CN107512813B - 一种冶炼烟气制酸废水的多途径回收利用方法 - Google Patents
一种冶炼烟气制酸废水的多途径回收利用方法 Download PDFInfo
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
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- 238000010521 absorption reaction Methods 0.000 claims description 17
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
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- 238000002360 preparation method Methods 0.000 claims description 9
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- 238000007599 discharging Methods 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 2
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- 239000002244 precipitate Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
本发明公开了一种冶炼烟气制酸废水的多途径回收利用方法,属于化工技术领域。本发明首先利用净化系统内部循环浓缩的方法对酸性废水进行第一次减排,然后利用一次硫化、中和、二次硫化的工艺对酸性废水进行处理,依次去除酸水中重金属、砷、硫酸、铁和锌,再根据市场需求,既可通过冷却结晶生产七水硫酸镁,又可通过蒸发浓缩配制硫酸溶液,最终实现酸性废水零排放的目的。该工艺流程运行可靠,可通过两种不同的途径对酸水进行回收再利用;运行成本低,产生新的废弃物量较小,并可生产多种产品产生利润,不同阶段产生的渣均有不同的利用价值,真正实现了酸性废水多种途径回收利用的目的。
Description
技术领域
本发明属于化工技术领域,涉及有色金属冶炼中的废水处理,具体是一种冶炼烟气制酸废水的多途径回收利用方法。
背景技术
有色金属冶炼烟气制酸湿法净化洗涤过程中,会产生大量的酸性废水,常规的酸水处理工艺流程长、投资大,且会继续产生大量的废弃物,酸水处理运行成本过高,严重影响制酸成本。因此,亟需一种可减少净化酸水排放、降低酸水处理的投资和运行费用的方法。
发明内容
本发明的目的是为了解决上述技术问题,提供一种冶炼烟气制酸废水的多途径回收利用方法,以减少净化酸水排放、降低酸水处理的投资和运行费用。
为达到上述目的,本发明采用以下技术方案:一种冶炼烟气制酸废水多途径回收利用的方法,具体包括以下步骤:
A、将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排80-85%,一次压滤产出的铅渣回收提取铅;
B、将步骤A中一次清液输送至管式反应器与硫化钠溶液反应后进行脱气、二次压滤,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;
C、步骤B中二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,三次压滤产出的少量渣为废弃物;
D、步骤C中三次压滤产出的三次清液输送至管式反应器再次与硫化钠溶液反应后进行四次压滤,滤渣回收提取有价元素镉、铁、锌,四次清液采取以下任一回收方法回收利用:a、将所述四次清液经蒸发浓缩、冷却结晶后离心,沉淀物烘干,得到七水硫酸镁,作为化肥原料包装出售;b、将所述四次清液输送至绝热蒸发塔,同时将双转双吸制酸系统二吸塔出口烟气通过换热器与制酸转化工段出口高温烟气换热,换热后的热烟气送入绝热蒸发塔中与所述四次清液逆流接触,四次清液蒸发浓缩的同时,除去其中部分氟化氢和氯化氢气体,该气体经碱吸收达标后高空排放,浓缩液输送至配酸槽与制酸系统生产的98%的硫酸溶液混合后配制成一定浓度的硫酸溶液,入库装车出售。
上述步骤B和步骤D中,硫化钠溶液的质量体积浓度为10-12%,该浓度范围下硫化钠溶液加入量最小,避免了向酸性废中水另外填加水量,确保酸性废水排放量最小。
步骤B中,一次清液与硫化钠溶液的体积比为22-100:1,可确保酸性废水中铜元素的去除率达到100%,砷元素的去除率达到99%以上。
步骤C中,二次清液与氧化镁的体积质量比为15-48:1,可使三次压滤产出的三次清液基本呈中性,从而确保三次清液硫化过程中镉、铁和锌元素较高的去除率。
步骤D中,三次清液与硫化钠溶液的体积比为60-225:1,可确保酸性废水中镉元素的去除率达到98%以上,铁和锌元素的去除率达到99%以上。
本发明相比于现有技术具有以下有益效果:本发明首先利用净化系统内部循环浓缩的方法对酸性废水进行第一次减排,然后利用一次硫化、中和、二次硫化的工艺对酸性废水进行处理,依次去除酸水中重金属、砷、硫酸、铁和锌,再根据市场需求,既可通过冷却结晶生产七水硫酸镁,又可通过蒸发浓缩配制硫酸溶液,最终实现酸性废水零排放的目的。该工艺流程运行可靠,可通过两种不同的途径对酸水进行回收再利用;运行成本低,产生新的废弃物量较小,并可生产多种产品产生利润,不同阶段产生的渣均有不同的利用价值,真正实现了酸性废水多种途径回收利用的目的。
具体实施方式
下面结合具体实施例对本发明冶炼烟气制酸废水的多途径回收利用方法作进一步说明。
实施例1
将本发明冶炼烟气制酸废水多途径回收利用方法应用于某低浓度制酸废水(铜含量:106mg/L,铅含量:11.8mg/L,砷含量:486mg/L,酸度:43.71g/L,镉含量:36mg/L,铁含量:174mg/L,锌含量:508mg/L,氟含量:948.65 mg/L,氯含量:2.06 g/L,流量:15m3/h)的回收中,由于该酸性废水酸度较低,可采用蒸发浓缩配酸的方法进行回收利用,具体包括以下步骤:将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排85%,一次压滤产出的铅渣回收提取铅;一次清液输送至管式反应器与质量体积浓度为10%的硫化钠溶液反应后进行脱气、二次压滤,一次清液与硫化钠溶液的体积比为100:1,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,二次清液与氧化镁的体积质量比为48:1,三次压滤产出的少量渣为废弃物;三次压滤产出的三次清液输送至管式反应器再次与质量体积浓度为10%的硫化钠溶液反应后进行四次压滤,三次清液与硫化钠溶液的体积比为225:1,滤渣回收提取有价元素镉、铁、锌,四次清液(铜含量:未检出,铅含量:1.24mg/L,砷含量:0.32mg/L,镉含量:0.18mg/L,铁含量:1.58mg/L,锌含量:1.46mg/L,pH值:7.94)中重金属、铁、锌以及砷的含量已基本达标,输送至绝热蒸发塔,同时将双转双吸制酸系统二吸塔出口烟气通过换热器与制酸转化工段出口高温烟气换热,换热后的热烟气送入绝热蒸发塔中与四次清液逆流接触,四次清液蒸发浓缩的同时,带走部分氟化氢和氯化氢(氟含量:351.82mg/L,氯含量:1.17g/L)气体,该气体经尾气吸收塔通过碱吸收达标后高空排放,浓缩后浓度为30%的稀酸以6.4 m3/h的流量输送至配酸槽与制酸系统生产的98%的硫酸溶液混合,配制成93%硫酸溶液,入库装车出售。
实施例2
将本发明冶炼烟气制酸废水多途径回收利用方法应用于某低浓度制酸废水(铜含量:146.9mg/L,铅含量:9.62mg/L,砷含量:894mg/L,酸度:104g/L,镉含量:55.8mg/L,铁含量:184.6mg/L,锌含量:602mg/L,氟含量:1346.69 mg/L,氯含量:2.96 g/L,流量:18m3/h)的回收中,由于该酸性废水酸度较低,可采用蒸发浓缩配酸的方法进行回收利用,具体包括以下步骤:将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排83%,一次压滤产出的铅渣回收提取铅;一次清液输送至管式反应器与质量体积浓度为11%的硫化钠溶液反应后进行脱气、二次压滤,一次清液与硫化钠溶液的体积比为80:1,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,二次清液与氧化镁的体积质量比为35:1,三次压滤产出的少量渣为废弃物;三次压滤产出的三次清液输送至管式反应器再次与质量体积浓度为11%的硫化钠溶液反应后进行四次压滤,三次清液与硫化钠溶液的体积比为180:1,滤渣回收提取有价元素镉、铁、锌,四次清液(铜含量:<0.1 mg/L,铅含量:<0.1 mg/L,砷含量:0.6mg/L,镉含量:0.32mg/L,铁含量:0.81mg/L,锌含量:1.28mg/L,pH值:7.04)中重金属、铁、锌以及砷的含量已基本达标,输送至绝热蒸发塔,同时将双转双吸制酸系统二吸塔出口烟气通过换热器与制酸转化工段出口高温烟气换热,换热后的热烟气送入绝热蒸发塔中与四次清液逆流接触,四次清液蒸发浓缩的同时,带走部分氟化氢和氯化氢(氟含量:395.99mg/L,氯含量:1.21g/L)气体,该气体经尾气吸收塔通过碱吸收达标后高空排放,浓缩后浓度为30%的稀酸以8.1 m3/h的流量输送至配酸槽与制酸系统生产的98%的硫酸溶液混合,配制成93%硫酸溶液,入库装车出售。
实施例3
将本发明冶炼烟气制酸废水多途径回收利用方法,另应用于某高浓度制酸废水(铜含量:496mg/L,铅含量:11.3mg/L,砷含量:1604mg/L,酸度:165.6g/L,镉含量:61.8mg/L,铁含量:258mg/L,锌含量:502mg/L,氟含量:3144.93 mg/L,氯含量:5.4 g/L,流量:15m3/h)的回收中,由于酸水酸度较高,且氟、氯含量也较高,因此采用蒸发冷却结晶的方法进行回收,具体包括以下步骤:将制酸净化产生的酸性废水通过在净化工序体内进行循环浓缩后,将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排80%,一次压滤产出的铅渣回收提取铅;一次清液输送至管式反应器与质量体积浓度为12%的硫化钠溶液反应后进行脱气、二次压滤,一次清液与硫化钠溶液的体积比为22:1,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,二次清液与氧化镁的体积质量比为15:1,三次压滤产出的少量渣为废弃物;三次压滤产出的三次清液输送至管式反应器再次与质量体积浓度为12%的硫化钠溶液反应后进行四次压滤,三次清液与硫化钠溶液的体积比为60:1,滤渣回收提取有价元素镉、铁、锌,四次清液(铜含量:<0.1mg/L,铅含量:<0.1 mg/L,砷含量:<0.1 mg/L,镉含量:0.75mg/L,铁含量:0.58mg/L,锌含量:1.92mg/L,pH值:7.5)中重金属、铁、锌以及砷的含量已基本达标,其中硫酸镁含量达234g/L,输送至蒸发器蒸发浓缩后,进入结晶罐进行冷却降温结晶,再通过离心分离机分离、烘干机烘干后,得到七水硫酸镁产品6.2t/h,作为化肥原料包装出售。
实施例4
将本发明冶炼烟气制酸废水多途径回收利用方法,同样应用于某高浓度制酸废水(铜含量:266mg/L,铅含量:8mg/L,砷含量:1304mg/L,酸度:106g/L,镉含量:63.2mg/L,铁含量:180mg/L,锌含量:480mg/L,氟含量:2889.19 mg/L,氯含量:3.26g/L,流量:18m3/h)的回收中,由于酸水酸度较高,且氟、氯含量也较高,因此采用蒸发冷却结晶的方法进行回收,具体包括以下步骤:将制酸净化产生的酸性废水通过在净化工序体内进行循环浓缩后,将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排81%,一次压滤产出的铅渣回收提取铅;一次清液输送至管式反应器与质量体积浓度为12%的硫化钠溶液反应后进行脱气、二次压滤,一次清液与硫化钠溶液的体积比为45:1,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,二次清液与氧化镁的体积质量比为30:1,三次压滤产出的少量渣为废弃物;三次压滤产出的三次清液输送至管式反应器再次与质量体积浓度为12%的硫化钠溶液反应后进行四次压滤,三次清液与硫化钠溶液的体积比为120:1,滤渣回收提取有价元素镉、铁、锌,四次清液(铜含量:<0.1 mg/L,铅含量:<0.1 mg/L,砷含量:<0.1 mg/L,镉含量:0.67mg/L,铁含量:0.48mg/L,锌含量:1.33mg/L,pH值:7.45)中重金属、铁、锌以及砷的含量已基本达标,其中硫酸镁含量达149g/L,输送至蒸发器蒸发浓缩后,进入结晶罐进行冷却降温结晶,再通过离心分离机分离、烘干机烘干后,得到七水硫酸镁产品5.5t/h,作为化肥原料包装出售。
Claims (2)
1.一种冶炼烟气制酸废水的多途径回收利用方法,其特征在于,该方法包括以下步骤:
A、将净化洗涤产生的酸性废水在净化系统内部进行循环浓缩、一次压滤,一次清液减排80-85%,一次压滤产出的铅渣回收提取铅;
B、将步骤A中一次清液输送至管式反应器与硫化钠溶液反应后进行脱气、二次压滤,脱除的硫化氢气体经碱吸收达标后高空排放,二次压滤产出的铜砷渣回收提取铜和砷;所述一次清液与硫化钠溶液的体积比为22-100:1;
C、步骤B中二次压滤产出的二次清液进入中和反应罐与氧化镁发生中和反应后进行三次压滤,三次压滤产出的渣为废弃物;
D、步骤C中三次压滤产出的三次清液输送至管式反应器再次与硫化钠溶液反应后进行四次压滤,滤渣回收提取有价元素镉、铁、锌,四次清液采取以下任一回收方法回收利用:a、将所述四次清液经蒸发浓缩、冷却结晶后离心,沉淀物烘干,得到七水硫酸镁,作为化肥原料包装出售;b、将所述四次清液输送至绝热蒸发塔,同时将双转双吸制酸系统二吸塔出口烟气通过换热器与制酸转化工段出口高温烟气换热,换热后的热烟气送入绝热蒸发塔中与所述四次清液逆流接触,四次清液蒸发浓缩的同时,除去其中部分氟化氢和氯化氢气体,该气体经碱吸收达标后高空排放,浓缩液输送至配酸槽与制酸系统生产的98%硫酸溶液混合后配制成硫酸溶液,入库装车出售;所述三次清液与硫化钠溶液的体积比为60-225:1;
步骤B和步骤D中,所述硫化钠溶液的质量体积浓度为10-12%。
2.根据权利要求1所述的一种冶炼烟气制酸废水的多途径回收利用方法,其特征在于:步骤C中,所述二次清液与氧化镁的体积质量比为15-48:1。
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