CN106187146A - 一种干法解毒铬渣的工艺 - Google Patents

一种干法解毒铬渣的工艺 Download PDF

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CN106187146A
CN106187146A CN201610592884.3A CN201610592884A CN106187146A CN 106187146 A CN106187146 A CN 106187146A CN 201610592884 A CN201610592884 A CN 201610592884A CN 106187146 A CN106187146 A CN 106187146A
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slag
chromium slag
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宁平
何力为
李彬
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Kunming University of Science and Technology
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Abstract

本发明涉及一种干法解毒铬渣的工艺,属于铬渣干法解毒技术以及有害固体废物处置领域。采用Al2O3含量为96%以上的氧化铝粉占30~50wt%、QM‑95以上级别轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%制备添加剂,然后与铬渣混合焙烧,使铬渣中的六价铬还原为三价铬并将其在常温下固定。该方法组成材料均为市售商品,制作成本较低,用于铬渣干法解毒工艺,掺加量较少,可有效降低干法解毒工艺过程所需温度,促进终含镁渣尖晶石结构形成,采用一段式工艺处理即可达标,终渣不返黄。

Description

一种干法解毒铬渣的工艺
技术领域
本发明涉及一种干法解毒铬渣的工艺,属于铬渣干法解毒技术以及有害固体废物处置领域。
背景技术
铬渣由于含有高毒、致癌性的Cr(Ⅵ)而具有毒性。铬渣中Cr(Ⅵ)随雨水浸出,进入周围的河流、土壤,对环境和人的健康造成巨大的危害。铬渣中有害六价铬有多种存在状态,在硅酸钙-铬酸钙固溶体、铁铝酸钙-铬酸钙固溶体中,铬酸钙(CaCrO4)存在于硅酸钙或铁铝酸钙晶格内,属于酸溶Cr6+。要消除这两种Cr6+,必须破坏硅酸钙和铁铝酸钙晶格,或在极高温度特别是有酸性氧化物存在下使六价铬游离而分解,或者利用还原性气体(如CO,H2)于高温下扩散将硅酸钙和铁铝酸钙晶格内CrO4 2-还原为Cr3+
铬渣干法解毒是采用回转窑或立窑作为煅烧设备,在高温下利用还原性物质将铬渣中的六价铬还原为三价铬并将其在常温下固定的工艺过程。目前国内一般采用高温炉窑处置含铬废弃物,但该工艺所需温度较高,一般在1300℃以上,且出渣容易返黄,需用硫酸亚铁等还原剂进一步还原,以保证终渣的稳定性。
发明内容
有鉴于现有干法解毒工艺的不足,本发明的目的在于提供一种干法解毒铬渣的工艺,有效降低干法解毒铬渣工艺所需温度,并使还原成三价后的铬有效固定在尖晶石晶格中,无需后续还原处理。
本发明通过以下技术方案实现:
(1)添加剂制备:Al2O3含量为96%以上的氧化铝粉(粒径≤75μm)占30~50wt%、QM-95以上级别轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%,三种原料自由水含水率≤5%;先将氧化铝粉和无烟煤粉进行混合,再加入轻烧镁粉混合后共磨成粉(粒径≤3mm),即得添加剂;
(2)还原焙烧:将步骤(1)制得的添加剂与铬渣(粒径≤3mm,含水率<5%)按照质量比为0.05~0.15:1混合均匀,混合后的碱度,即(MgO wt%+CaO wt%)/(SiO2 wt%+Al2O3 wt%)的比值,控制在1.0~1.3之间;然后在还原性气氛下600~1000℃焙烧20~40min。
本发明与现有技术相比有如下显著效果:
(1)本发明通过添加一定配比的氧化镁粉、氧化铝粉、无烟煤粉混合物,可以使还原反应在相对较低的温度即可高效完成还原过程,且还原后终渣无需进行后续还原处理即可保证稳定达标;
(2)本发明根据冶金反应工程学原理,以控制混合料的化学组分为核心,使终渣形成稳定的含铬尖晶石,克服了现有技术中解毒铬渣返黄问题,且终渣可得到资源化综合利用,无二次污染。
(3)本方法所用原料均为市售商品,且掺加量较少,采用一段式工艺处理即可达标,工艺成本较低。
附图说明
图1 为本发明工艺流程图。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1-3所采用的配料及配比如表1-表3所示:
表1 各实施例配料及配比
表2 铬渣铬形态及含量(%)
表3 铬渣化学成分分析(%)
将氧化铝粉、轻烧镁粉、无烟煤粉烘干至自由水含水率≤5%;将铬渣烘干至含水率低于5%,磨细至粒径≤3mm。
实施例1
按表1配比,取氧化铝粉和轻烧镁粉混合后共磨至粒径≤3mm制得添加剂,将添加剂与铬渣混合均匀,碱度为1.23,放入真空管式炉,控制还原性气体CO含量为80~90%,在600℃下还原焙烧30min,测定反应后六价铬浸出毒性为0.130mg/kg,置于自然条件下放置3个月后测定六价铬浸出毒性为0.137mg/kg。
实施例2
按表1配比,先将氧化铝粉和无烟煤粉进行混合,再加入轻烧镁粉混合后共磨至粒径≤3mm制得添加剂,将添加剂与铬渣混合均匀,碱度为1.28,放入真空管式炉,控制还原性气体CO含量为80~90%,在800℃下还原焙烧30min,测定反应后六价铬浸出毒性为0.064mg/kg,置于自然条件下放置3个月后测定六价铬浸出毒性为0.067mg/kg。
实施例3
按表1配比,先将氧化铝粉和无烟煤粉进行混合,再加入轻烧镁粉混合后共磨至粒径≤3mm制得添加剂,将添加剂与铬渣混合均匀,碱度为1.17,放入真空管式炉,控制还原性气体CO含量为80~90%,在1000℃下还原焙烧20min,测定反应后六价铬浸出毒性为0.011mg/kg,置于自然条件下放置3个月后测定六价铬浸出毒性为0.015mg/kg。

Claims (7)

1.一种干法解毒铬渣的工艺,包括以下步骤:
(1)添加剂制备:氧化铝粉占30~50wt%、轻烧镁粉占30~50wt%、无烟煤粉占0~40wt%,先将氧化铝粉和无烟煤粉进行混合,再加入轻烧镁粉混合后共磨成粉,即得添加剂;
(2)还原焙烧:将步骤(1)制得的添加剂与铬渣按照质量比为0.05~0.15:1混合均匀后,在还原性气氛下600~1000℃焙烧20~40min。
2.根据权利要求1所述的工艺,其特征在于,氧化铝粉粒径≤75μm,且其中Al2O3含量为96%以上。
3.根据权利要求1所述的工艺,其特征在于,轻烧镁粉为QM-95以上级别。
4.根据权利要求1所述的工艺,其特征在于,步骤(1)中三种原料自由水含水率≤5%。
5.根据权利要求1所述的工艺,其特征在于,步骤(1)中三种原料混合后共磨成粉,粒径≤3mm。
6.根据权利要求1所述的工艺,其特征在于,步骤(2)中的铬渣粒径≤3mm,含水率<5%。
7.根据权利要求1所述的工艺,其特征在于,步骤(2)中添加剂与铬渣混合后的碱度,即(MgO wt%+CaO wt%)/(SiO2 wt%+Al2O3 wt%)的比值为1.0~1.3。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107234125A (zh) * 2017-07-11 2017-10-10 中州大学 一种处理有毒性铬渣的工艺方法
CN114558271A (zh) * 2022-01-12 2022-05-31 湖南国发控股有限公司 一种两步法铬渣解毒配方及协同工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528532A (zh) * 2003-10-10 2004-09-15 匡少平 铬渣的无害化和资源化处理方法及其应用
CN101138670A (zh) * 2006-09-08 2008-03-12 隋智通 工业废渣高温还原解毒铬渣新方法
CN101376051A (zh) * 2007-08-27 2009-03-04 天津市大钧科技开发有限公司 立窑1100℃±100℃高温煅烧11-15%铬渣干法解毒技术
CN103638629A (zh) * 2013-12-10 2014-03-19 西南科技大学 一体化还原固化铬渣的工艺
CN105399331A (zh) * 2015-10-27 2016-03-16 广东省生态环境与土壤研究所(广东省土壤科学博物馆) 一种用于铬渣中铬双重固定解毒的玻璃陶瓷化方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1528532A (zh) * 2003-10-10 2004-09-15 匡少平 铬渣的无害化和资源化处理方法及其应用
CN101138670A (zh) * 2006-09-08 2008-03-12 隋智通 工业废渣高温还原解毒铬渣新方法
CN101376051A (zh) * 2007-08-27 2009-03-04 天津市大钧科技开发有限公司 立窑1100℃±100℃高温煅烧11-15%铬渣干法解毒技术
CN103638629A (zh) * 2013-12-10 2014-03-19 西南科技大学 一体化还原固化铬渣的工艺
CN105399331A (zh) * 2015-10-27 2016-03-16 广东省生态环境与土壤研究所(广东省土壤科学博物馆) 一种用于铬渣中铬双重固定解毒的玻璃陶瓷化方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王绍文等: "《固体废弃物资源化技术与应用》", 30 June 2003, 冶金工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107234125A (zh) * 2017-07-11 2017-10-10 中州大学 一种处理有毒性铬渣的工艺方法
CN114558271A (zh) * 2022-01-12 2022-05-31 湖南国发控股有限公司 一种两步法铬渣解毒配方及协同工艺
CN114558271B (zh) * 2022-01-12 2023-11-28 湖南国发控股有限公司 一种两步法铬渣解毒配方及协同工艺

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Application publication date: 20161207