CN110407179B - 一种同步固化稳定化硫化砷渣和硫资源回收的方法 - Google Patents
一种同步固化稳定化硫化砷渣和硫资源回收的方法 Download PDFInfo
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
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Abstract
本文公开了一种同步固化稳定化硫化砷渣和硫资源回收的方法,本文主要采用水热法,通过引入矿化剂硫酸铝将砷渣快速转化成砷钠明矾石,对转化条件进行优化并评估砷钠明矾石的长期稳定性。钠明矾石是一类极其稳定的矿物,其化学式一般为NaAl3(SO4)2(OH)6,利用砷酸根(AsO4 3‑)与钠明矾石结构中的硫酸根(SO4 2‑)之间的类质同象取代而形成砷钠明矾石固溶体(NaAl3(SO4)2‑x(AsO4)x(OH)6),从而实现砷的固化和稳定化。实验结果表明砷钠明矾石固溶体中x可达到0.154,其砷的质量分数为2.85%,废渣的体积减容达60%以上;硫的回收率达到90%以上,其纯度超过95%。对砷钠明矾石固溶体的砷浸出毒性进行评估,结果表明砷的浸出浓度为0.1~0.5mg/L,满足危险废弃物堆存要求,表明了该技术对砷渣的稳定化处理经济有效。
Description
技术领域
本发明属于砷废渣的固化稳定化处理及硫磺的回收利用领域。
背景技术
我国有色金属冶炼过程中产生大量的高浓度含砷废液,对于这种高浓度含砷废酸主要是采用沉淀工艺处理,该工艺简单,处理效果好因此被广泛使用。然而过程中产生大量含砷废渣属于剧毒物质,其中包括硫化砷渣,分子式As2S3,成分As 60.9%,S 39.1%,天然产物称为雌黄,黄色或橙黄色固体。该物品剧毒,易致癌。易溶于碱金属氢氧化物、碳酸盐、与过氧化物和浓硝酸作用氧化成砷酸而溶解。在纯水中的溶解度1.81mol/L,严重超出危险废弃物毒性浸出标准限值(5mg/L)。由于这些含砷废渣凝胶颗粒小难过滤,在堆放过程中向空气中散发硫化氢气体,并且其中的砷极易被氧化释放到环境中,造成土壤、水体污染。对人类和环境产生极大的影响。如果砷废渣不能得到妥善的处理和处置,不仅限制企业酸性废水的硫化处理工艺运行,而且砷渣存在极大的安全隐患,非常容易造成二次污染。因此,含砷废渣的减容和稳定固化显得尤为重要,其固化稳定化技术更能够有效的对砷渣进行安全处置。
关于钠明矾石固砷的研究国内外已有报道。据热力学手册,钠明矾石矿物的溶度积为2.00×10-80,显著低于砷酸钙化合物、砷铁共沉淀物、臭葱石的溶度积。钠明矾石矿物沉淀除砷,有望成为固砷的新的发展方向,具有潜在的环境意义。
目前含砷废渣的处理主要有两类方法,一类是通过稳定化、固化来降低砷渣的环境风险和毒性;另一类是将砷渣中的砷反应生成氧化砷、单质砷或者砷酸盐实现资源化回收利用。资源化处理又可分为火法处理与湿法处理两大类。火法处理主要包括氧化焙烧、还原焙烧及真空焙烧等;湿法主要有硫酸酸浸、硫酸铜置换法、硫酸铁法和碱浸法等。
对于含砷废渣的资源化,方法如下:
杜冬云等利用氧化脱硫浸出-酸化还原工艺,然后在酸性条件下加入氯化亚锡还原制备单质砷(杜冬云,崔杰,郭莉等.一种从硫化砷渣中回收单质砷的方法[Z].CN103388076B)。刘维等人以砷酸盐为原料,砷酸盐物料与碳质还原剂混合均匀后,置于惰性或还原气氛中,在负压条件下,进行还原焙烧,收集焙烧烟气,即得砷产品(刘维,梁超,焦芬等.一种含砷物料直接还原焙烧制备砷的方法[Z].CN106636678A)。马艳荣等将硫化砷渣碱溶后,并通过鼓入氧气将硫离子氧化生成单质,砷酸溶液再进行通入二氧化硫还原成亚砷酸溶液,亚砷酸溶液通过减压蒸馏和冷却结晶制备三氧化二砷(马艳荣.一种用硫化砷废渣制备三氧化二砷的方法[Z].CN102115166A)虽然砷渣废能够实现资源化,但是资源化的产品目前市场较少,且工艺过程复杂、能耗大,因此硫化砷渣的稳定化固化、安全填埋技术是目前亟需解决且更具现实意义。
砷废渣固化稳定化技术目前应用如下:
闵小波等通过调节硫化砷渣的液固比、pH、氧化还原电位,然后进入高温高压水热反应釜进行固化反应,实现硫化砷渣的水热稳定固化(闵小波,柴立元,姚理为等.一种硫化砷渣水热稳定固化处理方法[Z].CN106823238A)。此方法虽然在短期内可以实现硫化砷渣的稳定,但是不适宜长时间堆放。陈小凤等将硫化砷渣与硫化钠反应,后加入氧化剂氧化再加入铁盐或铝盐,最后采用水泥固化,降低了砷浸出毒性(一种硫化砷渣无害化处理的方法[Z].CN105963902A)。但是此方法大大增加了固体的体积,给堆存填埋造成一定的压力。张立宏等通过对硫化砷渣加入硫酸亚铁溶液,通入空气加热氧化反应生成臭葱石,从而降低渣的浸出毒性便于安全堆存(一种硫化砷渣浸出及同步稳定化的方法[Z].CN105967232A)。臭葱石的毒性浸出测试表明短期内臭葱石较稳定,但是长期稳定性欠佳,并且只有在酸性条件下才能维持稳定的状态,在pH值近中性或者碱性环境中,臭葱石有不同程度的溶解。
本技术处理含砷废渣是采用固化稳定化技术将硫化砷渣中的砷转化到砷钠明矾石中,从而降低砷渣的浸出毒性。将无定型的纳米级的砷渣转化为微米级的易沉淀的大颗粒晶态砷钠明矾石,并且大大减少了固体的体积,同时反应后实现硫单质资源化回收。因此,此方法一步实现了含砷废渣的稳定化处置,并且对硫资源进行回收再利用。
发明内容
本发明的目的是提供一种含砷废渣固相转化与固化稳定化、同时回收硫磺的方法,是在水热过程中,砷渣中溶出硫离子、三价砷分别被氧化成硫磺和五价砷,然后利用砷酸根(AsO4 3-)与钠明矾石结构中的硫酸根(SO4 2-)之间的类质同象,取代钠明矾石(NaAl3(SO4)2(OH)6)中SO4 2-的位置,而形成砷钠明矾石固溶体(NaAl3(SO4)2-x(AsO4)x(OH)6),从而实现砷的固化和稳定化。本发明操作简单,生成的砷钠明矾石晶体,颗粒大易沉淀、体积小和稳定性高,结果表明在pH 1~11范围内砷的浸出浓度为0.1~0.5mg/L,远小于危险废弃物毒性浸出(浸出方法参见HJT 299-2007)标准限值(5mg/L),满足危险废弃物堆存要求,表明了该技术对砷渣的稳定化处理经济有效。同时,生成的单质硫易回收,作为硫磺再利用。
本发明涉及到的反应方程式如下:
As2S3+4H2O2=2AsO4 3-+3S↓+8H+
Na++3Al3++(2-x)(SO4 2-)+xAsO4 3-+6H2O=NaAl3(SO4)2-x(AsO4)x(OH)6+6H+
本发明的技术方案如下:
一种含砷废渣固相转化与固化稳定化方法,在酸性条件下,将砷废渣加入到配置好的一定浓度的或氧化氢、硫酸铝和硫酸钠的混合溶液,溶液移至高压反应釜中。最终生成砷钠明矾石与单质硫,达到固砷和回收硫磺的目的。具体步骤如下:
配置含有10~15%过氧化氢、0.05~0.1mol/L硫酸钠、0.05~0.16mol/L十二水合硫酸铝的混合溶液,用硫酸调节pH值1~3,然后将砷废渣加入到混合液中搅拌均匀(固液比1:150~1:80g/ml);
将上述所得混合液移至水热反应釜中,将其放置180~200℃的烘箱中反应1.5~6h。反应后冷却至室温。通过水热处理后,通过离心分离洗涤干燥,得到白色沉淀砷钠明矾石和可回收的黄色固体硫单质。
附图说明
图1是实施案例1处理前硫化砷渣的固体渣的XRD与标准卡片的对比
图2是实施案例1处理前硫化砷渣固体渣的SEM图
图3是实施案例1处理后砷钠明矾石的XRD与标准卡片的对比
图4是实施案例1、2、3、4处理后砷钠明矾石分别对应的SEM图分别对应图a,b,c,d
图5是实施案例1处理后硫单质的XRD与标准卡片的对比
图6是实施案例1处理后硫单质的SEM图
图7是实施案例1处理后砷钠明矾石在不同pH值下的浸出实验
具体实施方式
以下结合实施例对本发明作进一步地说明,但本发明的实施方式不限于此。
具体操作步骤如下:
实施案例1
取0.1g含模拟硫化砷渣于反应釜中,加入含有10%的过氧化氢,硫酸铝、硫酸钠浓度分别为0.08mol/L,0.08mol/L的混合溶液,使得固液比为1:150g/ml,调节pH=2,搅拌均匀后,将反应釜放入200℃下反应2h,自然冷却至室温。通过清洗浮选,最终分离得到黄色结块硫磺、砷钠明矾石固体,硫的回收率达到90%,其纯度超过95%;其砷的质量分数为2.85%,废渣的体积减容60%;砷的毒性浸出为0.1mg/L。
实施案例2
以福建省某冶炼厂的酸性废水处理产物硫化砷污泥为研究对象。全元素质量分析显示砷渣中主要元素有As 53.4%、S 42%、Na 1.5%、Ni 1.3%、Cu 0.98%,取0.1g含砷废渣于反应釜中,加入含有10%的过氧化氢,硫酸铝、硫酸钠浓度分别为0.08mol/L,0.08mol/L的混合溶液,使得固液比为1:150g/ml,调节pH=2,搅拌均匀后,将反应釜放入200℃下反应2h,自然冷却至室温。通过清洗浮选,最终分离得到黄色结块硫磺、砷钠明矾石固体,硫的回收率达到90%,其纯度超过95%;其砷的质量分数为2.38%,废渣的体积减容60%;砷的毒性浸出为0.16mg/L。
实施案例3
以河南省某有色金属冶炼厂污酸废水硫化沉淀后产生的硫化砷渣为研究对象。全元素质量分析显示砷渣中主要元素有As 11.35%、S 37.96%、O 26.09%、Cu 23.53%、Al1.07%,取0.2g含砷废渣于反应釜中,加入含有10%的过氧化氢,硫酸铝、硫酸钠浓度分别为0.08mol/L,0.08mol/L的混合溶液,使得固液比为1:80g/ml,调节pH=2,搅拌均匀后,将反应釜放入200℃下反应2h,自然冷却至室温。通过清洗浮选,最终分离得到黄色结块硫磺、砷钠明矾石固体,硫的回收率达到90%,其纯度超过96%;其砷的质量分数为5.64%,废渣的体积减容60%;砷的毒性浸出为0.26mg/L。
实施案例4
以某工业废水含砷废水硫化沉淀后产生的硫化砷渣为研究对象。全元素质量分析显示砷渣中主要元素有As 12.45%、S 11.09%、Na 13.76%、O 60.65%、Cu 1.68%、Si0.74%,取0.2g含砷废渣于反应釜中,加入含有10%的过氧化氢,硫酸铝、硫酸钠浓度分别为0.08mol/L,0.08mol/L的混合溶液,使得固液比为1:80g/ml,调节pH=1,搅拌均匀后,将反应釜放入200℃下反应2h,自然冷却至室温。通过清洗浮选,最终分离得到黄色结块硫磺、砷钠明矾石固体,硫的回收率达到90%,其纯度超过97%;其砷的质量分数为5.00%,废渣的体积减容80%;砷的毒性浸出为0.23mg/L。
同理,根据权利要求限定的保护范围和本说明书给出的技术解决方案,还能给出多个实施案例。对于本技术领域的普通技术和研究人员来说,在不脱离本发明原理和主体工艺的前提下,还可以做出若干改进和润饰,这些改进和润饰应视为本发明的保护范围。
Claims (3)
1.一种同步固化稳定化硫化砷渣和硫资源回收的方法,包括以下步骤:
(1)配置0.05~0.16mol/L硫酸铝、0.05-0.1mol/L硫酸钠、10%-15%过氧化氢的混合液,调节pH值为1~3并搅拌均匀;
(2)以固液比1:150~1:80g/ml将硫化砷渣加入到步骤(1)中的混合液,搅拌混合均匀;
(3)将步骤(2)中混合液移至高压反应釜中,在180~200℃温度下反应1.5~6小时后自然冷却至室温;
(4)反应后得到含砷滤渣、上清液、以及漂浮在上清液的黄色固体,分别将两种固体洗涤后干燥,得到黄色固体为单质硫和白色滤渣为砷钠明矾石。
2.如权利要求1所述的一种同步固化稳定化硫化砷渣和硫资源回收的方法,其特征在于:将混合液和含砷废渣在高压反应釜中水热处理,一步将砷渣固化稳定化并回收硫。
3.如权利要求1所述的一种同步固化稳定化硫化砷渣和硫资源回收的方法,其特征在于:所述含砷废渣物料是有色金属行业产生的高浓度含砷废酸或高浓度含砷电解液,通过沉淀工艺处理产生的。
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