CN116947235B - Nickel removal method used before biochemical water inflow of electroplating wastewater station - Google Patents
Nickel removal method used before biochemical water inflow of electroplating wastewater station Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 154
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000009713 electroplating Methods 0.000 title claims abstract description 23
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 31
- 231100000719 pollutant Toxicity 0.000 claims abstract description 31
- 239000003814 drug Substances 0.000 claims abstract description 26
- 238000004364 calculation method Methods 0.000 claims abstract description 20
- 238000012544 monitoring process Methods 0.000 claims abstract description 14
- 238000005070 sampling Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 54
- 238000007254 oxidation reaction Methods 0.000 claims description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 238000004062 sedimentation Methods 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 22
- 238000005189 flocculation Methods 0.000 claims description 22
- 230000016615 flocculation Effects 0.000 claims description 22
- 230000001105 regulatory effect Effects 0.000 claims description 18
- 239000011790 ferrous sulphate Substances 0.000 claims description 16
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000010802 sludge Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 229940079593 drug Drugs 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003311 flocculating effect Effects 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- -1 Cu 2+ Chemical class 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to the technical field of wastewater treatment, and discloses a nickel removal method used before biochemical water inflow of an electroplating wastewater station, which mainly comprises the steps of determining the content of pollutants and the addition amount of medicines, carrying out UV/Fenton treatment and flocculating and precipitating water, respectively sampling and measuring various pollutant indexes such as COD value, TP value and the like in wastewater by an online monitoring system, respectively calculating the addition amount of various medicines by a medicine addition amount calculation and addition system according to the measured content of the pollutants, and then carrying out on-time accurate and accurate medicine addition in the subsequent UV/Fenton treatment and flocculating and precipitating water outlet stages. The method has the advantages that various pollutant indexes of the wastewater treated by the method are reduced to a certain extent, no toxic or harmful gas is generated in the treatment process, the chromaticity of the wastewater is greatly reduced, compared with the common Fenton treatment method, the effect is better, and the total nickel content can stably meet the discharge limit requirement that the total nickel of the wastewater is not higher than 0.5mg/L specified in the discharge standard of electroplating pollutants (GB 21900-2008) in Table 2.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a nickel removal method used before biochemical water inflow of an electroplating wastewater station.
Background
The electroplating wastewater is characterized by high salt content, large water content and high pollutant content. The main pollutants in the electroplating wastewater are organic matters, nitrogen, phosphorus, heavy metal ions such as Cu 2+、Cr6+/Cr3+、Zn2+, ni 2+ and the like, and heavy metal ion nickel is a pollutant which is highly difficult to remove in the wastewater. The common process flow of treating electroplating wastewater in the electroplating wastewater centralized wastewater treatment station is to firstly classify and treat different types of wastewater, and then collect the wastewater into comprehensive wastewater to enter a biochemical system for treatment after the treatment is finished. The waste water entering the biochemical system has low index B/C (B: biochemical oxygen demand, biochemical oxygen demand, C: COD) for representing the biodegradability of COD (chemical oxygen demand ) value in the waste water. The nickel ions which are most difficult to degrade and remove can fluctuate in the vicinity of 0.5mg/L until exceeding 1mg/L or even higher in the comprehensive wastewater.
For the purposes of improving the biochemical indexes B/C of the wastewater and the like, nitrogen and phosphorus are removed through biochemical treatment, so that the COD value of the effluent after the biochemical treatment, total nitrogen, total phosphorus and the like meet the drainage standard, and a large amount of carbon sources such as sodium acetate and the like are generally added into the biochemical inflow water. Biochemical systems have little removal capacity for heavy metal ions.
Ultraviolet (UV) catalysis technology has been operated in many engineering fields of wastewater treatment, wherein UV/Fenton has been operated in the fields of wastewater treatment of cosmetic synthetic wastewater, PVA (polyvinyl alcohol or vinylalcohol polymer, polyvinyl alcohol) wastewater, UV/O 3 in nuclear power industry laundry wastewater and UV/H 2O2 in wastewater treatment fields of organic waste gas spray wastewater, etc. in Shanghai, guangdong, fujian, etc. Compared with the common Fenton oxidation, the UV/Fenton technology has the main advantages of greatly reducing the sludge quantity and improving the oxidation effect or oxidation capability of the hydrogen peroxide. In the oxidation of organic pollutants such as PVA waste water, silver plating waste water of terminal electrodes of paster electronic elements, liquid detergent synthetic waste water and the like, fe 3+ in the waste water can be completely reduced into Fe 2+ even under the action of UV (ultraviolet) due to the rapid and efficient oxidation of the organic pollutants. In this case, the utilization ratio of the oxidizing agent is greatly improved and the activity of the catalyst is improved.
The invention provides a nickel removal method used before biochemical water inflow of an electroplating wastewater station to solve the problems, wherein various pollutant indexes of wastewater after biochemical treatment, particularly total nickel content, are reduced to stably meet the discharge limit value of the wastewater with total nickel content not higher than 0.5mg/L specified in the discharge standard of electroplating pollutants (GB 21900-2008) in Table 2, which is a difficult problem of electroplating wastewater treatment industry.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a nickel removal method for electroplating wastewater station before biochemical water inflow, various pollutant indexes of wastewater treated by the method are reduced to a certain extent, no toxic or harmful gas is generated in the treatment process, the chromaticity of the wastewater is greatly reduced, compared with the common Fenton treatment method, the effect is better, the total nickel content can stably meet the discharge limit requirement that the total nickel of the wastewater is not higher than 0.5mg/L specified in the discharge standard of electroplating pollutants (GB 21900-2008) in Table 2.
(II) technical scheme
The invention provides the following technical scheme: the nickel removing method for the electroplating wastewater station before biochemical water inflow comprises the following steps:
1) The method comprises the steps that wastewater enters an adjusting tank before entering a UV/Fenton treatment system, after enough wastewater is collected by the adjusting tank, an online monitoring system is used for sampling and measuring various pollutant indexes such as COD (chemical oxygen demand) value and TP (transport stream) value in the wastewater, and according to the measured pollutant content, various medicine adding amounts are calculated by a medicine adding amount calculating and adding system;
2) The wastewater in the regulating tank enters an oxidation tank in a UV/Fenton treatment system, ferrous sulfate is added after enough wastewater is collected in the oxidation tank, and then acid or alkali is added into the oxidation tank to regulate the pH 1 of the wastewater in the oxidation tank to be between 1 and 10;
3) After the pH 1 is regulated, starting a UV lamp system in the UV/Fenton treatment system, adding hydrogen peroxide into the oxidation pond, and continuously starting the UV lamp system after the hydrogen peroxide is added, wherein the total starting time of the UV lamp system is 1-10h;
4) After the starting time of the UV lamp system is up, the UV lamp system is closed, the wastewater in the oxidation tank is discharged into a dosing tank in the flocculation precipitation system, after the dosing tank collects enough wastewater, A is added into the dosing tank, after the addition of A is finished, alkali is added into the dosing tank to adjust the pH 2 value of the wastewater in the dosing tank, and after the addition of alkali is finished, the pH 2 value range of the wastewater in the dosing tank is 9-13;
5) Adding a sufficient amount of PAM into the dosing tank after the pH 2 is regulated, and discharging the wastewater in the dosing tank into a sedimentation tank in a flocculation sedimentation system after the PAM is added, wherein the residence time of the wastewater in the sedimentation tank is 1-5h;
6) After the residence time of the wastewater in the sedimentation tank is finished, discharging upper clear water to a pH value callback tank in a flocculation sedimentation system, discharging lower sludge to a filter press in the flocculation sedimentation system, starting the filter press after the filter press collects enough sludge, discharging clear water filtered by the filter press to the pH value callback tank, and additionally treating dry sludge filtered by the filter press;
7) After the pH value callback pond collects enough waste water, adding acid into the pH value callback pond until the pH 3 of the waste water in the pH value callback pond is between 6 and 9, and discharging the waste water in the pH value callback pond to a biochemical treatment system after the pH value of the waste water in the pH value callback pond is regulated.
Preferably, the preferred value range of the pH 1 is between 2 and 5.
Preferably, the preferred value range of the UV lamp system on-time is between 1.5 and 5 hours.
Preferably, the preferred value range of the pH 2 is between 9 and 10.
Preferably, the A is inorganic salt, and the mass percentage content of the hydrogen peroxide is 27.5%.
Preferably, the method for calculating the addition amount of the ferrous sulfate (FeSO 4·7H2 O) comprises the following steps:
m1 ＝ 2.34 × COD (1)
The unit of m 1 in the formula (1) is kg/m 3 or kg/t, the unit of COD is g/L, and the volume unit of wastewater m 3 (cubic meters) is equivalent to the weight unit of t (tons);
m2 ＝ 9.86 × TP (2)
The unit of m 2 in the formula (2) is kg/m 3 or kg/t, the TP is the total phosphorus content in the wastewater, and the unit of the TP is g/L;
Comparing the sizes of m 1 and m 2, taking the larger one of m 1 and m 2, and marking the larger one of m 1 and m 2 as m 0;
Calculating the addition amount of ferrous sulfate by combining the effective volume in the oxidation pond:
M ＝ U × m0 (3)
The effective volume of the oxidation pond is U, the unit of U is M 3 or t, the result M calculated by the calculation formula (3) is the amount of ferrous sulfate to be added in the oxidation pond, and the unit is: kg.
Preferably, the calculation method of the hydrogen peroxide addition amount comprises the following steps:
v0 ＝ 13.241 × COD × n (4)
In the formula (4), the unit of COD is g/L, n is a coefficient, the value range of n is 0.06-0.4, and the unit of v 0 in the formula (4) is L/m 3 or L/t;
Calculating the adding amount of hydrogen peroxide by combining the effective volume in the oxidation pond:
V ＝ U × v0 (5)
The effective volume of the oxidation pond is U, the unit of U is m 3 or t, the result V calculated by the calculation formula (5) is the volume of hydrogen peroxide to be added in the oxidation pond, and the unit is: l.
Preferably, the preferred value range of n in formula (4) is between 0.19 and 0.25.
Preferably, the method for calculating the addition amount of the A is as follows:
c0 ＝ 11.9 × TP (6)
The unit of c 0 in the formula (6) is kg/m 3 or kg/t, the TP is the total phosphorus content in the wastewater, and the unit of TP is g/L;
Calculating the addition amount of A by combining the effective volume in the oxidation pond:
C ＝ U × c0 (7)
The effective volume of the oxidation tank is U, the unit of U is m 3 or t, the result C calculated by the calculation formula (7) is the amount of A to be added in the dosing tank, and the unit is: kg.
The invention aims to solve the other technical problem of providing a nickel removal system for implementing the nickel removal method, which comprises an adjusting tank, an online monitoring system, a medicine adding amount calculating and adding system, a UV/Fenton treatment system, a flocculation precipitation system and a biochemical treatment system;
The UV/Fenton treatment system comprises a UV lamp system and an oxidation pond;
The flocculation precipitation system comprises a dosing tank, a sedimentation tank, a pH value callback tank and a filter press;
The wastewater sequentially passes through an adjusting tank, an oxidation tank, a dosing tank, a sedimentation tank, a pH value callback tank and a biochemical treatment system during treatment;
The online monitoring system is used for sampling and measuring various pollutant indexes such as COD value and TP value in the wastewater respectively, and the medicine adding amount calculating and adding system is used for calculating various medicine adding amounts respectively according to the pollutant content measured by the online monitoring system and accurately adding the medicine on time.
(III) beneficial effects
Compared with the prior art, the invention provides a nickel removal method used before biochemical water inflow of an electroplating wastewater station, which has the following beneficial effects:
1. the wastewater before biochemical water inflow is treated by the electroplating wastewater treatment industry usually through conventional physicochemical processes such as cyanogen breaking, reduction, precipitation and the like, then all the wastewater is directly collected and enters a biochemical treatment system, after the conventional treatment processes are treated, the TP, total nickel and COD values of the wastewater are usually very high, and after the treatment by adopting the method, the content of the pollutants is greatly reduced, so that the stable standard-reaching discharge of the wastewater after the subsequent biochemical treatment is facilitated;
2. after the treatment by the method, the total nickel content of the wastewater can be stably maintained within 0.5mg/L, and the total nickel content of the wastewater after biochemical treatment is unchanged, so that the total nickel content of the final effluent after biochemical treatment can be stably maintained within 0.5 mg/L;
3. The use of the UV/Fenton treatment method improves the treatment effect, and the B/C value of the treated wastewater is greatly improved, so that the subsequent biochemical treatment is facilitated.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the invention provides a nickel removal method for a plating wastewater station before biochemical water inflow, which aims to treat wastewater before entering a biochemical treatment system and reduce the total nickel content in the wastewater, and mainly comprises determination of pollutant content and medicine addition amount, UV/Fenton treatment and flocculation precipitation water outlet.
The online monitoring system is used for sampling and measuring various pollutant indexes such as COD value and TP value in the wastewater, then the drug adding amount calculation and adding system is used for calculating various drug adding amounts according to the measured pollutant content, the wastewater enters the regulating tank before entering the UV/Fenton treatment system, the whole measuring and calculating process is completed in the regulating tank stage, and in the subsequent UV/Fenton treatment and flocculation precipitation water outlet stage, the drug is accurately and precisely added by the drug adding amount calculation and adding system.
The chemical to be added into the wastewater is ferrous sulfate, hydrogen peroxide and A, wherein A is/is nontoxic, harmless, cheap and easily available inorganic salt, A does not have negative influence on the wastewater treatment process, A does not add pollutants after wastewater treatment, and the mass percentage content of the hydrogen peroxide is 27.5%.
It should be noted that, in the above measurement and calculation process, all data calculation and comparison are automatically performed by each parameter set in advance, without manual intervention, and all the addition amounts of each batch of medicines are calculated and added by the system according to the water amount processed by the post-stage, which is a conventional technology known to the public in the prior art, and the process is not described in detail.
After measurement and calculation are finished, the wastewater in the regulating tank enters an oxidation tank in a UV/Fenton treatment system, the effective volume of the oxidation tank is U, the unit of U is m 3 or t, the UV/Fenton treatment adopts a batch treatment mode, the treatment capacity of the UV/Fenton system is U of each batch, after enough wastewater is collected in the oxidation tank, ferrous sulfate is added, then acid or alkali is added into the oxidation tank to regulate the pH 1 value of the wastewater in the oxidation tank to be 1-10, and the preferable value range of pH 1 is 2-5.
The method for calculating the addition amount of ferrous sulfate (FeSO 4·7H2 O) comprises the following steps:
m1 ＝ 2.34 × COD (1)
In the formula (1), the unit of m 1 is kg/m 3 or kg/t, the unit of COD is g/L, and the volume unit of wastewater m 3 (cubic meters) is equivalent to the weight unit of t (ton);
m2 ＝ 9.86 × TP (2)
In the formula (2), the unit of m 2 is kg/m 3 or kg/t, TP is the total phosphorus content in the wastewater, and the unit of TP is g/L;
Comparing the sizes of m 1 and m 2, taking the larger one of m 1 and m 2, and marking the larger one of m 1 and m 2 as m 0;
Calculating the addition amount of ferrous sulfate by combining the effective volume in the oxidation pond:
M ＝ U × m0 (3)
the result M calculated by the calculation formula (3) is the amount of ferrous sulfate required to be added in the oxidation pond, and the unit is: kg.
After the pH 1 is regulated, starting a UV lamp system in the UV/Fenton treatment system, adding hydrogen peroxide into the oxidation pond, and continuously starting the UV lamp system after the hydrogen peroxide is added, wherein the total starting time of the UV lamp system is 1-10h, and the preferable value range of the starting time of the UV lamp system is 1.5-5 h.
The calculation method of the hydrogen peroxide addition amount comprises the following steps:
v0 ＝ 13.241 × COD × n (4)
In the formula (4), the unit of COD is g/L, n is a coefficient, the value range of n is 0.06-0.4, and the unit of v 0 in the formula (4) is L/m 3 or L/t;
Calculating the adding amount of hydrogen peroxide by combining the effective volume in the oxidation pond:
V ＝ U × v0 (5)
The result V calculated by the calculation formula (5) is the volume of hydrogen peroxide to be added in the oxidation pond, and the unit is: l.
After the starting time of the UV lamp system is up, the UV lamp system is closed, the wastewater in the oxidation tank is discharged into a dosing tank in the flocculation precipitation system, after the dosing tank collects enough wastewater, A is added into the dosing tank, after the addition of A is finished, alkali is added into the dosing tank to adjust the pH 2 value of the wastewater in the dosing tank, and after the addition of alkali is finished, the pH 2 value range of the wastewater in the dosing tank is 9-13.
The calculation method of the addition amount of A is as follows:
c0 ＝ 11.9 × TP (6)
The unit of c 0 in the formula (6) is kg/m 3 or kg/t, TP is the total phosphorus content in the wastewater, and the unit of TP is g/L;
Calculating the addition amount of A by combining the effective volume in the oxidation pond:
C ＝ U × c0 (7)
the result C calculated by the calculation formula (7) is the amount of A to be added in the dosing tank, and the unit is: kg.
After the pH 2 is regulated, adding enough PAM into the dosing tank, discharging the wastewater in the dosing tank into a sedimentation tank in a flocculation sedimentation system, wherein the residence time of the wastewater in the sedimentation tank is 1-5h, discharging clear water at the upper part into a pH value callback tank in the flocculation sedimentation system after the residence time of the wastewater in the sedimentation tank is finished, discharging sludge at the lower part into a filter press in the flocculation sedimentation system, starting the filter press after the filter press collects enough sludge, discharging clear water filtered out by the filter press into the pH value callback tank, additionally treating dry sludge filtered out by the filter press, after the pH value callback tank collects enough wastewater, adding acid into the pH value callback tank until the pH 3 of the wastewater in the pH value callback tank is in a range of 6-9, and discharging the wastewater in the pH value callback tank into a biochemical treatment system after the pH value regulation of the wastewater in the pH value callback tank is finished.
Wherein, the preferable value range of the pH 2 is determined through experiments, and the relation between the total nickel content of the wastewater effluent of the sedimentation tank and the pH 2 is shown in the following table 1 for a certain wastewater through experiments:
TABLE 1 relation between total Nickel content in wastewater and precipitation pH
* N/A indicates that the total nickel content exceeds the detection limit
Comparing the data in Table 1, the relationship between total nickel content and pH value of the wastewater can be concluded: the total nickel content of the wastewater decreases with increasing pH before the pH is below 11, and the total nickel content of the wastewater increases with increasing pH after the pH is above 11, and the preferred range of pH 2 is between 9 and 10 from the viewpoint of dosing cost and the like.
The wastewater treated by the method has the advantages that various pollutant indexes are reduced to a certain extent, no toxic or harmful gas is generated in the treatment process, the chromaticity of the wastewater is greatly reduced, compared with the common Fenton treatment method, the effect is better, and the total nickel content can stably meet the discharge limit requirement that the total nickel of the wastewater is not higher than 0.5mg/L specified in the discharge Standard of electroplating pollutants (GB 21900-2008) in Table 2.
The invention also provides a nickel removal system for implementing the nickel removal method, which comprises an adjusting tank, an online monitoring system, a medicine adding amount calculating and adding system, a UV/Fenton treatment system, a flocculation precipitation system and a biochemical treatment system.
The UV/Fenton treatment system comprises a UV lamp system and an oxidation tank, the flocculation precipitation system comprises a dosing tank, a sedimentation tank, a pH value callback tank and a filter press, and wastewater sequentially passes through the adjustment tank, the oxidation tank, the dosing tank, the sedimentation tank, the pH value callback tank and the biochemical treatment system during treatment;
the online monitoring system is used for sampling and measuring various pollutant indexes such as COD value and TP value in the wastewater respectively, and the medicine adding amount calculating and adding system is used for calculating various medicine adding amounts respectively according to the pollutant content measured by the online monitoring system and accurately adding the medicine on time.
Experimental example:
the design wastewater treatment capacity of a certain electroplating wastewater treatment plant in the four-meeting city is 2000m 3/d, the wastewater mainly comprises chromium-containing wastewater, nickel-containing wastewater, heavy metal ion-containing comprehensive wastewater, cyanide-containing wastewater, chemical nickel wastewater, alkaline degreasing wastewater and the like, the wastewater is respectively treated and mixed into comprehensive wastewater, the comprehensive wastewater directly enters a biochemical system for treatment, the total nickel content of the comprehensive wastewater before entering the biochemical system basically fluctuates near 0.5mg/L, and the requirement that the total nickel content is not more than 0.5mg/L is difficult to meet in all time periods.
The nickel removal method is adopted to carry out transformation, the UV/Fenton oxidation flow is added to remove nickel before water inflow is generated, the effective volume of an oxidation tank is 300m 3, and the power of a UV lamp system is 57.6kW.
Before a biochemical pond, an online monitoring system is adopted to detect main pollution parameters of wastewater in an adjusting pond, ferrous sulfate, hydrogen peroxide and A are all calculated and added according to parameters given by the online monitoring system by adopting a medicine adding amount calculation and adding system, and the specific steps are as follows:
1) Determination of pollutant content and determination of drug addition:
after the regulating tank collects enough wastewater, an online monitoring system respectively samples and measures various pollutant indexes such as COD value, TP value and the like in the wastewater, and according to the measured pollutant content, the medicine adding amount is calculated and the adding system respectively calculates various medicine adding amounts;
2) UV/Fenton treatment:
The waste water in the regulating tank enters an oxidation tank in the UV/Fenton treatment system, after enough waste water is collected in the oxidation tank, ferrous sulfate is added, after the addition of the ferrous sulfate is finished, acid or alkali is added in the oxidation tank to regulate the pH 1 value of the waste water in the oxidation tank to 3-4, after the pH 1 is regulated, a UV lamp system is started, after the UV lamp system is started, hydrogen peroxide is added in the oxidation tank, after the addition of the hydrogen peroxide is finished, the UV lamp system is continuously started, and the total starting duration of the UV lamp system is 2 hours;
3) Flocculating and precipitating effluent:
After the starting time of the UV lamp system is up, closing the UV lamp system, discharging the wastewater in the oxidation tank into a dosing tank in the flocculation precipitation system, collecting enough wastewater in the dosing tank, adding A in the dosing tank, adding alkali to adjust the pH 2 value of the wastewater in the dosing tank after the adding is finished, opening a filter press, discharging the filter press to a pH callback tank, performing pressure filtration on the dry sludge, after the collecting of the pH callback tank is finished, adding enough PAM in the dosing tank, discharging the wastewater in the dosing tank into a sedimentation tank in the flocculation precipitation system, keeping the retention time in the sedimentation tank for 2 hours, discharging clear water at the upper part into the pH callback tank in the flocculation precipitation system after the retention time in the sedimentation tank is finished, discharging lower sludge into a filter press in the flocculation precipitation system, opening the filter press after the filter press is finished, discharging the clear water filtered out by the filter press to the pH callback tank, performing pressure filtration on the dry sludge, and performing pressure filtration on the filter press, and callback tank, after the pH callback tank is sufficiently collected, discharging the clear water into the pH callback tank, and adjusting the pH value to the pH value between the wastewater and the pH callback tank and the pH value of the wastewater after the wastewater is adjusted to be in the pH value of 3, and the wastewater is discharged to the biochemical system after the pH value is adjusted to be adjusted to the pH value is adjusted to be in the waste water.
Sampling and detecting the wastewater in the pH value regulating tank at different days, wherein the total nickel, COD value or TP value is changed before and after treatment as shown in the following table 2:
TABLE 2 variation of the pollutant content before and after wastewater treatment
Wherein:
1 Determination of Water quality chemical oxygen demand quick digestion spectrophotometry (HJ 399-2007)
2 Determination of Nickel in Water quality flame atomic absorption spectrophotometry (GB/T11912-1989)
3 Five-day biochemical oxygen demand measurement dilution and inoculation method of water quality (HJ 505-2009)
4 Determination of total phosphorus in Water flow injection-ammonium molybdate spectrophotometry (HJ 671-2013)
Comparing the data in table 2, the continuous operation of the equipment and the data monitoring show that after treatment, the total nickel, COD value and total phosphorus ratio of the wastewater in the pH value regulating tank are reduced, the index B/C for representing the biodegradability of the wastewater is improved, and the total nickel content of the wastewater after treatment stably meets the set target of not higher than 0.5 mg/L.
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, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A method for removing nickel before biochemical water inflow of an electroplating wastewater station, which is characterized by comprising the following steps:
1) The method comprises the steps that wastewater enters an adjusting tank before entering a UV/Fenton treatment system, after enough wastewater is collected by the adjusting tank, an online monitoring system is used for sampling and measuring COD value and TP value pollutant indexes in the wastewater respectively, and various medicine adding amounts are calculated by a medicine adding amount calculation and adding system according to the measured pollutant content;
2) The wastewater in the regulating tank enters an oxidation tank in a UV/Fenton treatment system, ferrous sulfate is added after enough wastewater is collected in the oxidation tank, and then acid or alkali is added into the oxidation tank to regulate the pH 1 of the wastewater in the oxidation tank to be between 2 and 5;
3) After the pH 1 is regulated, starting a UV lamp system in the UV/Fenton treatment system, adding hydrogen peroxide into the oxidation pond, and continuously starting the UV lamp system after the hydrogen peroxide is added, wherein the total starting time of the UV lamp system is 1-10h;
4) After the starting time of the UV lamp system is up, the UV lamp system is closed, the wastewater in the oxidation tank is discharged into a dosing tank in the flocculation precipitation system, after the dosing tank collects enough wastewater, A is added into the dosing tank, after the addition of A is finished, alkali is added into the dosing tank to adjust the pH 2 value of the wastewater in the dosing tank, and after the addition of alkali is finished, the pH 2 value range of the wastewater in the dosing tank is 9-13;
5) Adding a sufficient amount of PAM into the dosing tank after the pH 2 is regulated, and discharging the wastewater in the dosing tank into a sedimentation tank in a flocculation sedimentation system after the PAM is added, wherein the residence time of the wastewater in the sedimentation tank is 1-5h;
6) After the residence time of the wastewater in the sedimentation tank is finished, discharging upper clear water to a pH value callback tank in a flocculation sedimentation system, discharging lower sludge to a filter press in the flocculation sedimentation system, starting the filter press after the filter press collects enough sludge, discharging clear water filtered by the filter press to the pH value callback tank, and additionally treating dry sludge filtered by the filter press;
7) Adding acid into the pH value callback pond until the pH 3 of the wastewater in the pH value callback pond is within 6-9 after the sufficient wastewater is collected in the pH value callback pond, and discharging the wastewater in the pH value callback pond to a biochemical treatment system after the pH value of the wastewater in the pH value callback pond is regulated;
the method for calculating the addition amount of the ferrous sulfate (FeSO 4·7H2 O) comprises the following steps:
m1 = 2.34 × COD （1）
The unit of m 1 in the formula (1) is kg/m 3 or kg/t, the unit of COD is g/L, and the volume unit of wastewater m 3 (cubic meters) is equivalent to the weight unit of t (tons);
m2 = 9.86 × TP （2）
The unit of m 2 in the formula (2) is kg/m 3 or kg/t, the TP is the total phosphorus content in the wastewater, and the unit of the TP is g/L;
Comparing the sizes of m 1 and m 2, taking the larger one of m 1 and m 2, and marking the larger one of m 1 and m 2 as m 0;
Calculating the addition amount of ferrous sulfate by combining the effective volume in the oxidation pond:
M = U × m0 （3）
The effective volume of the oxidation pond is U, the unit of U is M 3 or t, the result M calculated by the calculation formula (3) is the amount of ferrous sulfate to be added in the oxidation pond, and the unit is: kg;
The calculation method of the addition amount of the A is as follows:
c0 = 11.9 × TP （6）
The unit of c 0 in the formula (6) is kg/m 3 or kg/t, the TP is the total phosphorus content in the wastewater, and the unit of TP is g/L;
Calculating the addition amount of A by combining the effective volume in the oxidation pond:
C = U × c0 （7）
the effective volume of the oxidation tank is U, the unit of U is m 3 or t, the result C calculated by the calculation formula (7) is the amount of A to be added in the dosing tank, and the unit is: kg.
2. The method for removing nickel before biochemical water inflow in an electroplating wastewater station according to claim 1, wherein the starting time of the UV lamp system is in a range of 1.5-5 h.
3. A method for nickel removal prior to biochemical feed water to an electroplating wastewater station according to claim 1, wherein the pH 2 is in the range of 9-10.
4. The method for removing nickel before biochemical water inflow of an electroplating wastewater station according to claim 1, wherein A is inorganic salt and the mass percentage content of hydrogen peroxide is 27.5%.
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