CN113716768A - 一种含铬含氰电镀废水的以废治废处理方法 - Google Patents
一种含铬含氰电镀废水的以废治废处理方法 Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 60
- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 34
- 238000009713 electroplating Methods 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000006228 supernatant Substances 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 238000007747 plating Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000006479 redox reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010812 mixed waste Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- ZFXTZKMYLJXJDY-UHFFFAOYSA-N copper;oxalonitrile Chemical compound [Cu].N#CC#N ZFXTZKMYLJXJDY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000925 very toxic Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C02F2101/18—Cyanides
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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Abstract
本发明提供了一种含铬含氰电镀废水的以废治废处理方法,包括:(a)按铬元素与铜元素的摩尔比=8~18:1,将酸性含铬电镀废水边搅拌边加入到镀铜的含氰废水中,超声进行氧化还原反应,静置沉降,分离后得到Cr(OH)3沉淀和上层清液;(b)在步骤(a)所得的上层清液中加入酸液直至pH<5,静置沉降,分离后得到Cu(I)沉淀和上层清液;(c)在步骤(b)所得上层清液中加入碱液直至pH为8.0‑8.5,沉降后得到Cu(OH)2和Cr(OH)3沉淀,所得的上层废液经检测合格后直接排放。本发明通过精准调节反应中组分含量及pH,超声激活氧化还原反应,以废治废,实现了镀铜、镀铬废水低成本处理及安全排放。
Description
技术领域
本发明涉及电镀废水处理技术领域,具体地说是涉及一种含铬含氰电镀废水的以废治废处理方法。
背景技术
镀铬废水呈酸性,pH=2~6;铬主要以Cr(VI)的形式存在,毒性大,对人体具有致癌和诱发基因突变的危险。传统的处理法是在pH=2~3条件下向废水中加入如亚硫酸氢钠、焦亚硫酸钠、亚硫酸钠等还原剂,使Cr(Ⅵ)还原为Cr(III),然后再加入强碱NaOH或絮凝剂,沉淀分离除去废水中Cr(Ⅲ)。此法的优点是处理含铬废水后能达标排放,可回收利用氢氧化铬,操作比较简单。但是,在应用的过程中处理量较大,会产生部分污泥,由于沉渣堆积会再次造成污染,且试剂费用高,成本较大。
在镀铜废水方面,为得到高质量的铜镀膜,通常要降低溶液中游离铜离子的浓度,因此镀铜液中需加入配位剂。CN-是镀铜溶液广泛使用的配位剂。因此镀铜废水中的主要污染物为氰和铜(I),溶液呈碱性pH=8~11。HCN的pKa=9.21,为防止pH<7时氰化物分解出剧毒氢氰酸。一般控制pH≥8时采用氧化破氰法,如液氯、次氯酸钠等碱性氧化剂将CN-破坏转化成CO2和N2,从而达到出去氰化物的目的。
公知的Cr(VI)和Cr(III)氧化还原半反应是:
Cr(VI)在强酸性介质中有氧化性,因此,在本领域中,Cr(VI)在pH≥8时没被考虑过是否可以选为处理CN-的氧化剂。有些技术人员甚至得出结论,两种电镀废水不能混合处理。现有技术中处理含氰废水以及电镀铬废水时,通常将两者分开处理后再混合,特别是对于本身既含有氰化物又含有六价铬的含氰电镀铬废水的处理工序更加繁琐,且除杂效率不高。综上可知,研究一种含铬含氰电镀废水的以废治废处理方法具有重要的现实意义。
发明内容
本发明的目的是提供一种含铬含氰电镀废水的以废治废处理方法,以解决现有技术中,含铬电镀废水和含氰电镀废水需分开处理,工序繁琐,效率低,成本高的问题。
本发明技术方案为:一种含铬含氰电镀废水的以废治废处理方法,包括以下步骤:
(a)按铬元素与铜元素的摩尔比=8~18:1,将酸性含铬电镀废水边搅拌边加入到镀铜的含氰废水中,超声条件下进行氧化还原反应20-70min,之后静置沉降5~12h,分离后得到Cr(OH)3沉淀和上层清液;
(b)在步骤(a)所得的上层清液中加入酸液直至pH<5,之后静置沉降5-12h,分离后得到Cu(I)沉淀和上层清液;
(c)在步骤(b)所得上层清液中加入碱液直至pH为7.5-8.5,沉降后得到Cu(OH)2和Cr(OH)3沉淀,所得的上层废液经检测合格后直接排放。
步骤(a)中,酸性含铬电镀废水与镀铜的含氰废水的混合废液pH为7.5-8.5。
步骤(b)中,所述酸液为硫酸。
步骤(c)中,所述碱液为NaOH溶液。
步骤(a)至(c)中,采用静置法分离沉淀。
本发明通过精准调节反应中组分含量及pH,超声激活氧化还原反应,以废治废,解决了现有技术中以多个工艺步骤来单独降低排放水中Cr(VI)和CN-的含量的问题,实现了镀铜、镀铬废水低成本处理及安全排放的矛盾统一,充分做到了废物回收利用,节能环保。本发明选用特定的酸液和碱液进行pH调节,避免对反应产生影响。
现有技术忽略了一个重要问题,Cr(OH)3的在溶液pH=6~10的范围内,Cr(III)主要以Cr(OH)3存在;pH=10时分布分数δ=0.995,即使高到pH=11时也可达到分布分数δ=0.95。所以在该区域内Cr(VI)和Cr(III)的氧化还原半反应应该为:
由于Cr(OH)3的形成降低了溶液中还原剂Cr3+的浓度,使得Cr(VI)/Cr(III)的电极电势值增大,即使在pH=8~10的范围内,Cr(VI)以CrO4 2-存在时氧化性依然较强。所以从热力学角度看,在弱碱性介质中混合CN-和Cr(VI)的电镀废液中,Cr(VI)完全可以氧化CN-。具体实施过程中需创造条件达到可适用的动力学条件。
具体实施方式
下面结合实施例对本发明做进一步的阐述,在下述实施例中未详细描述的过程和方法是本领域公知的常规方法,实施例中所用原料或试剂除另有说明外均为市售品,可通过商业渠道购得。本发明实施例中废水取自于江西省南昌市进贤县文港电镀集中工业区。
实施例1
将装有铜氰镀液废水600ml(pH=10.50,铜元素为3mmol/L)的1000ml烧杯放入超声清洗机中,然后边搅拌边加入40ml六价铬镀液废水(pH=2.19,总铬为9mmol/L),混合液pH=8.17,超声进行氧化还原反应70min,溶液为黄绿色,之后静置5h,沉出墨绿色沉淀。在所得的600ml上层清液(pH=8.53)中加0.6M的H2SO4溶液调节至pH=4,黄色退去,静置8h,沉出白色沉淀。上层清液用0.5M的NaOH溶液调节pH=8,沉出蓝绿色沉淀,经检测为氢氧化铬和氢氧化铜。上层清液无色透明,采用硝酸银滴定法(GB/T 7486-1987)测定上层清液中的CN-,其含量是0.1mg/L,采用原子吸收分光光度法方法测定上层清液中的总铬和总铜,其含量分别是0.5mg/L和0.3mg/L,均达到《电镀污染物排放标准》(GB21900-2008)排放标准。
实施例2
向装有氰铜镀液废水800ml(pH=11,铜元素为3.7mmol/L)的1000ml烧杯放入超声清洗机中,然后加入45ml六价铬镀液废水(pH=3,总铬为7.92mmol/L),混合液pH=7.5,超声进行氧化还原反应50min,溶液为黄绿色,之后静置12h,沉出墨绿色沉淀。在所得的800ml上层清液(pH=8)中加入0.6M的H2SO4溶液调节至pH=4,黄色退去,静置12h,沉出白色沉淀。所得上层清液用0.5M的NaOH溶液调节pH=8,沉出蓝绿色沉淀,经检测为氢氧化铬和氢氧化铜。上层清液无色透明,采用硝酸银滴定法(GB/T 7486-1987)测定上层清液中的CN-,其含量是0.2mg/L,原子吸收分光光度法方法测定上层清液中的总铬和总铜,其含量分别是0.8mg/L和0.4mg/L,均达到《电镀污染物排放标准》(GB21900-2008)排放标准。
Claims (5)
1.一种含铬含氰电镀废水的以废治废处理方法,其特征在于,包括以下步骤:
(a)按铬元素与铜元素的摩尔比=8~18:1,将酸性含铬电镀废水边搅拌边加入到镀铜的含氰废水中,超声条件下进行氧化还原反应20-70min,之后静置沉降5~12h,分离后得到Cr(OH)3沉淀和上层清液;
(b)在步骤(a)所得的上层清液中加入酸液直至pH<5,之后静置沉降5-12h,分离后得到Cu(I)沉淀和上层清液;
(c)在步骤(b)所得上层清液中加入碱液直至pH为8.0-8.5,沉降后得到Cu(OH)2和 Cr(OH)3沉淀,所得的上层废液经检测合格后直接排放。
2.根据权利要求1所述的含铬含氰电镀废水的以废治废处理方法,其特征在于,步骤(a)中,酸性含铬电镀废水与镀铜的含氰废水的混合废液pH为7.5-8.5。
3.根据权利要求1所述的含铬含氰电镀废水的以废治废处理方法,其特征在于,步骤(b)中,所述酸液为硫酸。
4.根据权利要求1所述的含铬含氰电镀废水的以废治废处理方法,其特征在于,步骤(c)中,所述碱液为NaOH溶液。
5.根据权利要求1所述的含铬含氰电镀废水的以废治废处理方法,其特征在于,步骤(a)至(c)中,采用静置法分离沉淀。
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