WO2021093491A1 - Method for electric field enhanced harmless treatment of electrolytic manganese residue - Google Patents
Method for electric field enhanced harmless treatment of electrolytic manganese residue Download PDFInfo
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- WO2021093491A1 WO2021093491A1 PCT/CN2020/120186 CN2020120186W WO2021093491A1 WO 2021093491 A1 WO2021093491 A1 WO 2021093491A1 CN 2020120186 W CN2020120186 W CN 2020120186W WO 2021093491 A1 WO2021093491 A1 WO 2021093491A1
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- Prior art keywords
- electrolytic manganese
- filtrate
- manganese slag
- electric field
- slurry system
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000005684 electric field Effects 0.000 title claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 44
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 5
- 235000012054 meals Nutrition 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Definitions
- the invention relates to the field of the harmless treatment of solid waste, and is a method for enhancing the harmless treatment of electrolytic manganese slag by an electric field.
- Electrolytic manganese slag is the acidic residue produced after acid leaching, neutralization, and filter press in the process of producing metal manganese by electrolysis. Due to historical and technical reasons, most of the electrolytic manganese slag in my country is currently stored in open air. The electrolytic manganese slag is washed by rain or naturally infiltrated during the storage process, forming a large amount of leachate. The leachate contains high concentrations of manganese ( 1000 ⁇ 3000mg/L) and ammonia nitrogen (500 ⁇ 2000mg/L), once these pollutants enter the environment, they will seriously threaten the surrounding ecological environment.
- Sodium hypochlorite is a strong alkaline oxidizing agent, it can be oxidized to form manganese oxide of manganese ions precipitate principle is related reactions H 2 O + Mn 2+ + ClO - ⁇ MnO 2 + Cl - + 2H +; sodium hypochlorite can be oxidized and removed in addition ammonia, and its main principle is the reaction 3ClO - + 2NH 4 + ⁇ N 2 + 3Cl - + H 2 O + 2H +.
- the addition of sodium hypochlorite can speed up the reaction rate, shorten the treatment time, and has a significant treatment effect, which greatly improves the removal efficiency of manganese and ammonia nitrogen.
- excessive sodium hypochlorite is added, a large amount of by-products such as nitrate, nitrite, residual chlorine and free chlorine will remain in the wastewater, causing serious secondary pollution.
- DSA electrode is the focus of electrocatalytic oxidation reaction.
- Ti-based lead oxide, iridium oxide, tin antimony oxide and other electrodes are currently valuable DSA electrodes.
- This patent uses the Ti/RuO 2 -IrO 2 electrode as the anode, and the Cu electrode plate mainly reduces nitrate to ammonia nitrogen, which is then oxidized by sodium hypochlorite to form nitrogen and be removed.
- NH 4 + -N can be oxidized directly or indirectly.
- Direct oxidation means that NH 4 + is adsorbed on the anode surface and is directly oxidized to form N 2 ; indirect oxidation means that Cl - is oxidized to ClO - or HClO in the presence of chloride ions, and then oxidized to remove ammonia nitrogen.
- the invention firstly uses alkaline materials to remove high-concentration ammonia nitrogen and manganese in the electrolytic manganese slag leachate, and reduces the cost of strengthening the removal of manganese and ammonia nitrogen in the back-end electric field intensified leachate wastewater.
- the present invention uses DSA material as the anode plate and copper plate as the cathode plate, which has excellent electrocatalytic oxidation ability and can further cooperate with hypochlorite to enhance the efficient removal of manganese and ammonia nitrogen in the leachate.
- alkaline materials to adjust the pH of the slurry system 1# to ensure that the pH of the slurry is maintained at 8.5-11.5 to obtain slurry system 2#;
- the alkaline material is 0.2-2.0 parts by weight of the burning raw meal, 0.2-2.0 One or more parts by weight of calcium oxide and 0.5 to 2.0 parts by weight of low-grade magnesium oxide;
- the burning raw meal refers to the intermediate product of the new type dry cement rotary kiln decomposition furnace in the cement production process. Its main components are CaO (67-75%), SiO 2 (6-11%), SO 3 (3 ⁇ 5%), Al 2 O 3 (3 ⁇ 6%) and Fe 2 O 3 (2 ⁇ 6%). Compared with industrial grade calcium oxide, the burning raw meal used in the present invention has the advantages of high activity and low cost. .
- Fig. 1 is a process flow diagram of a method for enhancing the harmless treatment of electrolytic manganese slag provided by the present invention.
- FIG. 1 The flow chart of a method for enhancing the harmless treatment of electrolytic manganese slag provided by the present invention is shown in Fig. 1.
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Disclosed is a method for electric field enhanced harmless treatment of an electrolytic manganese residue. The method involves firstly fully mixing an electrolytic manganese residue with water in a certain proportion to obtain a mixed ore pulp; then adjusting the pH of the ore pulp system with a basic material, aerating the ore pulp system for a period of time, and then subjecting same to a solid-liquid separation, wherein the filter residue can be resourcefully utilized, and overflowing gas is absorbed by dilute sulfuric acid; and finally, adding sodium hypochlorite to the filtrate and applying an electric field, sufficiently reacting same for a period of time, and then subjecting same to a solid-liquid separation, wherein the filtrate is used for the leaching of the next batch of electrolytic manganese residue. The method has the advantages such as being completely harmless, a simple process, a high removal rate for manganese and ammonia nitrogen, and producing less by-products.
Description
本发明涉及固体废物无害化处理领域，是一种电场强化电解锰渣无害化处理的方法。The invention relates to the field of the harmless treatment of solid waste, and is a method for enhancing the harmless treatment of electrolytic manganese slag by an electric field.
电解锰渣是电解法生产金属锰的过程中经酸浸、中和、压滤工序后产生的酸性残渣。由于历史与技术原因，目前我国电解锰渣现多为露天堆存排放，电解锰渣在堆存过程中被雨水冲刷或自然渗透，形成了大量的渗滤液，渗滤液中含有高浓度的锰(1000～3000mg/L)和氨氮(500～2000mg/L)，这些污染物一旦进入环境将严重威胁周边生态环境。Electrolytic manganese slag is the acidic residue produced after acid leaching, neutralization, and filter press in the process of producing metal manganese by electrolysis. Due to historical and technical reasons, most of the electrolytic manganese slag in my country is currently stored in open air. The electrolytic manganese slag is washed by rain or naturally infiltrated during the storage process, forming a large amount of leachate. The leachate contains high concentrations of manganese ( 1000～3000mg/L) and ammonia nitrogen (500～2000mg/L), once these pollutants enter the environment, they will seriously threaten the surrounding ecological environment.
至今，国内外学者对电解锰渣的无害化处理开展了大量的研究工作，其中主要包括硫酸回浸法、生物还原浸取法、逆流洗涤法、清水洗涤—铵盐沉淀法等方法。陶金晶等人提出了一种电解锰渣渗滤液无害化处理的方法(申请号：201610528699.8)，该方法对环境的二次污染小，操作简单，但反应效率仍有待提高。曹兴提出的一种电解锰渣无害化处理方法(申请号：201811585423.9)，该方法经济效益高，对环境的二次污染小，但对电解锰渣中氨氮和锰没有进行预处理，影响电解锰渣后续资源化利用。王毅提出的一种处理电解锰渣无害化的方法(申请号：201710916632.6)，该方法处理效果好，对环境污染小，处理后的锰渣能够直接用于农业。So far, domestic and foreign scholars have carried out a lot of research work on the harmless treatment of electrolytic manganese slag, which mainly include sulfuric acid back leaching method, biological reduction leaching method, countercurrent washing method, clean water washing-ammonium salt precipitation method and other methods. Tao Jinjing et al. proposed a method for the harmless treatment of electrolytic manganese slag leachate (application number: 201610528699.8). This method has little secondary pollution to the environment and is simple to operate, but the reaction efficiency still needs to be improved. Cao Xing proposed a harmless treatment method for electrolytic manganese slag (application number: 201811585423.9). This method has high economic benefits and small secondary pollution to the environment, but it does not pre-treat the ammonia nitrogen and manganese in the electrolytic manganese slag. Follow-up resource utilization of electrolytic manganese slag. Wang Yi proposed a method for harmless treatment of electrolytic manganese slag (application number: 201710916632.6), which has good treatment effect and low environmental pollution, and the treated manganese slag can be directly used in agriculture.
次氯酸钠是一种碱性强氧化剂，它能够将锰离子氧化形成锰氧化物沉淀，相关反应原理为H
2O+Mn
2++ClO
-→MnO
2+Cl
-+2H
+；此外次氯酸钠能够氧化去除氨氮，其主要反应原理为3ClO
-+2NH
4
+→N
2+3Cl
-+H
2O+2H
+。添加次氯酸钠可加快反应速率，缩短处理的时间，且处理效果显著，极大地提高了锰和氨氮的去除效率。然而添加过量的次氯酸钠，废水中将残留大量的硝酸盐，亚硝酸盐、残余氯以及游离氯等副产物，造成严重的二次污染。
Sodium hypochlorite is a strong alkaline oxidizing agent, it can be oxidized to form manganese oxide of manganese ions precipitate principle is related reactions H 2 O + Mn 2+ + ClO - → MnO 2 + Cl - + 2H +; sodium hypochlorite can be oxidized and removed in addition ammonia, and its main principle is the reaction 3ClO - + 2NH 4 + → N 2 + 3Cl - + H 2 O + 2H +. The addition of sodium hypochlorite can speed up the reaction rate, shorten the treatment time, and has a significant treatment effect, which greatly improves the removal efficiency of manganese and ammonia nitrogen. However, if excessive sodium hypochlorite is added, a large amount of by-products such as nitrate, nitrite, residual chlorine and free chlorine will remain in the wastewater, causing serious secondary pollution.
DSA电极是当今电催化氧化反应的重点，Ti基氧化铅、氧化铱、锡锑氧化物等电极是目前有研究价值的DSA电极。本专利将Ti/RuO
2-IrO
2电极作为阳极，Cu极板主要将硝酸根还原成氨氮，氨氮再被次氯酸钠氧化形成氮气去除。在水溶液中，NH
4
+-N可以通过直接或间接的方式氧化。直接氧化是指NH
4
+被吸附到阳极表面被直接氧化形成N
2；间接氧化是指在氯离子存在下，Cl
-被氧化成ClO
-或HClO等氧化物，再氧化去除氨氮。
DSA electrode is the focus of electrocatalytic oxidation reaction. Ti-based lead oxide, iridium oxide, tin antimony oxide and other electrodes are currently valuable DSA electrodes. This patent uses the Ti/RuO 2 -IrO 2 electrode as the anode, and the Cu electrode plate mainly reduces nitrate to ammonia nitrogen, which is then oxidized by sodium hypochlorite to form nitrogen and be removed. In an aqueous solution, NH 4 + -N can be oxidized directly or indirectly. Direct oxidation means that NH 4 + is adsorbed on the anode surface and is directly oxidized to form N 2 ; indirect oxidation means that Cl - is oxidized to ClO - or HClO in the presence of chloride ions, and then oxidized to remove ammonia nitrogen.
目前电解锰渣的无害化处理研究，仍存在处理能力低、锰和氨氮处理不彻底、处理后副产物多等问题。因此，寻找一种处理能力高、副产物少、成本低且符合可持续发展的方法是当务之急。The current research on the harmless treatment of electrolytic manganese slag still has problems such as low treatment capacity, incomplete treatment of manganese and ammonia nitrogen, and many by-products after treatment. Therefore, it is imperative to find a method with high processing capacity, few by-products, low cost and in line with sustainable development.
发明内容Summary of the invention
本发明首先利用碱性物料将电解锰渣渗滤液中的高浓度氨氮和锰去除，降低了后端电场强化渗滤液废水中锰和氨氮去除的成本。此外，本发明采用DSA材料为阳极板，铜板为阴极板，其拥有优良的电催化氧化能力，能够进一步协同次氯酸根强化渗滤液中锰和氨氮的高效去除。The invention firstly uses alkaline materials to remove high-concentration ammonia nitrogen and manganese in the electrolytic manganese slag leachate, and reduces the cost of strengthening the removal of manganese and ammonia nitrogen in the back-end electric field intensified leachate wastewater. In addition, the present invention uses DSA material as the anode plate and copper plate as the cathode plate, which has excellent electrocatalytic oxidation ability and can further cooperate with hypochlorite to enhance the efficient removal of manganese and ammonia nitrogen in the leachate.
一种电场强化电解锰渣无害化处理的方法，该方法步骤如下：An electric field-enhanced method for the harmless treatment of electrolytic manganese slag. The steps of the method are as follows:
(1)将电解锰渣与水按照一定质量比进行均匀混合，得到矿浆体系1#；其中电解锰渣与水按照质量比＝1：5～10混合；(1) The electrolytic manganese slag and water are uniformly mixed according to a certain mass ratio to obtain slurry system 1#; wherein the electrolytic manganese slag and water are mixed according to the mass ratio=1:5-10;
(2)采用碱性物料调节矿浆体系1#pH，确保浆体pH值维持在8.5～11.5，得到矿浆体系2#；其中碱性物料为0.2～2.0重量份的灼烧生料，0.2～2.0重量份的氧化钙，0.5～2.0重量份的低品位氧化镁其中一种或者多种；(2) Use alkaline materials to adjust the pH of the slurry system 1# to ensure that the pH of the slurry is maintained at 8.5-11.5 to obtain slurry system 2#; the alkaline material is 0.2-2.0 parts by weight of the burning raw meal, 0.2-2.0 One or more parts by weight of calcium oxide and 0.5 to 2.0 parts by weight of low-grade magnesium oxide;
(3)向矿浆体系2#中曝气1～4h，采用稀硫酸收集溢出的气体，通过板框压滤进行固液分离，得到滤渣和滤液3#，滤渣可进行资源化利用；其中曝气的液气比为0.38～0.85，稀硫酸的质量比为15％～30％。(3) Aerate the slurry system 2# for 1～4h, collect the overflowing gas with dilute sulfuric acid, and separate the solid-liquid through plate and frame filter press to obtain filter residue and filtrate 3#. The filter residue can be used as resources; among them, aeration The liquid to gas ratio is 0.38 to 0.85, and the mass ratio of dilute sulfuric acid is 15% to 30%.
(4)向滤液3#中添加体积比为0.1％～1.0％的次氯酸钠溶液，并引入电流密度为0～40mA/cm
2的电场，反应1～3h后，通过板框压滤进行固液分离，得到滤液4#。
(4) # 3 was added to the filtrate in a volume ratio of 0.1 to 1.0% sodium hypochlorite solution, and the introduction of electric current density is 0 ~ 40mA / cm 2, and after the reaction is 1 ~ 3h, solid-liquid separation by a frame filter press , To obtain filtrate 4#.
(5)将得到的滤液4#循环用于下一批电解锰渣浸出。(5) Recycle the obtained filtrate 4# for the next batch of electrolytic manganese slag leaching.
本发明中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，其主要成分是CaO(67～75％)，SiO
2(6～11％)，SO
3(3～5％)，Al
2O
3(3～6％)以及Fe
2O
3(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。
In the present invention, the burning raw meal refers to the intermediate product of the new type dry cement rotary kiln decomposition furnace in the cement production process. Its main components are CaO (67-75%), SiO 2 (6-11%), SO 3 (3 ～5%), Al 2 O 3 (3～6%) and Fe 2 O 3 (2～6%). Compared with industrial grade calcium oxide, the burning raw meal used in the present invention has the advantages of high activity and low cost. .
图1是本发明提供的一种电场强化电解锰渣无害化处理的方法工艺流程图。Fig. 1 is a process flow diagram of a method for enhancing the harmless treatment of electrolytic manganese slag provided by the present invention.
本发明提供的一种电场强化电解锰渣无害化处理的方法流程见图1。The flow chart of a method for enhancing the harmless treatment of electrolytic manganese slag provided by the present invention is shown in Fig. 1.
实例1：Example 1:
(1)取电解锰渣20kg与水200kg均匀混合，得到矿浆体系1#；该体系中测得锰含量为2800mg/L，氨氮含量为2994mg/L，均超过《综合污水排放标准》(GB 8978—1996)所规定的排放阈值数倍。(1) Take 20kg of electrolytic manganese slag and 200kg of water and mix uniformly to obtain slurry system 1#; the measured manganese content in this system is 2800mg/L, and the ammonia nitrogen content is 2994mg/L, both of which exceed the "Comprehensive Wastewater Discharge Standard" (GB 8978). —1996) multiples of the emission threshold specified.
(2)采用2重量份的氢氧化钠调节矿浆体系1#pH，确保浆体pH值维持在11.0，得到矿浆体系2#；(2) Use 2 parts by weight of sodium hydroxide to adjust the pH of the slurry system 1# to ensure that the pH of the slurry is maintained at 11.0 to obtain slurry system 2#;
(3)向矿浆体系2#中曝气3h，其中曝气的液气比为0.55，溢出的气体采用浓度为30％ 的稀硫酸收集，通过板框压滤进行固液分离，得到压滤渣和滤液3#，滤渣可进行资源化利用；(3) Aerate into the slurry system 2# for 3 hours, in which the liquid-to-air ratio of the aeration is 0.55, and the overflowing gas is collected by dilute sulfuric acid with a concentration of 30%, and solid-liquid separation is carried out by plate and frame filter press to obtain filter press residue and Filtrate 3#, the filter residue can be used as resources;
(4)向滤液3#中添加0.8％的次氯酸钠溶液，并加入电流密度为25mA/cm
2的电场，反应2h，通过板框压滤进行固液分离，得到滤液4#。
(4) 0.8% sodium hypochlorite solution was added to the filtrate, # 3, and adding electric current density of 25mA / cm 2, the reaction 2h, solid-liquid separation by a frame filter press to give a filtrate # 4.
(5)将得到的滤液4#循环用于下一批电解锰渣浸。经过处理后，渗滤液pH值为7.6，其中的锰含量为1.5mg/L，氨氮为10mg/L，均达到《综合污水排放标准》(GB 8978—1996)所规定的一级排放标准。(5) Recycle the obtained filtrate 4# for the next batch of electrolytic manganese slag leaching. After treatment, the pH value of the leachate was 7.6, the manganese content was 1.5mg/L, and the ammonia nitrogen was 10mg/L, both of which reached the first-level discharge standard stipulated in the "Comprehensive Wastewater Discharge Standard" (GB 8978-1996).
实例2：Example 2:
(1)取电解锰渣20kg与水200kg均匀混合，得到矿浆体系1#；该体系中测得锰含量为2800mg/L，氨氮含量为2994mg/L，均超过《综合污水排放标准》(GB 8978—1996)所规定的排放阈值数倍。(1) Take 20kg of electrolytic manganese slag and 200kg of water and mix uniformly to obtain slurry system 1#; the measured manganese content in this system is 2800mg/L, and the ammonia nitrogen content is 2994mg/L, both of which exceed the "Comprehensive Wastewater Discharge Standard" (GB 8978). —1996) multiples of the emission threshold specified.
(2)采用2重量份的灼烧生料调节矿浆体系1#pH，确保浆体pH值维持在10.5，得到矿浆体系2#；(2) Adjust the pH of the slurry system 1# by using 2 parts by weight of burning raw meal to ensure that the pH value of the slurry is maintained at 10.5 to obtain the slurry system 2#;
(3)向矿浆体系2#中曝气3h，其中曝气的液气比为0.65，溢出的气体采用浓度为30％的稀硫酸收集，通过板框压滤进行固液分离，得到压滤渣和滤液3#，滤渣可进行资源化利用；(3) Aerate into the slurry system 2# for 3 hours, in which the liquid-to-air ratio of the aeration is 0.65, and the overflowing gas is collected by dilute sulfuric acid with a concentration of 30%, and solid-liquid separation is carried out through plate and frame filter press to obtain filter press residue and Filtrate 3#, the filter residue can be used as resources;
(4)向滤液3#中添加0.7％的次氯酸钠溶液，并加入电流密度为35mA/cm
2的电场，反应3h，通过板框压滤进行固液分离，得到滤液4#。
(4) 0.7% solution of sodium hypochlorite was added to the filtrate, # 3, and adding electric current density of 35mA / cm 2, the reaction 3h, solid-liquid separation by a frame filter press to give a filtrate # 4.
(5)将得到的滤液4#循环用于下一批电解锰渣浸。经过处理后，渗滤液pH值为9.14，其中的锰含量为0.8mg/L，氨氮为5mg/L，均达到《综合污水排放标准》(GB 8978—1996)所规定的一级排放标准。(5) Recycle the obtained filtrate 4# for the next batch of electrolytic manganese slag leaching. After treatment, the pH value of the leachate was 9.14, the manganese content was 0.8mg/L, and the ammonia nitrogen was 5mg/L, both of which reached the first-level discharge standard stipulated in the "Comprehensive Wastewater Discharge Standard" (GB 8978-1996).
实例3：Example 3:
(1)取电解锰渣20kg与水200kg均匀混合，得到矿浆体系1#；该体系中测得锰含量为2800mg/L，氨氮含量为2994mg/L，均超过《综合污水排放标准》(GB 8978—1996)所规定的排放阈值数倍。(1) Take 20kg of electrolytic manganese slag and 200kg of water and mix evenly to obtain slurry system 1#; the measured manganese content in this system is 2800mg/L, and the ammonia nitrogen content is 2994mg/L, both of which exceed the "Comprehensive Wastewater Discharge Standard" (GB 8978). —1996) the emission threshold specified in several times.
(2)采用2重量份的氢氧化钠调节矿浆体系1#pH，确保浆体pH值维持在11.0，得到矿浆体系2#；(2) Use 2 parts by weight of sodium hydroxide to adjust the pH of the slurry system 1# to ensure that the pH of the slurry is maintained at 11.0 to obtain slurry system 2#;
(3)向矿浆体系2#中曝气4h，其中曝气的液气比为0.75，溢出的气体采用浓度为30％的稀硫酸收集，通过板框压滤进行固液分离，得到压滤渣和滤液3#，滤渣可进行资源化利用；(3) Aerate into the slurry system 2# for 4 hours, where the liquid-to-air ratio of the aeration is 0.75, and the overflowing gas is collected by dilute sulfuric acid with a concentration of 30%, and solid-liquid separation is carried out through plate and frame filter press to obtain filter press residue and Filtrate 3#, the filter residue can be used as resources;
(4)向滤液3#中添加1.0％的次氯酸钠溶液，并加入电流密度为40mA/cm
2的电场，反应3h，通过板框压滤进行固液分离，得到滤液4#。
(4) 1.0% sodium hypochlorite solution was added to the filtrate, # 3, and adding electric current density of 40mA / cm 2, the reaction 3h, solid-liquid separation by a frame filter press to give a filtrate # 4.
(5)将得到的滤液4#循环用于下一批电解锰渣浸。经过处理后，渗滤液pH值为6.7，未检测出锰与氨氮，达到《综合污水排放标准》(GB 8978—1996)所规定的一级排放标准。(5) Recycle the obtained filtrate 4# for the next batch of electrolytic manganese slag leaching. After treatment, the pH value of the leachate was 6.7, and manganese and ammonia nitrogen were not detected, which reached the first level discharge standard specified in the "Comprehensive Wastewater Discharge Standard" (GB 8978-1996).
Claims (1)
- 一种电场强化电解锰渣无害化处理的方法，该方法步骤如下：An electric field-enhanced method for the harmless treatment of electrolytic manganese slag. The steps of the method are as follows:(1)将电解锰渣与水按照一定质量比进行均匀混合，得到矿浆体系1#；其中电解锰渣与水按照质量比＝1：5～10；(1) The electrolytic manganese slag and water are uniformly mixed according to a certain mass ratio to obtain slurry system 1#; wherein the electrolytic manganese slag and water are according to the mass ratio=1:5-10;(2)采用碱性物料调节矿浆体系1#pH，确保浆体pH值维持在8.5～11.5，得到矿浆体系2#；其中碱性物料为0.2～2.0重量份的灼烧生料，0.2～2.0重量份的氧化钙，0.5～2.0重量份的低品位氧化镁其中一种或者多种；(2) Use alkaline materials to adjust the pH of the slurry system 1# to ensure that the pH of the slurry is maintained at 8.5-11.5 to obtain slurry system 2#; the alkaline material is 0.2-2.0 parts by weight of the burning raw meal, 0.2-2.0 One or more parts by weight of calcium oxide and 0.5 to 2.0 parts by weight of low-grade magnesium oxide;(3)向矿浆体系2#中曝气1～4h，采用稀硫酸收集溢出的气体，通过板框压滤进行固液分离，得到滤渣和滤液3#，滤渣可进行资源化利用；其中曝气的液气比为0.38～0.85，稀硫酸的质量比为15％～30％；(3) Aerate the slurry system 2# for 1～4h, collect the overflowing gas with dilute sulfuric acid, and separate the solid-liquid through plate and frame filter press to obtain filter residue and filtrate 3#. The filter residue can be used as resources; among them, aeration The liquid-gas ratio is 0.38～0.85, and the mass ratio of dilute sulfuric acid is 15%～30%;(4)向滤液3#中添加体积比为0.1％～1.0％的次氯酸钠溶液，并引入电流密度为0～40mA/cm 2的电场，反应1～3h后，通过板框压滤进行固液分离，得到滤液4#； (4) # 3 was added to the filtrate in a volume ratio of 0.1 to 1.0% sodium hypochlorite solution, and the introduction of electric current density is 0 ~ 40mA / cm 2, and after the reaction is 1 ~ 3h, solid-liquid separation by a frame filter press , Get filtrate 4#;(5)将得到的滤液4#循环用于下一批电解锰渣浸出。(5) Recycle the obtained filtrate 4# for the next batch of electrolytic manganese slag leaching.
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