WO2022082814A1 - Complexed heavy metal wastewater treatment process - Google Patents
Complexed heavy metal wastewater treatment process Download PDFInfo
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- WO2022082814A1 WO2022082814A1 PCT/CN2020/123589 CN2020123589W WO2022082814A1 WO 2022082814 A1 WO2022082814 A1 WO 2022082814A1 CN 2020123589 W CN2020123589 W CN 2020123589W WO 2022082814 A1 WO2022082814 A1 WO 2022082814A1
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- heavy metal
- wastewater
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 51
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000004062 sedimentation Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 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 description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001226 reprecipitation Methods 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 3
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the invention relates to the technical field of wastewater treatment, in particular to a complex heavy metal wastewater treatment process.
- Complex heavy metal wastewater comes from a wide range of sources, and industrial wastewater discharge is the most important source of complex heavy metal pollution in the environment.
- Industrial wastewater containing a large amount of complex heavy metals mainly includes wastewater discharged from the metal smelting industry, printed circuit board industry, printing and dyeing industry, paper industry, electroplating industry and other industries.
- the combination of OH-, Cl-, SO42-, NH4+, organic acid, amino acid, humic acid and fulvic acid will generate various complexes or chelates.
- complex heavy metal ions In heavy metal ion wastewater, complex heavy metal ions, especially complex nickel wastewater, have a wide range of sources and are difficult to treat. At present, the vast majority of electroplating wastewater is difficult to meet the standard after treatment. The main reason is that electroplating wastewater is complex and contains a large amount of inorganic and organic complexes such as ammonia nitrogen, carboxylic acid, alcohol, organic phosphoric acid, EDTA and nicotinic acid. It can form a dissolved stable complex with nickel ions in water (herein referred to as complex nickel), which leads to an increase in the difficulty of wastewater treatment. However, it is difficult to completely break the complex with common methods, such as chemical precipitation. The vast majority of complex nickel wastewater in China is generally broken by sodium sulfide or heavy metal scavengers. However, a large amount of complexing agent is still difficult to be completely eliminated, so that the effluent cannot be discharged up to the standard.
- the object of the present invention is to provide a kind of complex heavy metal wastewater treatment process, to solve the problem proposed in the above-mentioned background technology.
- a process for the treatment of complex heavy metal wastewater comprising the following steps:
- the obtained supernatant is passed through the activated carbon filter in turn, and the heavy metal ions remaining in the supernatant are filtered out through the activated carbon filter, and then the filtered filtrate is discharged.
- the heavy metal reduction replacement reagent can be one or both of sodium sulfite and sodium sulfide.
- the heavy metal complex breaking replacement reagent can be one or more of ferric chloride, ferric sulfate, ferric nitrate and ferrous chloride.
- the heavy metal scavenger can be one or more of cationic polyacrylamide, neutral polyacrylamide, amphoteric polyacrylamide and polyaluminum ferric sulfate.
- the pH value of the waste water after adding the heavy metal reduction and replacement reagent is between 2 and 3.
- the pH value of the supernatant is adjusted between 8 and 9 after adding lime in the neutralization tank.
- the wastewater is preliminarily precipitated through a sedimentation tank, and then the heavy metal reduction and replacement reagent and the heavy metal decomplexing and replacement agent are added, the wastewater is reprecipitated, and then the heavy metal catching agent is added, and the pH value of the wastewater is adjusted at the same time, and the wastewater is finally precipitated, and finally
- the activated carbon filter is used for filtration.
- the wastewater treatment process goes through three precipitations and one filtration in sequence. The method is simple, easy to operate, low in cost, and has a good treatment effect, and can achieve stable discharge up to the standard for a long time.
- Embodiment, the present invention provides the following technical scheme: a kind of complex heavy metal wastewater treatment process, comprises the following steps:
- the obtained supernatant is passed through the activated carbon filter in turn, and the heavy metal ions remaining in the supernatant are filtered out through the activated carbon filter, and then the filtered filtrate is discharged.
- the heavy metal reduction replacement reagent can be one or both of sodium sulfite and sodium sulfide.
- sodium sulfite or sodium sulfide can replace the heavy metals Ni2+, Zn2+, Pb2+ or Cu2+ in the wastewater, so that the heavy metal ions are free in the wastewater, which is convenient for precipitation and filtration.
- the heavy metal complex breaking replacement reagent can be one or more of ferric chloride, ferric sulfate, ferric nitrate and ferrous chloride.
- the complexed heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ can be reacted with ferric chloride, ferric sulfate, ferric nitrate or ferrous chloride, thereby destroying the link between the complexing of heavy metal ions, which is convenient for the The heavy metal ions in the wastewater are replaced.
- the heavy metal scavenger can be one or more of cationic polyacrylamide, neutral polyacrylamide, amphoteric polyacrylamide and polyaluminum ferric sulfate.
- the heavy metal scavenger can effectively precipitate metal ions and reduce the concentration of metal ions in wastewater.
- the pH value of the wastewater after adding the heavy metal reduction and replacement reagent is between 2 and 3.
- the pH value is between 2 and 3
- the heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ will be released from the complex.
- the pH value of the supernatant liquid is adjusted between 8 and 9 after adding lime in the neutralization tank; when the pH value is between 2 and 3, heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ will precipitate.
- the wastewater treatment process preliminarily precipitates wastewater through a sedimentation tank, and then adds heavy metal reduction and replacement reagents and heavy metal decomplexation replacement reagents, reprecipitates the wastewater, and then adds heavy metal catching agents, while adjusting the PH value of the wastewater. , the wastewater is finally precipitated, and finally filtered with an activated carbon filter.
- the wastewater treatment process through three times of precipitation and one filtration, is simple, easy to operate, low in cost, and has a good treatment effect, and can achieve stable discharge up to the standard for a long time.
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A complexed heavy metal wastewater treatment process, comprising the following steps: S1, discharging complexed heavy metal wastewater into a sedimentation tank for preliminary precipitation to precipitate out impurities and wastes in the wastewater, and then discharging the wastewater into a reaction tank; and S2, uniformly adding a heavy metal reduction and replacement reagent into the reaction tank, so that a heavy metal in the wastewater is replaced out. According to the present invention, the wastewater is preliminarily precipitated by the sedimentation tank, then the heavy metal reduction and replacement reagent and a heavy metal decomplexation and replacement reagent are added to reprecipitate the wastewater, a heavy metal capturing agent is added, the PH value of the wastewater is adjusted at the same time, the wastewater is precipitated for the last time, and finally, an active carbon filter is used for filtering. The wastewater treatment process sequentially comprises three times of precipitation and one time of filtration, and is simple in method, easy to operate, low in cost, good in treatment effect and capable of achieving stable standard discharge for a long time.
Description
本发明涉及废水处理技术领域，具体为一种络合重金属废水处理工艺。 The invention relates to the technical field of wastewater treatment, in particular to a complex heavy metal wastewater treatment process.
络合重金属废水来源广泛，工业废水排放是环境中络合重金属污染最主要的来源。含有大量络合重金属的工业废水主要包括金属冶炼业、印刷电路板业、印染业、造纸业、电镀业等行业排放的废水，工业废水中的自由金属离子排入水体后，与天然水体中的OH-、Cl-、SO42-、NH4+、有机酸、氨基酸、腐殖酸和富里酸等结合会生成各种络合物或螯合物。Complex heavy metal wastewater comes from a wide range of sources, and industrial wastewater discharge is the most important source of complex heavy metal pollution in the environment. Industrial wastewater containing a large amount of complex heavy metals mainly includes wastewater discharged from the metal smelting industry, printed circuit board industry, printing and dyeing industry, paper industry, electroplating industry and other industries. The combination of OH-, Cl-, SO42-, NH4+, organic acid, amino acid, humic acid and fulvic acid will generate various complexes or chelates.
在重金属离子废水中，络合重金属离子，尤其是络合镍废水来源广、难处理，一直是环保领域处理的难点和热点。目前绝大多数的电镀废水经处理后很难达标，究其原因，主要因为电镀废水较复杂，含有大量氨氮、羧酸、醇、有机磷酸、乙二胺四乙酸和烟酸等无机和有机络合剂，能与水中的镍离子生成溶解的稳定络合物(在此简称络合镍)，导致废水处理难度的增加。而采用一般方法处理，如化学沉淀法等很难实现完全破络。国内绝大多数络合镍废水，一般采用硫化钠或重金属捕捉剂进行破络。但是大量的络合剂，仍然难以很好的完全破除，以致出水不能达标排放。In heavy metal ion wastewater, complex heavy metal ions, especially complex nickel wastewater, have a wide range of sources and are difficult to treat. At present, the vast majority of electroplating wastewater is difficult to meet the standard after treatment. The main reason is that electroplating wastewater is complex and contains a large amount of inorganic and organic complexes such as ammonia nitrogen, carboxylic acid, alcohol, organic phosphoric acid, EDTA and nicotinic acid. It can form a dissolved stable complex with nickel ions in water (herein referred to as complex nickel), which leads to an increase in the difficulty of wastewater treatment. However, it is difficult to completely break the complex with common methods, such as chemical precipitation. The vast majority of complex nickel wastewater in China is generally broken by sodium sulfide or heavy metal scavengers. However, a large amount of complexing agent is still difficult to be completely eliminated, so that the effluent cannot be discharged up to the standard.
[0004] 本发明的目的在于提供一种络合重金属废水处理工艺，以解决上述背景技术中提出的问题。
The object of the present invention is to provide a kind of complex heavy metal wastewater treatment process, to solve the problem proposed in the above-mentioned background technology.
为实现上述目的，本发明提供如下技术方案：一种络合重金属废水处理工艺，包括以下步骤：In order to achieve the above purpose, the present invention provides the following technical solutions: a process for the treatment of complex heavy metal wastewater, comprising the following steps:
S1、将络合重金属废水排放到沉淀池内，进行初步沉淀，将废水中的杂质和废料沉淀出，然后将废水排放到反应池内；S1, discharge the complex heavy metal wastewater into the sedimentation tank, carry out preliminary precipitation, precipitate the impurities and wastes in the wastewater, and then discharge the wastewater into the reaction tank;
S2、向反应池内均匀加入重金属还原置换试剂，使得废水中的重金属被置换出，同时向反应池内加入重金属破络置换试剂，使得废水中的重金属游离在废水中，然后再次沉淀；S2, uniformly adding a heavy metal reduction and replacement reagent into the reaction tank, so that the heavy metals in the waste water are replaced, and at the same time, add a heavy metal complex breaking and replacement reagent into the reaction tank, so that the heavy metals in the waste water are freed in the waste water, and then precipitated again;
S3、将再次沉淀得到的上清液排放到中和池内，向上清液中加入重金属捕捉剂，使得上清液中的重金属离子释放出来；S3, discharging the supernatant obtained by reprecipitation into the neutralization tank, and adding a heavy metal scavenger to the supernatant, so that the heavy metal ions in the supernatant are released;
S4、然后向中和池内加入石灰，调整上清液的PH值，同时上清液进行芬顿反应，在中和池内进行最后沉淀；S4, then add lime into the neutralization tank, adjust the pH value of the supernatant, and carry out the Fenton reaction in the supernatant simultaneously, and carry out final precipitation in the neutralization tank;
S5、在最后沉淀后，将得到的上清液依次通过活性炭过滤器，通过活性炭过滤器将上清液残留的重金属离子过滤出，然后将过滤出的滤液排放。S5. After the final precipitation, the obtained supernatant is passed through the activated carbon filter in turn, and the heavy metal ions remaining in the supernatant are filtered out through the activated carbon filter, and then the filtered filtrate is discharged.
其中，所述重金属还原置换试剂可以是亚硫酸钠和硫化钠中的一种或两种。Wherein, the heavy metal reduction replacement reagent can be one or both of sodium sulfite and sodium sulfide.
其中，所述重金属破络置换试剂可以是氯化铁、硫酸铁、硝酸铁和氯化亚铁中的一种或多种。Wherein, the heavy metal complex breaking replacement reagent can be one or more of ferric chloride, ferric sulfate, ferric nitrate and ferrous chloride.
其中，所述重金属捕捉剂可以是阳离子聚丙烯酰胺、中性聚丙烯酰胺、两性聚丙烯酰胺和聚合硫酸铝铁中的一种或多种。Wherein, the heavy metal scavenger can be one or more of cationic polyacrylamide, neutral polyacrylamide, amphoteric polyacrylamide and polyaluminum ferric sulfate.
其中，所述废水中添加重金属还原置换试剂后的PH值为2～3之间。Wherein, the pH value of the waste water after adding the heavy metal reduction and replacement reagent is between 2 and 3.
其中，所述中和池内加入石灰后调整上清液的PH值为8～9之间。Wherein, the pH value of the supernatant is adjusted between 8 and 9 after adding lime in the neutralization tank.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明通过沉淀池对废水进行初步沉淀，然后加入重金属还原置换试剂和重金属破络置换试剂后，对废水再次沉淀，接着加入重金属铺捉剂，同时调节废水的PH值，对废水最后沉淀，最后使用活性炭过滤器进行过滤，该废水处理工艺，依次经过三次沉淀和一次过滤，方法简单，容易操作，成本低，而且处理效果良好，可长时间实现稳定达标排放。In the present invention, the wastewater is preliminarily precipitated through a sedimentation tank, and then the heavy metal reduction and replacement reagent and the heavy metal decomplexing and replacement agent are added, the wastewater is reprecipitated, and then the heavy metal catching agent is added, and the pH value of the wastewater is adjusted at the same time, and the wastewater is finally precipitated, and finally The activated carbon filter is used for filtration. The wastewater treatment process goes through three precipitations and one filtration in sequence. The method is simple, easy to operate, low in cost, and has a good treatment effect, and can achieve stable discharge up to the standard for a long time.
[0007] 下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
[0007] Below in conjunction with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described, obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例，本发明提供如下技术方案：一种络合重金属废水处理工艺，包括以下步骤：Embodiment, the present invention provides the following technical scheme: a kind of complex heavy metal wastewater treatment process, comprises the following steps:
S1、将络合重金属废水排放到沉淀池内，进行初步沉淀，将废水中的杂质和废料沉淀出，然后将废水排放到反应池内；S1, discharge the complex heavy metal wastewater into the sedimentation tank, carry out preliminary precipitation, precipitate the impurities and wastes in the wastewater, and then discharge the wastewater into the reaction tank;
S2、向反应池内均匀加入重金属还原置换试剂，使得废水中的重金属被置换出，同时向反应池内加入重金属破络置换试剂，使得废水中的重金属游离在废水中，然后再次沉淀；S2, uniformly adding a heavy metal reduction and replacement reagent into the reaction tank, so that the heavy metals in the waste water are replaced, and at the same time, add a heavy metal complex breaking and replacement reagent into the reaction tank, so that the heavy metals in the waste water are freed in the waste water, and then precipitated again;
S3、将再次沉淀得到的上清液排放到中和池内，向上清液中加入重金属捕捉剂，使得上清液中的重金属离子释放出来；S3, discharging the supernatant obtained by reprecipitation into the neutralization tank, and adding a heavy metal scavenger to the supernatant, so that the heavy metal ions in the supernatant are released;
S4、然后向中和池内加入石灰，调整上清液的PH值，同时上清液进行芬顿反应，在中和池内进行最后沉淀；S4, then add lime into the neutralization tank, adjust the pH value of the supernatant, and simultaneously carry out the Fenton reaction of the supernatant, and carry out final precipitation in the neutralization tank;
S5、在最后沉淀后，将得到的上清液依次通过活性炭过滤器，通过活性炭过滤器将上清液残留的重金属离子过滤出，然后将过滤出的滤液排放。S5. After the final precipitation, the obtained supernatant is passed through the activated carbon filter in turn, and the heavy metal ions remaining in the supernatant are filtered out through the activated carbon filter, and then the filtered filtrate is discharged.
其中，重金属还原置换试剂可以是亚硫酸钠和硫化钠中的一种或两种。Wherein, the heavy metal reduction replacement reagent can be one or both of sodium sulfite and sodium sulfide.
其中，亚硫酸钠或硫化钠能够将废水中的重金属Ni2+、Zn2+、Pb2+或Cu2+置换出，使得重金属离子游离在废水中，方便沉淀过滤。Among them, sodium sulfite or sodium sulfide can replace the heavy metals Ni2+, Zn2+, Pb2+ or Cu2+ in the wastewater, so that the heavy metal ions are free in the wastewater, which is convenient for precipitation and filtration.
其中，重金属破络置换试剂可以是氯化铁、硫酸铁、硝酸铁和氯化亚铁中的一种或多种。Wherein, the heavy metal complex breaking replacement reagent can be one or more of ferric chloride, ferric sulfate, ferric nitrate and ferrous chloride.
其中，通过氯化铁、硫酸铁、硝酸铁或氯化亚铁能够使得络合后的重金属离子Ni2+、Zn2+、Pb2+或Cu2+与之反应，从而破坏重金属离子络合之间的链接，方便了将废水中的重金属离子置换出。Among them, the complexed heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ can be reacted with ferric chloride, ferric sulfate, ferric nitrate or ferrous chloride, thereby destroying the link between the complexing of heavy metal ions, which is convenient for the The heavy metal ions in the wastewater are replaced.
其中，重金属捕捉剂可以是阳离子聚丙烯酰胺、中性聚丙烯酰胺、两性聚丙烯酰胺和聚合硫酸铝铁中的一种或多种。Wherein, the heavy metal scavenger can be one or more of cationic polyacrylamide, neutral polyacrylamide, amphoteric polyacrylamide and polyaluminum ferric sulfate.
其中，重金属捕捉剂可以有效沉淀金属离子，使废水中的金属离子浓度降低。Among them, the heavy metal scavenger can effectively precipitate metal ions and reduce the concentration of metal ions in wastewater.
其中，废水中添加重金属还原置换试剂后的PH值为2～3之间，当PH值在2～3之间时，重金属离子Ni2+、Zn2+、Pb2+或Cu2+会从络合物中游离出来。Among them, the pH value of the wastewater after adding the heavy metal reduction and replacement reagent is between 2 and 3. When the pH value is between 2 and 3, the heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ will be released from the complex.
其中，中和池内加入石灰后调整上清液的PH值为8～9之间；当PH值在2～3之间时，重金属离子Ni2+、Zn2+、Pb2+或Cu2+会产生沉淀。Among them, the pH value of the supernatant liquid is adjusted between 8 and 9 after adding lime in the neutralization tank; when the pH value is between 2 and 3, heavy metal ions Ni2+, Zn2+, Pb2+ or Cu2+ will precipitate.
综上所述：该废水处理工艺通过沉淀池对废水进行初步沉淀，然后加入重金属还原置换试剂和重金属破络置换试剂后，对废水再次沉淀，接着加入重金属铺捉剂，同时调节废水的PH值，对废水最后沉淀，最后使用活性炭过滤器进行过滤，该废水处理工艺，依次经过三次沉淀和一次过滤，方法简单，容易操作，成本低，而且处理效果良好，可长时间实现稳定达标排放。To sum up: the wastewater treatment process preliminarily precipitates wastewater through a sedimentation tank, and then adds heavy metal reduction and replacement reagents and heavy metal decomplexation replacement reagents, reprecipitates the wastewater, and then adds heavy metal catching agents, while adjusting the PH value of the wastewater. , the wastewater is finally precipitated, and finally filtered with an activated carbon filter. The wastewater treatment process, through three times of precipitation and one filtration, is simple, easy to operate, low in cost, and has a good treatment effect, and can achieve stable discharge up to the standard for a long time.
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。It should be noted that, in this document, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any relationship between these entities or operations. any such actual relationship or sequence exists. Moreover, the terms "comprising", "comprising" or any other variation thereof are intended to encompass a non-exclusive inclusion such that a process, method, article or device that includes a list of elements includes not only those elements, but also includes not explicitly listed or other elements inherent to such a process, method, article or apparatus.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made in these embodiments without departing from the principle and spirit of the invention and modifications, the scope of the present invention is defined by the appended claims and their equivalents.
Claims (6)
- 一种络合重金属废水处理工艺，其特征在于，包括以下步骤：A process for treating complex heavy metal wastewater, comprising the following steps:S1、将络合重金属废水排放到沉淀池内，进行初步沉淀，将废水中的杂质和废料沉淀出，然后将废水排放到反应池内；S1, discharge the complex heavy metal wastewater into the sedimentation tank, carry out preliminary precipitation, precipitate the impurities and wastes in the wastewater, and then discharge the wastewater into the reaction tank;S2、向反应池内均匀加入重金属还原置换试剂，使得废水中的重金属被置换出，同时向反应池内加入重金属破络置换试剂，使得废水中的重金属游离在废水中，然后再次沉淀；S2, uniformly adding a heavy metal reduction and replacement reagent into the reaction tank, so that the heavy metals in the waste water are replaced, and at the same time, add a heavy metal complex breaking and replacement reagent into the reaction tank, so that the heavy metals in the waste water are freed in the waste water, and then precipitated again;S3、将再次沉淀得到的上清液排放到中和池内，向上清液中加入重金属捕捉剂，使得上清液中的重金属离子释放出来；S3, discharging the supernatant obtained by reprecipitation into the neutralization tank, and adding a heavy metal scavenger to the supernatant, so that the heavy metal ions in the supernatant are released;S4、然后向中和池内加入石灰，调整上清液的PH值，同时上清液进行芬顿反应，在中和池内进行最后沉淀；S4, then add lime into the neutralization tank, adjust the pH value of the supernatant, and carry out the Fenton reaction in the supernatant simultaneously, and carry out final precipitation in the neutralization tank;S5、在最后沉淀后，将得到的上清液依次通过活性炭过滤器，通过活性炭过滤器将上清液残留的重金属离子过滤出，然后将过滤出的滤液排放。S5. After the final precipitation, the obtained supernatant is passed through the activated carbon filter in turn, and the heavy metal ions remaining in the supernatant are filtered out through the activated carbon filter, and then the filtered filtrate is discharged.
- 根据权利要求1所述的一种络合重金属废水处理工艺，其特征在于：所述重金属还原置换试剂可以是亚硫酸钠和硫化钠中的一种或两种。The complex heavy metal wastewater treatment process according to claim 1, wherein the heavy metal reduction and replacement reagent can be one or both of sodium sulfite and sodium sulfide.
- 根据权利要求1所述的一种络合重金属废水处理工艺，其特征在于：所述重金属破络置换试剂可以是氯化铁、硫酸铁、硝酸铁和氯化亚铁中的一种或多种。A kind of complex heavy metal wastewater treatment process according to claim 1, is characterized in that: described heavy metal breaking complex replacement reagent can be one or more in ferric chloride, ferric sulfate, ferric nitrate and ferrous chloride .
- 根据权利要求1所述的一种络合重金属废水处理工艺，其特征在于：所述重金属捕捉剂可以是阳离子聚丙烯酰胺、中性聚丙烯酰胺、两性聚丙烯酰胺和聚合硫酸铝铁中的一种或多种。The complex heavy metal wastewater treatment process according to claim 1, wherein the heavy metal scavenger can be one of cationic polyacrylamide, neutral polyacrylamide, amphoteric polyacrylamide and polyaluminum ferric sulfate. one or more.
- 根据权利要求1所述的一种络合重金属废水处理工艺，其特征在于：所述废水中添加重金属还原置换试剂后的PH值为2～3之间。A process for treating wastewater with complex heavy metals according to claim 1, wherein the wastewater has a pH value between 2 and 3 after adding a heavy metal reduction and replacement reagent.
- 根据权利要求1所述的一种络合重金属废水处理工艺，其特征在于：所述中和池内加入石灰后调整上清液的PH值为8～9之间。The complex heavy metal wastewater treatment process according to claim 1, wherein the pH value of the supernatant is adjusted between 8 and 9 after adding lime in the neutralization tank.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5267159A (en) * | 1975-12-02 | 1977-06-03 | Takuma Co Ltd | Removing method of heavy metals in waste liquid |
| CN101723536A (en) * | 2009-12-31 | 2010-06-09 | 吴海兰 | Device for sterilizing, disinfecting and filtering rural safe drinking water |
| CN102259998A (en) * | 2011-07-28 | 2011-11-30 | 江苏南方涂装环保股份有限公司 | Treatment method for wastewater containing heavy metals |
| CN102311182A (en) * | 2010-07-06 | 2012-01-11 | 上海瑞勇实业有限公司 | Electroplating wastewater treatment method |
| CN103819023A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Treatment and recycling method of industrial wastewater containing a plurality of heavy metal ions |
| CN107364985A (en) * | 2016-05-13 | 2017-11-21 | 禾华环保科技（上海）有限公司 | A kind of method of complexation heavy metal ion in removal water body |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002355854B2 (en) * | 2001-08-03 | 2007-10-04 | Canadus Technologies, Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| CN104925987A (en) * | 2015-05-13 | 2015-09-23 | 中山大学 | Treatment method for complex metal wastewater |
| CN111039455A (en) * | 2019-12-24 | 2020-04-21 | 浙江海拓环境技术有限公司 | Independent standard-reaching treatment process for high-concentration strong-complexation nickel-containing wastewater |
| CN211688726U (en) * | 2020-01-18 | 2020-10-16 | 杭州传一科技有限公司 | Electroplating wastewater treatment device for treating metal-chelating agent complex |
-
2020
- 2020-10-21 CN CN202011129475.2A patent/CN112591926A/en active Pending
- 2020-10-26 WO PCT/CN2020/123589 patent/WO2022082814A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5267159A (en) * | 1975-12-02 | 1977-06-03 | Takuma Co Ltd | Removing method of heavy metals in waste liquid |
| CN101723536A (en) * | 2009-12-31 | 2010-06-09 | 吴海兰 | Device for sterilizing, disinfecting and filtering rural safe drinking water |
| CN102311182A (en) * | 2010-07-06 | 2012-01-11 | 上海瑞勇实业有限公司 | Electroplating wastewater treatment method |
| CN102259998A (en) * | 2011-07-28 | 2011-11-30 | 江苏南方涂装环保股份有限公司 | Treatment method for wastewater containing heavy metals |
| CN103819023A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Treatment and recycling method of industrial wastewater containing a plurality of heavy metal ions |
| CN107364985A (en) * | 2016-05-13 | 2017-11-21 | 禾华环保科技（上海）有限公司 | A kind of method of complexation heavy metal ion in removal water body |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611370A (en) * | 2022-10-24 | 2023-01-17 | 国网浙江省电力有限公司电力科学研究院 | Centrifugal electrochemical complex breaking and separating device and method |
| CN115611370B (en) * | 2022-10-24 | 2024-06-07 | 国网浙江省电力有限公司电力科学研究院 | Centrifugal electrochemical vein-breaking separation device and method |
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