CN109231859A - 一种含砷脱硫石膏渣资源化处理的方法 - Google Patents
一种含砷脱硫石膏渣资源化处理的方法 Download PDFInfo
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Abstract
本发明公开了一种含砷脱硫石膏渣资源化处理的方法,本发明将含砷脱硫石膏渣与石灰、铁矿渣混合后进行造球,得到含砷脱硫石膏渣球团,将含砷脱硫石膏渣球团进行微波活化,得到活化石膏渣,将活化石膏渣进行焙烧,焙烧过程中产生的烟尘用碱溶液吸收,焙烧后的尾渣排出后进行水淬得到水淬渣,水淬渣经粉碎得到矿粉,矿粉可用于制作水泥、免烧砖、加气砖等新型建筑材料,本发明有效实现了含砷脱硫石膏渣的资源化综合回收利用,促使含砷脱硫石膏渣由危险废物向一般II类工业固体废物转化,且同时获得了具有一定价值的水淬渣产品,本发明方法简单,易于操作,绿色环保,为含砷脱硫渣的处理提供了一条有效途径,具有广泛的应用前景。
Description
技术领域
本发明涉及一种含砷脱硫石膏渣资源化处理的方法,属于含重金属危险废物的治理技术领域。
背景技术
含砷脱硫石膏渣,又叫做砷钙渣,主要来源于有色金属冶炼及化工行业中,使用石灰、铁盐法处理含砷污酸时的产物,其主要组分是硫酸钙(CaSO4·2H2O),另外含有As、Cd、Pd、Cu、Zn、Hg、Se等重金属元素,属于危险固体废弃物,若不能加以有效处置,将会环境与资源造成二次污染,主要为对土壤、地下水资源等污染。据估计,中国铜冶炼行业每年要产生五十万吨左右的含砷石膏渣,而整个中国有色冶炼行业,历年堆存的含砷废料已达数千吨。含砷脱硫石膏渣(砷钙渣)的处理与处置成为社会关注度较高的课题。为此,工业和信息化部也制定了《工业和信息化部关于工业副产石膏综合利用的指导意见》,引导和鼓励相关企业推进副产石膏的综合利用。含砷石膏渣亟待进行无害化或资源化处理,意义重大。
目前国内处理含砷脱硫石膏渣(砷钙渣)的主要方法有:堆存、水泥固化、药剂固化和高温还原分解等方法。其中堆存是目前大部分企业最为常用的办法,但堆存对堆存渣场要求极高,而且后续的维护难度也相当大;水泥固化可将废渣的毒性浸出降低至满足国家毒性浸出要求的范围内,但存在体积增容比大,处理后的渣不能实现资源化利用;药剂固化目前适应性较差,仅在实验室针对部分原料开展实验工作,目前不能实现工业应用;高温还原分解方法因砷酸钙较为稳定,实际可操作性较差。故急需开发含砷脱硫石膏渣(砷钙渣)可资源化的处理新工艺。
发明内容
本发明的目的在于提供一种含砷脱硫石膏渣(砷钙渣)资源化处理的方法,本发明将含砷脱硫石膏渣(砷钙渣)与石灰、铁矿石等混合后,经造球、微波活化、焙烧、水淬工序处理后,得到水淬渣,水淬渣经粉碎后得到矿粉,矿粉可用于制作水泥、免烧砖、加气砖等新型建筑材料,本发明方法不仅解决了大量含砷脱硫石膏渣(砷钙渣)的堆存难、体积增容等问题,且制得了建筑材料,对环境友好。
本发明的技术方案是:一种含砷脱硫石膏渣资源化处理的方法,具体步骤如下:
(1)将含砷脱硫石膏渣与石灰、铁矿渣混合后进行造球,得到含砷脱硫石膏渣球团;
(2)将步骤(1)的含砷脱硫石膏渣球团进行微波活化,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣进行焙烧,焙烧过程中产生的烟尘用碱溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣粉碎后得到矿粉。
所述步骤(1)中含砷脱硫石膏渣与石灰的质量比为1:0.5~5。
所述步骤(1)造球所用设备为造球机。
所述步骤(2)中微波活化所用设备为微波反应器,微波活化的时间为5~30min,微波活化的频率为1~10GHz。
所述步骤(3)焙烧所用设备为回转窑、反射炉或烟化炉,焙烧的温度为700~1200℃,焙烧的时间为1~5h。
所述步骤(3)碱溶液为氢氧化钠、氢氧化钙、氢氧化钾中的一种或任意比几种的混合溶液。
与现有技术相比,本发明的有益效果是:
(1)本发明实现了含砷脱硫石膏渣(砷钙渣)的无害化处理,处理后砷等重金属经过高温烧结-水淬后,形成稳定的固化体。固化体经毒性浸出实验后,重金属的毒性浸出浓度均小于标准值,实现了由危险废物向一般II类工业固体废物转化。
(2)本发明有效实现了含砷脱硫石膏渣(砷钙渣)的资源化综合回收利用,产生的矿粉中含有铁、硅、钙等建筑材料所需原料,且经过高温烧结后,性质稳定,是建筑材料理想的原材料,可用作水泥、免烧砖、加气砖等新型建筑材料。
(3)本发明方法简单,易于操作,绿色环保,具有广泛的应用前景。
本发明通过将含砷脱硫石膏渣(砷钙渣)与石灰、铁矿渣混合,经造球、微波活化、焙烧、水淬处理后,实现了含砷脱硫石膏渣(砷钙渣)的“无害化、减量化、资源化”的目的,工艺绿色环保,同时具有较好的经济价值,为含砷脱硫渣的处理提供了一条有效途径。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合附图和实施例对本发明作进一步详细说明。
实施例1:本实施例对生产铜过程中使用石灰铁盐法处理的酸性废水得到的含砷石膏渣进行处理,如图1所示,具体步骤如下:
(1)将含砷石膏渣与与石灰、铁矿渣按照质量比为1:0.5:0.7的比例混合,然后置于造球机内进行造球,得到含砷脱砷石膏渣球团;
(2)将步骤(1)的含砷脱砷石膏渣球团置于微波反应器内进行微波活化,微波活化的时间为5 min,微波活化的频率为10 GHz,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣置于烟化炉内进行焙烧,焙烧的温度为700℃,焙烧的时间为5 h,焙烧过程中产生的烟尘用氢氧化钠溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣经粉碎得到矿粉,矿粉用于生产水泥。
经本方法处理后,解决了含砷脱硫石膏渣(砷钙渣)大量堆积对环境造成污染的问题,同时得到的矿粉可作为建筑材料用于生产水泥。
经检测,本实施例处理后的尾渣按照国家标准经毒性浸出试验,浸出液中砷浓度为0.48mg/L,由此可知,制得的水淬渣满足一般II类工业固体废物的要求,且粉碎后的矿粉用作建筑材料,实现了资源化利用。
实施例2:本实施例对冶炼铅过程中产生的含砷石膏渣进行处理,具体步骤如下:
(1)将含砷石膏渣与与石灰、铁矿粉按照质量比为1:2:0.4的比例混合,然后置于造球机内进行造球,得到含砷脱砷石膏渣球团;
(2)将步骤(1)的含砷脱砷石膏渣球团置于微波反应器内进行微波活化,微波活化的时间为10min,微波活化的频率为5 GHz,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣置于反射炉内进行焙烧,焙烧的温度为1000℃,焙烧的时间为3h,焙烧过程中产生的烟尘用氢氧化钙溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣经粉碎得到矿粉,矿粉可用于制作免烧砖。
经检测,本实施例处理后的尾渣按照国家标准经毒性浸出试验,浸出液中砷浓度为0.1mg/L,由此可知,制得的水淬渣无危害,且粉碎后的矿粉可用作建筑材料,实现了资源化利用。
实施例3:本实施例对冶炼锌过程中产生的含砷石膏渣进行处理,具体步骤如下:
(1)将含砷脱硫石膏渣与石灰、铁矿渣按照质量比为1:5:1的比例混合,然后置于造球机内进行造球,得到含砷脱砷石膏渣球团;
(2)将步骤(1)的含砷脱砷石膏渣球团置于微波反应器内进行微波活化,微波活化的时间为30min,微波活化的频率为1GHz,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣置于回转窑内进行焙烧,焙烧的温度为1200℃,焙烧的时间为1h,焙烧过程中产生的烟尘用氢氧化钾溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣经粉碎得到矿粉,矿粉用于加气砖的建筑材料。
经检测,本实施例处理后的尾渣按照国家标准经毒性浸出试验,浸出液中砷浓度为0.16mg/L,满足国家标准,制得的水淬渣无危害,且粉碎后的矿粉可用作建筑材料,实现了资源化利用。
实施例4:本实施例对冶炼锡过程中产生的含砷石膏渣进行处理,具体步骤如下:
(1)将含砷脱硫石膏渣与石灰、铁矿渣按照质量比为1:4:2的比例混合,然后置于造球机内进行造球,得到含砷脱砷石膏渣球团;
(2)将步骤(1)的含砷脱砷石膏渣球团置于微波反应器内进行微波活化,微波活化的时间为20min,微波活化的频率为6GHz,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣置于烟化炉内进行焙烧,焙烧的温度为1100℃,焙烧的时间为2h,焙烧过程中产生的烟尘用氢氧化钠与氢氧化钾按比例1:1混合后的混合溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣经粉碎得到矿粉,矿粉可用于制作加气砖。
经检测,本实施例处理后的尾渣按照国家标准经毒性进出试验,浸出液中砷浓度为0.15mg/L,满足国家标准,制得的水淬渣无危害,且粉碎后的矿粉可用作建筑材料,实现了资源化利用。
上面结合附图对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (6)
1.一种含砷脱硫石膏渣资源化处理的方法,其特征在于,具体步骤如下:
(1)将含砷脱硫石膏渣与石灰、铁矿渣混合后进行造球,得到含砷脱硫石膏渣球团;
(2)将步骤(1)的含砷脱硫石膏渣球团进行微波活化,得到活化石膏渣;
(3)将步骤(2)的活化石膏渣进行焙烧,焙烧过程中产生的烟尘用碱溶液吸收,焙烧后的尾渣进行水淬得到水淬渣,水淬渣经粉碎得到矿粉。
2.根据权利要求1所述的含砷脱硫石膏渣资源化处理的方法,其特征在于:所述步骤(1)中含砷脱硫石膏渣与石灰的质量比为1:0.5~5。
3.根据权利要求1所述的含砷脱硫石膏渣资源化处理的方法,其特征在于:所述步骤(1)造球所用设备为造球机。
4.根据权利要求1所述的含砷脱硫石膏渣资源化处理的方法,其特征在于:所述步骤(2)中微波活化所用设备为微波反应器,微波活化的时间为5~30min,微波活化的频率为1~10GHz。
5.根据权利要求1所述的含砷脱硫石膏渣资源化处理的方法,其特征在于:所述步骤(3)焙烧所用设备为回转窑、反射炉或烟化炉,焙烧的温度为700~1200℃,焙烧的时间为1~5h。
6.根据权利要求1所述的含砷脱硫石膏渣资源化处理的方法,其特征在于:所述步骤(3)碱溶液为氢氧化钠、氢氧化钙、氢氧化钾中的一种或任意比几种的混合溶液。
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