CN100590077C - A method for preparing copper arsenite or copper arsenate from waste water containing arsenic - Google Patents
A method for preparing copper arsenite or copper arsenate from waste water containing arsenic Download PDFInfo
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- CN100590077C CN100590077C CN200610032456A CN200610032456A CN100590077C CN 100590077 C CN100590077 C CN 100590077C CN 200610032456 A CN200610032456 A CN 200610032456A CN 200610032456 A CN200610032456 A CN 200610032456A CN 100590077 C CN100590077 C CN 100590077C
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 53
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229940030341 copper arsenate Drugs 0.000 title abstract description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 11
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 11
- 239000004571 lime Substances 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000004062 sedimentation Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 3
- 229940073643 cupric arsenite Drugs 0.000 claims 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 24
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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Abstract
一种利用含砷废水制备亚砷酸铜或砷酸铜的方法，采用苛性碱或石灰调节含砷废水pH值，经过沉降、过滤、除杂得到滤液；按照铜砷物质量的比加入硫酸铜至滤液中，充分搅拌再加入苛性碱或石灰调节溶液pH值后过滤，得亚砷酸铜或砷酸铜。本发明直接利用含砷废水转化为具有重要用途的亚砷酸铜或砷酸铜，使含砷废水得到利用，既简化了亚砷酸铜或砷酸铜的制备工艺，降低亚砷酸铜或砷酸铜的制备成本，又解决了含砷废水的污染难题，经处理后的含砷废水中砷含量低于国家排放标准。大大降低了含砷废水的处理费用。A method for preparing copper arsenite or copper arsenate from arsenic-containing wastewater, using caustic soda or lime to adjust the pH value of arsenic-containing wastewater, and obtaining filtrate through sedimentation, filtration, and impurity removal; adding copper sulfate according to the ratio of copper to arsenic substances into the filtrate, fully stirred, then add caustic soda or lime to adjust the pH value of the solution, and then filter to obtain copper arsenite or copper arsenate. The present invention directly converts arsenic-containing wastewater into copper arsenite or copper arsenate with important uses, so that arsenic-containing wastewater can be utilized, which not only simplifies the preparation process of copper arsenite or copper arsenate, but also reduces the cost of copper arsenite or copper arsenate. The preparation cost of copper arsenate also solves the pollution problem of arsenic-containing wastewater, and the arsenic content in the treated arsenic-containing wastewater is lower than the national discharge standard. The treatment cost of arsenic-containing wastewater is greatly reduced.
Description
技术领域 technical field
本发明涉及一种含砷废水的回收与处理技术，特别是一种利用含砷废水制备亚砷酸铜或砷酸铜的方法。The invention relates to a recovery and treatment technology of arsenic-containing wastewater, in particular to a method for preparing copper arsenite or copper arsenate from arsenic-containing wastewater.
背景技术 Background technique
含砷废水中除含砷外，还含有其它重金属离子，不经处理直接排放将造成水污染。砷及其化合物是剧毒物质，人体中毒途径主要是通过饮用水及食物进入消化系统。近年来，随着矿冶、陶瓷、皮革、农药等行业的快速发展，砷对水质的污染日益严重。为了控制砷对水体的污染，我国规定废水排放标准砷≤0.5mg·L-1。Arsenic-containing wastewater contains not only arsenic, but also other heavy metal ions, and direct discharge without treatment will cause water pollution. Arsenic and its compounds are highly toxic substances. The main route of human poisoning is to enter the digestive system through drinking water and food. In recent years, with the rapid development of industries such as mining and metallurgy, ceramics, leather, and pesticides, the pollution of arsenic to water quality has become increasingly serious. In order to control the pollution of arsenic to water bodies, China stipulates that the wastewater discharge standard is ≤0.5mg·L -1 .
含砷废水可用于提取砷，是制备砷及砷的化合物。但目前对含砷废水的处理主要采用石灰法或石灰-铁盐法，使砷以不溶性盐沉淀下来，通过固液分离，达到净化废水的目的，该方法产生的大量废渣需要安全填埋，其费用高，由于环境的变化和细菌的作用，含砷废渣中的砷将会溶出，存在二次污染的隐患。Arsenic-containing wastewater can be used to extract arsenic, which is the preparation of arsenic and arsenic compounds. However, at present, the lime method or lime-iron salt method is mainly used for the treatment of arsenic-containing wastewater, so that the arsenic is precipitated as an insoluble salt, and the purpose of purifying the wastewater is achieved through solid-liquid separation. A large amount of waste generated by this method needs to be safely landfilled. The cost is high, and due to environmental changes and the action of bacteria, the arsenic in the arsenic-containing waste residue will be dissolved, and there is a hidden danger of secondary pollution.
中国专利94110419.2提出利用硫化亚铁沉降含砷废水中的砷制备硫化砷，但硫化砷只是一种中间物料，不能直接利用，需要经过转化才能制备类似砷酸铜、三氧化二砷等终态产品。Chinese patent 94110419.2 proposes to use ferrous sulfide to settle arsenic in arsenic-containing wastewater to prepare arsenic sulfide. However, arsenic sulfide is only an intermediate material and cannot be used directly. It needs to be converted to produce final products such as copper arsenate and arsenic trioxide.
发明内容 Contents of the invention
为了消除污染，本发明提出一种利用含砷废水直接制备亚砷酸铜及砷酸铜的方法。In order to eliminate pollution, the present invention proposes a method for directly preparing copper arsenite and copper arsenate by utilizing arsenic-containing wastewater.
一种利用含砷废水制备亚砷酸铜或砷酸铜的方法，采用苛性碱或石灰调节含砷废水pH值，经过沉降、过滤、除杂得到滤液；在0～100℃下，按照铜砷物质量的比0.5～5∶1加入硫酸铜至滤液中，充分搅拌再加入苛性碱或石灰，调节溶液pH值后过滤，用水洗涤滤渣，得亚砷酸铜或砷酸铜；滤液用苛性碱或石灰调节pH值，加入聚合硫酸铁或绿矾、聚合氯化铝絮凝处理后排放。A method for preparing copper arsenite or copper arsenate from arsenic-containing wastewater, using caustic soda or lime to adjust the pH value of arsenic-containing wastewater, and obtaining a filtrate through sedimentation, filtration, and impurity removal; Add copper sulfate to the filtrate at a material ratio of 0.5 to 5:1, stir well, then add caustic soda or lime, adjust the pH of the solution and filter, wash the filter residue with water to obtain copper arsenite or copper arsenate; use caustic soda for the filtrate Or lime to adjust the pH value, add polyferric sulfate or green vitriol, polyaluminum chloride for flocculation treatment and then discharge.
所述苛性碱为固体或溶液；所述石灰为固体或石灰乳；The caustic is solid or solution; the lime is solid or milk of lime;
所述硫酸铜为固体或溶液。The copper sulfate is solid or solution.
本发明直接利用含砷废水转化为具有重要用途的亚砷酸铜或砷酸铜，使含砷废水得到利用，既简化了亚砷酸铜或砷酸铜的制备工艺，降低亚砷酸铜或砷酸铜的制备成本，又解决了含砷废水的污染难题，经处理后的含砷废水中砷含量低于国家排放标准。大大降低了含砷废水的处理费用。The present invention directly converts arsenic-containing wastewater into copper arsenite or copper arsenate with important uses, so that arsenic-containing wastewater can be utilized, which not only simplifies the preparation process of copper arsenite or copper arsenate, but also reduces the cost of copper arsenite or copper arsenate. The preparation cost of copper arsenate also solves the pollution problem of arsenic-containing wastewater, and the arsenic content in the treated arsenic-containing wastewater is lower than the national discharge standard. The treatment cost of arsenic-containing wastewater is greatly reduced.
附图说明 Description of drawings
图1：本发明工艺流程示意图。Figure 1: Schematic diagram of the process flow of the present invention.
具体实施方式：Detailed ways:
实施例1Example 1
取某冶炼厂制硫酸时洗涤净化二氧化硫所得到的含砷污酸20L，其中含砷4.4g·L-1，用石灰300克调节溶液pH至6.0，搅拌反应1小时后过滤得到石膏渣和含砷溶液。Take 20L of arsenic-containing polluted acid obtained by washing and purifying sulfur dioxide when a smelter produces sulfuric acid, which contains 4.4g·L -1 of arsenic, adjust the pH of the solution to 6.0 with 300g of lime, stir and react for 1 hour, and filter to obtain gypsum slag and Arsenic solution.
在含砷溶液中加入400g五水硫酸铜，搅拌使其充分溶解，加入氢氧化钠调节溶液pH值为8.0，在此条件下搅拌反应0.5h使反应完全。Add 400g of copper sulfate pentahydrate to the arsenic-containing solution, stir to make it fully dissolved, add sodium hydroxide to adjust the pH of the solution to 8.0, and stir for 0.5h under this condition to complete the reaction.
静置浓密，抽取上层清液后过滤、洗涤得到绿色亚砷酸铜，于110℃下烘8h，得到干燥的亚砷酸铜。Let it stand for thickening, extract the supernatant, filter and wash to obtain green copper arsenite, and bake at 110°C for 8 hours to obtain dry copper arsenite.
用石灰乳调节提取砷后的含砷废水至pH＝7.0，采用聚合硫酸铁絮凝处理。处理后废水含砷为0.15mg·L-1，最终pH值为7.0左右。处理后，排放废水中砷含量为0.17mg·L-1，低于国家排放标准。The arsenic-containing wastewater after arsenic extraction is adjusted to pH=7.0 with milk of lime, and treated with polyferric sulfate flocculation. The arsenic content of the treated wastewater was 0.15 mg·L -1 , and the final pH value was about 7.0. After treatment, the arsenic content in the discharged wastewater was 0.17mg·L -1 , lower than the national discharge standard.
实施例2Example 2
取某冶炼厂制硫酸时洗涤净化二氧化硫所得到的含砷污酸2m3，其中含砷4.4g·L-1，用NaOH 30kg调节溶液pH至6.0，搅拌反应1小时后过滤得到滤渣和含砷溶液。Take 2m 3 of arsenic-containing polluted acid obtained by washing and purifying sulfur dioxide in a smeltery, which contains 4.4g·L -1 of arsenic, adjust the pH of the solution to 6.0 with 30kg of NaOH, stir and react for 1 hour, and filter to obtain filter residue and arsenic-containing solution.
在含砷溶液中加入5kg五水硫酸铜，搅拌使其充分溶解，加入氢氧化钠调节溶液pH值为8.0，在此条件下搅拌反应0.5h使反应完全。Add 5 kg of copper sulfate pentahydrate to the arsenic-containing solution, stir to make it fully dissolved, add sodium hydroxide to adjust the pH value of the solution to 8.0, and stir for 0.5 h under this condition to complete the reaction.
静置浓密，抽取上层清液后过滤、洗涤得到绿色亚砷酸铜，于110℃下烘8h，得到干燥的亚砷酸铜。Let it stand for thickening, extract the supernatant, filter and wash to obtain green copper arsenite, and bake at 110°C for 8 hours to obtain dry copper arsenite.
用石灰乳调节提取砷后的含砷废水至pH＝7.0，采用绿矾絮凝处理。处理后分析知废水含砷为0.22mg·L-1，最终pH值为7.0左右。处理后，排放废水中砷含量为0.17mg·L-1，低于国家排放标准。The arsenic-containing wastewater after extracting arsenic is adjusted to pH=7.0 with milk of lime, and flocculated with green vitriol. After treatment, the arsenic content in the wastewater was analyzed to be 0.22 mg·L -1 , and the final pH value was about 7.0. After treatment, the arsenic content in the discharged wastewater was 0.17mg·L -1 , lower than the national discharge standard.
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