通过高温煅烧使得吸附剂碳化,提高样品的比表面积、碳氮比等增加吸附剂对污染物的亲和力。其次,铅锌尾矿属于金属氧化物混合物,对硫化氢具有一定的化学吸附作用。本吸附剂脱除硫化氢的机理主要包括两个方面:
一方面,经煅烧研磨筛分后的吸附剂孔隙度高、颗粒细小、比表面积大、活性组分的分散,提供丰富的硫化氢吸附位点,进而增加H2S的吸附率。
另一方面,吸附剂利用其化学吸附能力去除,碱性吸附剂及金属氧化物都可与H2S反应进而达到去除H2S的效果,以碱性添加剂为碳酸钠为例,本发明的吸附剂的主要化学反应方程式如下:
Na2CO3+H2S→NaHS+NaHCO3
ZnO+H2S→ZnS+H2O
H2S+3Fe2O3→Fe2S3+3H2O
MnO+H2S→MnS+H2O
CuO+H2S→CuS+H2O
本发明的有益效果是:与传统的H2S去除工艺不同,本发明遵循环保以废治废原则,以铅锌矿选矿后的废弃物为原材料制得了含硫恶臭污染气体的吸附剂,成本低,原料来源广,去除效果显著。与传统的H2S去除工艺相比,大大节约了成本,而且操作非常简单,只需将吸附剂放置于含有H2S气体的环境即可。
附图说明
图1是不同吸附时间H2S的去除效果。
具体实施方式
下面结合实施例对本发明作进一步说明,但并不因此而限制本发明。
下述实施例中的实验方法,如无特别说明,均为常规方法;所用化学试剂,如无特殊说明,均为本领域常规试剂。
本发明中所述黄药,英文名为xanthate,是硫化矿浮选常用的一种巯基扩捕收剂,学名为巯基黄原酸盐,可商购获得。
本发明中所用原料铅锌矿尾矿是广东省韶关市凡口铅锌矿区的硫化铅锌矿经浮选后得到的尾矿废弃物,是粘稠的矿浆,主要化学成分含有ZnO,Fe2S,CaCO3,SiO2等等。
凡口铅锌矿的浮选过程加的主要药剂量如下:5-6kg/t硫酸;腐殖酸钠,2号油,黄药,均为800g/t;硫酸铜,石灰,乙硫氮,均为140g/t。
实施例1
取适量铅锌矿尾矿样品于自然条件下风干作为本实施例的铅锌矿尾矿原料。制备如下实验组1-5的吸附剂样品:
实验组1:准确称取风干后的铅锌矿尾矿样品200g;
实验组2:准确称取200g碳酸钠;
实验组3:准确称取风干后的铅锌矿尾矿样品200g,于600℃下煅烧2h;
实验组4:准确称取200g碳酸钠,于600℃下煅烧2h;
实验组5:准确称取风干后的铅锌矿尾矿样品100g和100g碳酸钠,混合后于600℃下煅烧2h。
各组煅烧样品待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成100目的吸附剂样品备用。
用黄药在空气仓中模拟出含H2S恶臭气体的环境:称取0.8g黄药加入1L超纯水置于2L干燥器内,干燥器作为模拟空气仓,黄药在水中释放H2S气体,待空气仓中H2S浓度恒定不再变化时,取前面筛分得到的吸附剂样品100g放置于空气仓中,H2S的初始浓度为12.43mg/m3,检测吸附剂吸附1h后的H2S浓度。H2S浓度检测方法采用《JJG695-2003硫化氢气体检测仪》中的方法,检测结果如表1中所示。
表1添加不同吸附剂对H2S的去除效果
表1中结果表明,单NaCO3组煅烧或不煅烧,其对H2S去除效果没有实质的影响,而尾矿在煅烧后其去除效果得到提高;实验组5吸附效率最高,尾矿与碳酸钠混合后煅烧制得的吸附剂的硫化氢去除效果显著大于单尾矿组及单NaCO3组,采用两种成分经煅烧后吸附剂的H2S去除率得到显著的提升。
实施例2最佳碱性添加剂的确定
设计了以下实验研究进行验证:
取适量铅锌矿尾矿样品于自然条件下风干,准确称取风干后的样品100g于200mL坩埚中,分别于盛有100g尾矿样品的坩埚中分别加入10、20、40、60、80、100g的固体碳酸钠、氢氧化钠、氢氧化钾,分别配置成10:1、5:1、5:2、5:3、5:4、1:1的质量比充分混合后将坩埚放入马弗炉中煅烧,于600℃下煅烧2h,待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成100目的吸附剂样品备用。
用黄药在空气仓中模拟出含H2S恶臭气体的环境:称取0.8g黄药加入1L超纯水置于2L干燥器内,干燥器作为模拟空气仓,黄药在水中释放H2S气体,待空气仓中H2S浓度恒定不再变化时,取前面筛分得到的吸附剂样品100g放置于空气仓中,H2S的初始浓度为12.43mg/m3,检测吸附剂吸附1h后的H2S浓度。H2S浓度检测方法采用《JJG695-2003硫化氢气体检测仪》中的方法。
表2添加不同碱性添加剂及不同质量比对H2S的去除效果
表2中结果表明,在同种质量比情况下,添加NaCO3碱性添加剂对H2S的去除效果最好,且在质量比为5:2时去除效果最优。
在铅锌矿尾矿与碱性添加剂的质量比为10~2.5:1范围内,随着碱性添加剂的配比的增加,H2S的去除率明显提高,但是在2.5~1:1范围内,H2S的去除率与碱性添加剂的量并不成正比,其中质量比为5:2时,H2S的去除率最佳。当碱性添加剂采用碳酸钠时,方差分析证实铅锌矿尾矿与碱性添加剂的质量比在10:1~1:1区间内都具有尚佳的适用性,当碱性添加剂采用氢氧化钠或氢氧化钾时,铅锌矿尾矿与碱性添加剂的质量比在5:1~1:1区间内都具有尚佳的适用性。
实施例3最佳煅烧温度的确定
设计了以下实验研究进行验证:
取适量铅锌矿尾矿样品于自然条件下风干,准确称取5份风干后的样品100g于200mL坩埚中,分别于盛有100g尾矿样品的坩埚中分别加入40g的碳酸钠,配置成5:2的质量比,充分混合后将坩埚放入马弗炉中煅烧,分别于200、400、600、800、1000℃下煅烧2h,待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成100目的吸附剂样品。按照实施例2中的H2S去除实验方法检测不同煅烧温度下制得的吸附剂对于H2S的去除率,实验结果如表3所示。
表3不同煅烧温度制得的吸附剂对H2S的去除效果
表3中结果表明,在煅烧温度200~1000℃范围内,随着温度的增加,H2S的去除率明显提高,且于600℃后基于稳定,方差分析证实本发明在400~1000℃温度区间内都具有尚佳的适用性。为了节能,最优选择600℃煅烧条件。
实施例4最佳煅烧时间的确定
设计了以下实验研究进行验证:
取适量铅锌矿尾矿样品于自然条件下风干,分别准确称取5份风干后的样品100g于200mL坩埚中,分别于盛有100g尾矿样品的坩埚中分别加入40g的碳酸钠,配置成5:2的质量比,充分混合后将坩埚放入马弗炉中煅烧,于600℃下分别煅烧0.5h,1h,2h,4h,6h,待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成100目的吸附剂样品。按照实施例2中的H2S去除实验方法检测不同煅烧时间制得的吸附剂对于H2S的去除率,实验结果如表4所示。
表4不同煅烧时间制备的吸附剂对H2S的去除效果
表4中结果表明,在煅烧时间为0.5~6h范围内,随着时间的增加,H2S的去除率明显提高,且于2h后基于稳定,方差分析证实本发明在0.5~6h时间区间内都具有尚佳的适用性。为了节能,最优选择2h的煅烧时长。
实施例5最佳粒径的确定
设计了以下实验研究进行验证:
取适量铅锌矿尾矿样品于自然条件下风干,准确称取5份风干后的样品100g于200mL坩埚中,分别于盛有100g尾矿样品的坩埚中加入40g的碳酸钠,配置成5:2的质量比,充分混合后将坩埚放入马弗炉中煅烧,于600℃下煅烧2h,待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成10目、20目、60目、100目、200目的吸附剂样品。按照实施例2中的H2S去除实验方法检测不同粒径吸附剂对于H2S的去除率,实验结果如表5所示。
表5不同粒径吸附剂对H2S的去除效果
表5中结果表明,在吸附剂粒径目数在10~200目范围内,目数越大吸附剂粒径则越小,随着粒径的减小,H2S的去除率明显提高,且于100目后基于稳定,方差分析证实本发明在60~200目区间内都具有尚佳的适用性,且在100目时最稳定。
实施例6不同吸附时间的去除率检测
取适量铅锌矿尾矿样品于自然条件下风干,准确称取风干后的样品100g于200mL坩埚中,于盛有100g尾矿样品的坩埚中分别加入40g的碳酸钠,配置成5:2的质量比,充分混合后将坩埚放入马弗炉中煅烧,于600℃下煅烧2h待样品冷却后取出,用玛瑙研钵研磨,尼龙筛筛分成100目的吸附剂样品。
用黄药在空气仓中模拟出含H2S恶臭气体的环境:称取0.8g黄药加入1L超纯水置于2L干燥器内,干燥器作为模拟空气仓,黄药在水中释放H2S气体,在一个空气仓中放置制备的吸附剂,同时设置不放置吸附剂的对照空气仓,在黄药开始释放H2S气体后的不同时间(0.5,1,2,4,8,12,24,48h)检测空气仓的出口取样口处的H2S的出口浓度,计算H2S去除率,实验结果如图1所示,经吸附剂处理2h后,空气仓的出口取样口处的H2S的出口浓度趋于稳定,吸附剂的动态吸附率高达93.81%。
Claims (7)
1.一种吸附剂在去除恶臭气体中的应用,其特征在于:将所述吸附剂放置于含有含硫恶臭气体的环境中对恶臭气体进行吸附,所述含硫恶臭气体包含硫化氢;所述吸附剂是将铅锌矿尾矿与碱性添加剂混合后400~1000℃煅烧1~6 h、粉碎得到,所述铅锌矿尾矿是指铅锌矿经浮选工艺选矿后剩下的废弃物,所述碱性添加剂为碳酸钠或氢氧化钠,碱性添加剂为固体;所述吸附剂的粒度为80~200目;
当碱性添加剂为碳酸钠时,铅锌矿尾矿与碱性添加剂的配比为:干燥后的铅锌矿尾矿与固体碱性添加剂的质量比为1~3 : 1;
当碱性添加剂为氢氧化钠时,干燥后的铅锌矿尾矿与碱性添加剂的配比为2.5 : 1。
2.根据权利要求1所述的应用,其特征在于:所述吸附剂的煅烧温度为600~1000℃;煅烧时间为2~6 h。
3.根据权利要求1所述的应用,其特征在于:所述干燥后的铅锌矿尾矿与碳酸钠的质量比为1~2.5 : 1。
4.根据权利要求1所述的应用,其特征在于:所述吸附剂的粒度为100~200目。
5.根据权利要求1所述的应用,其特征在于:所述含有含硫恶臭气体的环境为铅锌矿选矿车间。
6.根据权利要求1所述的应用,其特征在于:所述吸附剂投放量按照环境中硫化氢浓度为5~20 mg/m3,投放80-120克吸附剂,吸附1h以上。
7.根据权利要求6所述的应用,其特征在于:
按照环境中硫化氢浓度为8~15 mg/m3,投放90-110克吸附剂,吸附1~50h。
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