CN112794510A - 一种无害化处理电解锰行业低浓度含锰氨氮废水的方法 - Google Patents
一种无害化处理电解锰行业低浓度含锰氨氮废水的方法 Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 50
- 239000011572 manganese Substances 0.000 title claims abstract description 50
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 21
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052741 iridium Inorganic materials 0.000 abstract description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical group [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
一种无害化处理电解锰行业低浓度含锰氨氮废水的方法,该方法是基于电催化氧化法技术,其特征在于阳极为镀钌铱的钛片,阴极为铜片。具体步骤如下:(1)将电解锰行业低浓度含锰氨氮废水排入无隔膜的电解槽内,在搅拌状态下,采用碱性药剂(生石灰、灼烧生料、氢氧化钠其中一种或多种)将废水pH调节至7.0~9.5,得到混合物A;(2)向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5~1h,得到混合物B;所述次氯酸钠与氨氮摩尔比为1:0.5~0.7,氯化钠与次氯酸钠摩尔比为0~1:1;(3)向混合物B体系中引入电流密度为5~25mA/cm2的电场,搅拌反应0.5~2h,反应液进行固液分离,滤渣可资源回收利用,滤液达到国家一级污水排放标准《GB8978‑1996》。与现有技术相比较,本发明具有流程简单、成本低、锰和氨氮去除率高、含氯中间产物少等优点。
Description
技术领域
本发明涉及电解锰行业低浓度含锰氨氮废水的处理方法。
背景技术
2018年我国电解锰渣生产量占世界的97%以上,电解金属生产过程将排放大量含有锰和氨氮的工业废水,这些废水排放到环境,将严重污染破坏当地生态系统。目前我国电解锰行业主要采用石灰沉淀法和吹脱方法处理高浓度含锰氨氮废水,处理后的废水中仍然含有低浓度锰和氨氮,这部分低浓度含锰氨氮废水再采用吹脱法和沉淀方法处理存在成本高、工艺复杂等问题。例如专利号201410069647.X,在电场作用下采用硝酸盐和亚硝酸盐处理电解锰废水,处理后废水达到国家排放标准,但该方法处理能耗较高;又如专利号CN201420525024.4,通过一种湿法电解锰生产过程中含锰废水的处理系统,该系统回收了废水中铵、锰等有价值物质,但是该方法主要针对高浓度锰和氨氮去除,对于低浓度含锰氨氮废水处理成本过高。专利号CN201620720017.9,涉及一种电解锰行业含氨氮废水处理系统,该系统操作简单方便、能耗低,滤后水能达标排放或根据需求回收利用,此外浓缩氨氮溶液能进行回收利用。专利号CN201420298955.5,公开了一种电解锰废水离子交换处理系统,该系统保证了设备的连续吸附,控制过程简单、稳定,能保证出水水质达标。
综上,目前针对高浓度含锰氨氮废水处理技术较为成熟,但是针对于低浓度含锰氨氮废水处理技术仍存在技术不成熟、成本高等一系列问题。本发明基于前期研究工作,开发出一种电场协同次氯酸根和氯离子同时去除废水中低浓度锰和氨氮的方法,其特点是阳极采用镀钌铱的钛极板,阴极采用铜板。此外相比传统含氯电催化氧化体系,本发明中锰主要以锰氧化沉淀方式进行去除,氨氮主要以氮气去除。总之,本发明具有流程简单、成本低、含氯中间产物少等优点。
发明内容
本发明主要是提供一种无害化处理电解锰行业低浓度含锰氨氮废水的方法,具体步骤如下:
(1)将电解锰行业低浓度含锰氨氮废水排入无隔膜的电解槽内,在搅拌状态下,采用碱性药剂(生石灰、灼烧生料、氢氧化钠其中一种或多种)将废水pH调节至7.0~9.5,得到混合物A;
(2)向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5~1h,得到混合物B;所述次氯酸钠与氨氮摩尔比为1:0.5~0.7,氯化钠与次氯酸钠摩尔比为0~1:1;
(3)向混合物B体系中引入电流密度为5~25mA/cm2的电场,搅拌反应0.5~2h,反应液进行固液分离,滤渣可资源回收利用,滤液达到国家一级污水排放标准。
本发明所使用的碱性药剂灼烧生料是指水泥生产过程中新型干法水泥回转窑分解炉的中间产物,主要成分是CaO(67~75%),SiO2(6~11%),SO3(3~5%),Al2O3(3~6%)以及Fe2O3(2~6%),相比工业级氧化钙,本发明使用的灼烧生料具有活性高,成本低等优势。
本发明的优势在于:电场作用下采用次氯酸钠和氯离子作为添加剂能够同时高效去除了废水中锰离子和氨氮,锰主要以锰氧化物进行资源回收利用,氨氮主要以氨气去除;此外,相比只有次氯酸钠或含有氯离子的电催化氧化体系,采用次氯酸钠和氯离子协同强化体系,能够同时高效去除废水中低浓度锰和氨氮的同时,废水中残留的余氯、总氯、硝酸根以及亚硝酸根含量均降低,且处理后废水中的锰离子、氨氮、余氯、总氯、硝酸根以及亚硝酸根浓度均达到国家一级废水排放标准。总之,本发明具有流程简单、成本低、锰和氨氮选择性去除率高、含氯中间产物少等优点,是电解锰企业废水处理处置的一项重要发明。
具体实施方式
实例1:
(1)将5L电解锰行业低浓度含锰氨氮废水(氨氮98mg/L,锰121mg/L)排入无隔膜的电解槽内,在搅拌状态下,采用生石灰,将废水pH调节至8.5,得到混合物A;
(2)向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5h,得到混合物B;添加的次氯酸钠与氨氮摩尔比为0.8:0.5,氯化钠与次氯酸钠摩尔比为1:1;
(3)向混合物B体系中引入电流密度为10mA/cm2的电场,搅拌反应1.5h,反应液进行固液分离,滤液中锰离子、氨氮、硝酸根、亚硝酸根、余氯和总氯达到国家一级污水排放标准《GB8978-1996》。
实例2:
(1)将5L电解锰行业低浓度含锰氨氮废水(氨氮98mg/L,锰121mg/L)排入无隔膜的电解槽内,在搅拌状态下,采用氢氧化钠,将废水pH调节至9.3,得到混合物A;
(2)向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5h,得到混合物B;添加的次氯酸钠与氨氮摩尔比为0.7:0.5,氯化钠与次氯酸钠摩尔比为0.5:1;
(3)向混合物B体系中引入电流密度为15mA/cm2的电场,搅拌反应1.5h,反应液进行固液分离,滤液中锰离子、氨氮、硝酸根、亚硝酸根、余氯和总氯达到国家一级污水排放标准《GB8978-1996》。
实例3:
(1)将5L电解锰行业低浓度含锰氨氮废水(氨氮98mg/L,锰121mg/L)排入无隔膜的电解槽内,在搅拌状态下,采用灼烧生料,将废水pH调节至9.5,得到混合物A;
(2)向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5h,得到混合物B;添加的次氯酸钠与氨氮摩尔量比为0.5:0.5,氯化钠与次氯酸钠摩尔比为1:1;
(3)向混合物B体系中引入电流密度为20 mA/cm2的电场,搅拌反应2 h,反应液进行固液分离,滤液中锰离子、氨氮、硝酸根、亚硝酸根、余氯和总氯达到国家一级污水排放标准《GB8978-1996》。
Claims (3)
1.将电解锰行业低浓度含锰氨氮废水排入无隔膜的电解槽内,在搅拌状态下,采用碱性药剂(生石灰、灼烧生料、氢氧化钠其中一种或多种)将废水pH调节至7.0~9.5,得到混合物A。
2.向混合物A中添加不同比例的次氯酸钠和氯化钠,搅拌反应0.5~1h,得到混合物B;所述次氯酸钠与氨氮摩尔比为1:0.5~0.7,氯化钠与次氯酸钠摩尔比为0~1:1。
3.向混合物B体系中引入电流密度为5~25mA/cm2的电场,搅拌反应0.5~2h,反应液进行固液分离,滤渣可资源回收利用,滤液达到国家一级污水排放标准《GB8978-1996》。与现有技术相比较,本发明具有流程简单、成本低、锰和氨氮去除率高、含氯中间产物少等优点。
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