CN102627346B - Adding control method of heavy metal trapping agent - Google Patents
Adding control method of heavy metal trapping agent Download PDFInfo
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- CN102627346B CN102627346B CN201210028199.XA CN201210028199A CN102627346B CN 102627346 B CN102627346 B CN 102627346B CN 201210028199 A CN201210028199 A CN 201210028199A CN 102627346 B CN102627346 B CN 102627346B
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- Prior art keywords
- heavy metal
- chelating agent
- metal chelating
- water
- absorbancy
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002351 wastewater Substances 0.000 claims abstract description 48
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims description 69
- 238000012545 processing Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000002835 absorbance Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000003814 drug Substances 0.000 description 24
- 239000000701 coagulant Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000012990 dithiocarbamate Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 239000013522 chelant Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000003352 sequestering agent Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- 230000001112 coagulating effect Effects 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000008676 import Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- -1 cycloalkyl dithiocar-bamate Chemical compound 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 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 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000012806 monitoring device Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Abstract
The invention aims to provide an adding control method of heavy metal trapping agent. In the method, waste water containing heavy metal is processed by utilizing aminodithioformic acid heavy metal trapping agent and the adding dose of the heavy metal trapping agent can be suitable. It is characterized in that the aminodithioformic acid heavy metal trapping agent is added in the waste water containing heavy metal. After adding the aminodithioformic acid heavy metal trapping agent , heavy metal compound is added into processed water that is separated to make heavy metal ion react with aminodithioformic acid heavy metal trapping agent and display color, and the absorbance or transmissivity of 400 nm to 700 nm wavelength is measured. The adding volume of the aminodithioformic acid heavy metal trapping agent is controlled according to the measuring result.
Description
Technical field
The present invention relates to a kind of dosing control method of heavy metal chelating agent, especially relate to the dosing control method of the dithiocarbamic acid class heavy metal chelating agent in a kind for the treatment of process of the waste water that contains heavy metal that removes the heavy metal composition in this waste water by add dithiocarbamic acid class heavy metal chelating agent in containing the waste water of heavy metal.
Background technology
The waste water that plating waste water, coating wastewater etc. contain heavy metal is the waste water that contains the heavy metals such as copper, chromium, zinc, lead, manganese, iron, nickel, cadmium.According to the dirt of < < water quality, prevent method (Water Pollution Control Law) > > etc., the waste water that row obligation contains heavy metal to these is suitably processed.
As the method for wastewater treatment that contains heavy metal, known have by adding using the method (patent documentation 1) that the dithiocarbamate-based inner complex class heavy metal chelating agent as main body carries out coagulating sedimentation processing.In use, have in the treatment process of the waste water that contains heavy metal of this dithiocarbamic acid class heavy metal chelating agent, no matter if how the waste water quality of contained heavy metal changes all process by quantitative interpolation inner complex class heavy metal chelating agent, when the addition of inner complex class heavy metal chelating agent is not enough or add when excessive, can reduce handled water quality.On the other hand, when interpolation is excessive, can increase in vain the cost of dithiocarbamic acid class heavy metal chelating agent.
In patent documentation 1, recorded a kind of method, that is: while adding inner complex class heavy metal chelating agent to remove the heavy metal composition in this waste water in the waste water that is containing heavy metal, in the waste water that contains heavy metal at this, add inner complex class heavy metal chelating agent, and measure the addition of this inner complex class heavy metal chelating agent and the redox potential variable quantity of this waste water before and after this inner complex class heavy metal chelating agent adds, according to this measurement result, determine required addition.
Inner complex class heavy metal chelating agent, the heavy metal ion having in inner complex formation group (dithiocarbamate-based) and this group and waste water reacts and becomes insoluble solution compound matter and generate precipitation.In this reaction process, redox potential (ORP) reduces.In the method for patent documentation 1, utilized the variation of above-mentioned ORP, that is: change to the concentration of processing the inner complex class heavy metal chelating agent adding in object waste water, and corresponding therewith, when the higher ORP of interpolation concentration of heavy metal chelating agent becomes lower.
In patent documentation 2, record: from landfill handled thing the like waste, gather sample, sample with respect to specified amount adds liquid sequestrant, heavy metal and chelate liquid mixture in sample are reacted, for the sample that is added with chelate liquid mixture, obtain for the absorbancy IB in the specificity wavelength of chelate liquid mixture, according to absorbancy 1B, obtain the amount B of unreacted chelate liquid mixture in sample, by blank test, obtain the absorbancy IA in the wavelength suitable with added chelate liquid mixture total amount, according to absorbancy IA, obtain the total amount A of added chelate liquid mixture, poor according to this total amount A and amount B, obtains the amount C of the chelate liquid mixture reacting with heavy metal, and being recently identified for of the specified amount based on this amount C and sample processed the suitable addition of the chelate liquid mixture of waste.In patent documentation 2, record: when sequestrant is dithiocarbamic acid class, this wavelength is 286nm, 257nm, 215nm.
In patent documentation 3, record: adopt dithiocarbamic acid class sequestrant, the flying dust that contains heavy metal (fly ash) is carried out to the heavy metal method that dissolving is not processed.In this patent documentation 3, record: according to the absorbancy of wavelength more than 330nm (particularly 350nm), measure sequestrant concentration in liquid (patent documentation 3 0018 section, 0028 section).
Prior art document
Patent documentation
Patent documentation 1: No. 2001-340874, TOHKEMY
Patent documentation 2: No. 10-337550, Japanese kokai publication hei
Patent documentation 3: No. 2010-260010, TOHKEMY
Summary of the invention
In patent documentation 2,3, employing absorbance method is quantitative to dithiocarbamic acid class sequestrant, that the absorbancy of dithiocarbamic acid class sequestrant self is detected, therefore, in the situation that the concentration of the dithiocarbamic acid class sequestrant in the processing of the waste water that contains heavy metal etc. is low or affect the organic concentration change in the check water of absorbancy, measures precision and reduce.
The object of the present invention is to provide a kind of dosing control method of heavy metal chelating agent, described method processes by dithiocarbamic acid class heavy metal chelating agent the waste water that contains heavy metal, wherein, can make the chemical feeding quantity of this heavy metal chelating agent reach neither too much nor too little appropriate.
The dosing control method of the heavy metal chelating agent of technical scheme 1 of the present invention, the method removes the heavy metal composition in this waste water for adding dithiocarbamic acid class heavy metal chelating agent at the waste water that contains heavy metal, and the method has been determined the required addition of this dithiocarbamic acid class heavy metal chelating agent, it is characterized in that, in the waste water that contains heavy metal at this, add dithiocarbamic acid class heavy metal chelating agent, and after adding this dithiocarbamic acid class heavy metal chelating agent, in the processing water of solid-liquid separation, add heavy metal compound, dithiocarbamic acid class heavy metal chelating agent in heavy metal ion and this processing water is reacted and after developing the color, measure absorbancy or the transmissivity of 400～700nm wavelength, based on this measurement result, control the addition of above-mentioned dithiocarbamic acid class heavy metal chelating agent.
The dosing control method of the heavy metal chelating agent of technical scheme 2 of the present invention, is characterized in that, in the dosing control method of the heavy metal chelating agent described in technical scheme 1, described heavy metal compound is water-soluble molysite.
The dosing control method of the heavy metal chelating agent of technical scheme 3 of the present invention, is characterized in that, in the dosing control method of the heavy metal chelating agent described in technical scheme 2, measures absorbancy or the transmissivity of 400～500nm wavelength.
The dosing control method of the heavy metal chelating agent of technical scheme 4 of the present invention, in the dosing control method of the heavy metal chelating agent in technical scheme 1 to 3 described in any one, control the addition of described heavy metal chelating agent so that the trapping agent concentration in the processing water of obtaining according to described absorbancy becomes 2～10mg/L.
The dosing control method of the heavy metal chelating agent of technical scheme 5 of the present invention, the method removes the heavy metal composition in this waste water for adding dithiocarbamic acid class heavy metal chelating agent at the waste water that contains heavy metal, and the method has been determined the required addition of this dithiocarbamic acid class heavy metal chelating agent, it is characterized in that, in the waste water that contains heavy metal at this, add dithiocarbamic acid class heavy metal chelating agent, and after adding this dithiocarbamic acid class heavy metal chelating agent, measure absorbancy or the transmissivity of 400～700nm wavelength of the processing water of solid-liquid separation, based on this measurement result, control the addition of above-mentioned dithiocarbamic acid class heavy metal chelating agent.
In the dosing control method of heavy metal chelating agent of the present invention, during addition in determining the waste water that dithiocarbamic acid class heavy metal chelating agent is containing heavy metal, in this waste water, add this trapping agent and carry out solid-liquid separation, and by after adding the heavy metal compounds such as water-soluble molysite, mantoquita in the processing water in solid-liquid separation and heavy metal ion and residual dithiocarbamic acid class heavy metal chelating agent being reacted develop the color, measure absorbancy or the transmissivity of 400～700nm wavelength.Thus, by heavy metal ion and dithiocarbamic acid class heavy metal chelating agent being reacted develop the color to measure absorbancy or the transmissivity of the visible region of 400～700nm wavelength, therefore, can not be subject to the impact of this trapping agent on visible absorption, even when the organic concentration change that affects absorbancy or transmissivity, also can precision detect well and quantitative residual trapping agent.And the absorbancy sensor of 400～700nm or transmissivity sensor, compare cheap with UV absorbancy sensor.
In addition, while being pre-existing in enough heavy metal ion in the processing water of solid-liquid separation, even if do not add heavy metal compound, can there is not color reaction yet, and can detect and quantitative this residual trapping agent.
Accompanying drawing explanation
Fig. 1 means the schema of the dosing control method of the heavy metal chelating agent in embodiment.
Fig. 2 means the schema of the dosing control method of the heavy metal chelating agent in other embodiment.
Fig. 3 means the graphic representation of the absorbancy of heavy metal chelating agent.
Fig. 4 means and adds Fe
2+time the graphic representation of absorbancy.
Fig. 5 means and adds Fe
2+time the graphic representation of absorbancy.
Fig. 6 means and adds Fe
2+time the graphic representation of absorbancy.
Fig. 7 means and adds Cu
2+time the graphic representation of absorbancy.
Fig. 8 means and adds Fe
3+, Al
3+or Ca
2+time the graphic representation of absorbancy.
Fig. 9 means and adds Cu
2+or Fe
2+time the graphic representation of absorbancy.
Figure 10 means and adds Cu
2+time the graphic representation of absorbancy.
Figure 11 means the Ni processing in water, the graphic representation of Zn concentration.
The explanation of Reference numeral
1 neutralizing well
2 reactive tanks
3 medicament storage tanks
4 coagulation tanks
5 coagulation tanks
6 settling tanks
7 measuring reservoirs
8 absorbancy meters
Embodiment
Below, further describe the present invention.
In the present invention, by add dithiocarbamic acid class heavy metal chelating agent in containing the waste water of heavy metal, heavy metal in this waste water and this trapping agent are reacted make its not dissolving, then carry out solid-liquid separation.
The waste water that contains heavy metal as this, can exemplify the waste water in following source, but be not limited thereto: the plating operation of iron steel or semi-conductor and automobile making; Fume cleaning, the control of dust operation in incinerating waste material factory (clear Sweep work Games) or power station; Battery, glass manufacture operation; The landfill that trade waste is processed field leaches water etc.
As the heavy metal in the above-mentioned waste water that contains heavy metal, can illustration mercury, cadmium, arsenic, lead, sexavalent chrome, selenium, copper, zinc, manganese, ferrous iron, nickel, ferric iron etc., but be not limited thereto.
Concentration of heavy metal ion in containing the waste water of heavy metal, is generally below about 100ppm, for example, in 1～50ppm left and right, but is not limited thereto.
As dithiocarbamic acid class heavy metal chelating agent, can illustration dithiocar-bamate, the dithiocar-bamate of dialkyl dithiocarbamate, cycloalkyl dithiocar-bamate, piperazine bisdithiocarbamic salt, tetren dithiocar-bamate, polyamines etc., but be not limited thereto.In addition, to they both can use separately a kind of also can be used together two or more.
As the compound matter of not dissolving generating for add above-mentioned trapping agent in containing the waste water of heavy metal, carry out solid-liquid separation solid-liquid separating method used, can use the method arbitrarily of precipitate and separate, filtration, centrifugation, membrane sepn etc.
As making an addition in the processing water of this solid-liquid separation and reacting with residual trapping agent and the heavy metal compound that develops the color, can enumerate: Fe
2+, Fe
3+, Cu
2+, Zn
2+, Pb
2-, Ni
2+, Cd
2+, Mn
2+deng the water-soluble salts such as vitriol, hydrochloride, but do not need the special viewpoint of processing, preferably Fe while discharging from colour developing degree or analyzing the end of job
2+or Fe
3+salt.
Conventionally, colour developing when adding above-mentioned heavy metal compound in rare (concentration the is low) aqueous solution at above-mentioned dithiocarbamic acid class heavy metal chelating agent, the addition that more increases this heavy metal compound develops the color denseer, more than the equivalent reaction amount that trapping agent total amount in water and add heavy metal compound react if reach, even if increase again the addition of heavy metal compound, can not make colour developing further thicken yet.Therefore, in the present invention, when solid-liquid separation being processed to residual trapping agent concentration in water, carry out when quantitative, preferably for example, in the mode of above-mentioned equivalent reaction amount above (, 1～10 of equivalent reaction amount times, especially 1.5～5 times of left and right), add heavy metal compound.
Measure after absorbancy adding heavy metal compound in mode more than equivalent reaction amount, according to the working curve of obtaining in advance (or calibration relation), obtain the residual trapping agent concentration in the processing water of solid-liquid separation.This working curve (or calibration relation) is to try to achieve according to add the absorbancy of measuring after heavy metal compound more than equivalent reaction amount in the trapping agent aqueous solution of concentration known.
By operation like this, the trapping agent concentration in the processing water of the solid-liquid separation based on obtained, controls the trapping agent addition to waste water.Above-mentioned control, carries out so that the trapping agent concentration in the processing water of solid-liquid separation reaches the mode of target concentration range.As the lower value of target concentration range for example 0～10mg/L, especially 2～5mg/L, as higher limit for example 8～50mg/L, especially 10～30mg/L left and right, but be not limited thereto.
In addition,, while whether remaining trapping agent in the processing water detecting in solid-liquid separation, can make the addition of heavy metal compound be less than above-mentioned equivalent reaction amount.
In addition, if because the heavy metal concentration height in waste water etc. is former thereby cause processing in water and remaining plurality of heavy metal in solid-liquid separation, even and trapping agent and residual heavy metal ion react while also developing the color, sometimes can not add heavy metal compound.
The mensuration wavelength of absorbancy or transmissivity is 400～700nm, is preferably 400～660nm, is particularly preferably 400～500nm.If be less than this scope, can be subject to also step-down of the impact of other organic compound in waste water and sensitivity.If be greater than this scope, sensitivity step-down.
By control the example of flow process of the method for wastewater treatment of the trapping agent addition in waste water with reference to Fig. 1, the trapping agent concentration of 2 Benqs in the processing water of solid-liquid separation.
In this Waste Water Treatment, by neutralizing well 1, in containing the waste water of heavy metal, interpolation acid (HCl etc.) or alkali (NaOH etc.) pH adjusting agent are carried out pH regulator, then, import in reactive tank 2, by dosing pump P, from medicament storage tank 3, add inner complex class heavy metal chelating agent so that react, in coagulation tank 4, by add inorganic coagulant in reaction solution, carry out coagulating treatment, then, in coagulation tank 5, by adding high-molecular coagulant adopting, carry out coagulating treatment, and in settling tank 6, coagulating treatment liquid is carried out to solid-liquid separation, and obtained upper strata clear water is discharged as processing water.And, adopt water extracter (not shown) etc., separated mud is carried out to processed.
A part of obtaining from the processing water of settling tank 6 by separation imports in measuring reservoir 7, adds heavy metal compound, and adopts absorbancy meter 8 to measure the absorbancy of 400～700nm.By in above-mentioned absorbancy input control device 9, calculate the required addition of inner complex class heavy metal chelating agent.Based on this calculation result, control dosing pump P, carry out the suitable dosing of inner complex class heavy metal chelating agent.
Absorbance measurement in measuring reservoir 7, both can carry out continous way mensuration, also can carry out intermittent type mensuration.
In addition, by the calculation result of absorbancy meter 8 and controller 9, through communication terminal, utilize telephone line to deliver letters to the central monitoring device of zone center mechanism at a distance, and by the setting changing from this central monitoring device (for example, the change of the control set(ting)value of the setting changing at measurement interval, correction factor etc. etc.) with telephone line, through communication terminal, to controller, deliver letters, also can hold and monitor the treatment situation in remote area and carry out teletype control by the mutual data corresponding of this locality/central authority.
In Fig. 1, by the processing water to from settling tank 6, add heavy metal compound and measure absorbancy, but also can as shown in Figure 2, fetching water by the top from coagulation tank 5, import in measuring reservoir 7 and add heavy metal compound and measure absorbancy.Now, preferably in groove 7, import to gather water and add heavy metal compound stirs after the standing coagulum that a little while makes precipitate, then, to supernatant water mensuration absorbancy.The method of Fig. 2 is compared with the method for Fig. 1, easily makes absorbancy meter stained, but adds after sequestrant to the time lag of measuring till absorbancy littlely, therefore can obtain precision good control.
In addition, in Fig. 1,2, used settling tank 6, but as mentioned above, as solid-liquid separating method, can make in all sorts of ways.In addition, in the processing water of solid-liquid separation, remain plurality of heavy metal and while not needing to add heavy metal compound, can discharge from the stream of the processing water of settling tank 6 on or in settling tank 6, absorbancy meter 8 is set.And, can also use transmission gage to replace absorbancy meter 8.
In Fig. 1, Fig. 2, take and further improve the water quality of processing water and by inorganic coagulant, carry out coagulating treatment as object is provided with coagulation tank 4, but adopting inorganic coagulant to carry out under the situation of coagulating treatment, sometimes based on inorganic coagulant, can remove unnecessary heavy metal chelating agent and become and be difficult to control, therefore, coagulation tank 4 is not set in this case and omits the processing that utilizes inorganic coagulant to carry out.In addition, sometimes in order to remove by the heavy metal chelating agent of excessive interpolation (residual heavy metal chelating agent), add inorganic coagulant.In the present invention, heavy metal chelating agent can be controlled to a small amount of residual degree, therefore, when adding inorganic coagulant with above-mentioned purpose, can omit the processing that utilizes inorganic coagulant to carry out.
As inorganic coagulant, can use bodied ferric sulfate, polymerize aluminum chloride, Tai-Ace S 150, iron(ic) chloride etc.As high-molecular coagulant adopting, can be used as multipolymer, sodium acrylate and the acrylamide of homopolymer, sodium acrylate and acrylamide of the acrylamide of anionic property high-molecular coagulant adopting and trimer of 2-acrylamide-2-methyl propane sulfonic acid etc.
As long as contain the heavy metal that can react with dithiocarbamic acid class heavy metal chelating agent, no matter the waste water that contains which kind of heavy metal, i.e. applicable method of the present invention.
Embodiment
Below, by enumerating experimental example and embodiment is described more specifically the present invention.
< experimental example 1>
For four kinds of medicaments 1～4 in the table 1 as dithiocarbamic acid class heavy metal chelating agent, measured absorbance spectrum and be shown in Fig. 3.As shown in the figure, any trapping agent all has strong absorption band and have extinction peak near about 240nm wavelength at 200～350nm wavelength place.And, very little in the absorbancy at the above wavelength of 400nm place.
Table 1
| Compound title | |
| Medicament 1 | Polyamines-dithiocar-bamate |
| Medicament 2 | Dithiocarbonic anhydride-sodium hydroxide modifier of polymine chlorobenzyl |
| Medicament 3 | Piperazine-bis--dithiocar-bamate |
| Medicament 4 | Tetren dithiocar-bamate |
< experimental example 2>
In the water of the medicament 3 as trapping agent that is dissolved with 30mg/L, as Fe
2+add the FeSO of 10mg/L
4, and measure absorbance spectrum.Show the result in table 4.In Fig. 4, illustrate in the lump and do not add FeSO
4time spectrum.
As shown in Figure 4, by adding Fe
2+, confirm to produce and to using the strong extinction of 420nm wavelength as peak.
Therefore the 30mg/L aqueous solution of, measuring with respect to medicament 3 changes FeSO
4addition time the absorbancy of 470nm wavelength, and be shown in Fig. 5.As shown in Figure 5, at Fe
2+addition be 10mg/L when above absorbancy reached the limit, and confirm Fe
2+with the equivalent reaction amount of the medicament 3 of 30mg/L be 10mg/L.
Therefore, the concentration of medicament 3 is made as to the scope of 3～30mg/L, and measures as Fe more than equivalent reaction amount
2+add the FeSO of 10mg/L
4time the absorbancy of 470nm wavelength, and show the result in Fig. 6.As shown in Figure 6, between the concentration of medicament 3 and absorbancy, there is linear relationship.Confirm thus, according to passing through to add Fe more than equivalent reaction amount
2+the absorbancy of measuring, concentration that can gauge water Chinese medicine 3.
< experimental example 3,4>
In order to confirm except Fe
2+the coloration of heavy metal ion in addition, is determined in the aqueous solution of medicament 3 of 30mg/L as Cu
2+add the CuSO of 20mg/L
4time spectrum and be shown in (experimental example 3) in Fig. 7.In addition, be determined in the aqueous solution of medicament 3 of 30mg/L as Fe
3+add the Fe of 10mg/L
2(SO
4)
3time spectrum and be shown in (experimental example 4) in Fig. 8.
Consequently, confirmed at Cu
2+, Fe
3+situation under also react at about 460nm (Cu with medicament 3
2+situation under) or 360nm (Fe
3+situation under) produce the colour developing with peak.And confirm, when adding Al
3+, Ca
2+time, do not produce as shown in Figure 8 colour developing.
< experimental example 5>
Preparation is as the aqueous solution of 3～36mg/L of the medicament 2 of trapping agent, and respectively as Cu
2+add the CuSO of 10mg/L
4or as Fe
2+add the FeSO of 10mg/L
4, and the absorbancy of 425nm wavelength is shown in Fig. 9.In Fig. 9, also show and do not add Cu
2+, Fe
2+absorbancy.As shown in Figure 9, confirmed the in the situation that of medicament 2 also and Cu
2+, Fe
2+react and develop the color, and have linear dependence relation between absorbancy and medicament 2 concentration, can be according to the concentration of absorbancy quantitative pharmacy 2.
< experimental example 6>
Except make similarly to have measured absorbancy with medicament 1 or 4 with experimental example 3 as trapping agent.Show the result in Figure 10.As shown in figure 10, confirmed the in the situation that of medicament 1,4 also and Cu
2+react and develop the color.
< experimental example 7>
By the Waste Water Treatment shown in Fig. 1, processed the simulated wastewater of the waste water that contains heavy metal (waste water that contains Ni, Zn) at simulated automotive workshop.That is, at NiSO that to contain as Ni be 5mg/L
4with the ZnSO that is 5mg/L as Zn
4the aqueous solution in, add the medicament 2 of 3mg/L, 6mg/L, 9mg/L, 12mg/L, 15mg/L, 18mg/L or 24mg/L, then, add inorganic coagulant (bodied ferric sulfate), anionic polymer coagulating agent (polyacrylamide) is processed.
By the Ni processing in water
2+, Zn
2+concentration is shown in Figure 11.As shown in figure 11, if confirm, adding 2 of 15～24mg/L medicaments in the situation that of this waste water does not have excessive dosing and can trap fully Ni and Zn.
< embodiment 1>
In above-mentioned experimental example 7, in the processing water from settling tank, add the Fe of 10mg/L
2+, measured the absorbancy of 425nm.And, when so that this absorbancy becomes 0.12～1 mode (that is, so that process the mode that the concentration of the medicament 2 in water becomes 5～25mg/L) when carrying out dosing and controlling, the Ni in processing water
2+and Zn
2+concentration all becomes below 0.1mg/L.
Claims (4)
1. the dosing control method of a heavy metal chelating agent, the method removes the heavy metal composition in this waste water for adding dithiocarbamic acid class heavy metal chelating agent at the waste water that contains heavy metal, and the method has been determined the required addition of this dithiocarbamic acid class heavy metal chelating agent, it is characterized in that
In the waste water that contains heavy metal at this, add dithiocarbamic acid class heavy metal chelating agent, and after adding this dithiocarbamic acid class heavy metal chelating agent, in the processing water of solid-liquid separation, add heavy metal compound,
Dithiocarbamic acid class heavy metal chelating agent in heavy metal ion and this processing water is reacted and after developing the color, measure absorbancy or the transmissivity of 400～700nm wavelength, based on this measurement result, so that the trapping agent concentration in the processing water of solid-liquid separation reaches the mode of target concentration range, control the addition of described dithiocarbamic acid class heavy metal chelating agent
And described heavy metal compound is Fe
2+, Fe3
+, Cu
2+, Zn
2+, Pb
2+, Ni
2+, Cd
2 +, Mn
2+water-soluble salt,
And described target concentration range is 0～50mg/L.
2. the dosing control method of heavy metal chelating agent as claimed in claim 1, is characterized in that, described heavy metal compound is water miscible molysite or water miscible mantoquita.
3. the dosing control method of heavy metal chelating agent as claimed in claim 2, is characterized in that, measures absorbancy or the transmissivity of 400～500nm wavelength.
4. the dosing control method of heavy metal chelating agent as claimed any one in claims 1 to 3, it is characterized in that, control the addition of described heavy metal chelating agent so that the trapping agent concentration in the processing water of obtaining according to described absorbancy or transmissivity becomes 10～30mg/L.
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| JP6044160B2 (en) * | 2012-07-31 | 2016-12-14 | 栗田工業株式会社 | Method and apparatus for treating wastewater containing heavy metals |
| JP5648759B2 (en) * | 2013-02-22 | 2015-01-07 | 栗田工業株式会社 | Method for measuring lysate concentration |
| JP2014215248A (en) * | 2013-04-26 | 2014-11-17 | 東ソー株式会社 | Determination device of necessary quantity of heavy metal treatment agent |
| JP6701085B2 (en) * | 2013-11-11 | 2020-05-27 | ナルコ カンパニー | Method of heavy metal removal from wastewater streams |
| WO2015114805A1 (en) * | 2014-01-31 | 2015-08-06 | 栗田工業株式会社 | Method and device for treating heavy-metal-containing wastewater |
| JP6314587B2 (en) * | 2014-03-26 | 2018-04-25 | 栗田工業株式会社 | Concentration measuring device and method for cleaning the concentration measuring device |
| JP5880625B2 (en) * | 2014-06-13 | 2016-03-09 | 栗田工業株式会社 | Method and apparatus for measuring heavy metal collector concentration |
| JP5962722B2 (en) * | 2014-08-29 | 2016-08-03 | 栗田工業株式会社 | Chelating agent addition amount determination device and chelating agent addition amount determination method |
| JP2016137429A (en) * | 2015-01-27 | 2016-08-04 | 王子ホールディングス株式会社 | Method and equipment for treating heavy metal-containing waste water |
| WO2016148218A1 (en) * | 2015-03-18 | 2016-09-22 | 栗田工業株式会社 | Dithiocarbamic acid-based heavy metal scavenger concentration measurement method and concentration measurement reagent |
| JP5962880B1 (en) * | 2015-03-18 | 2016-08-03 | 栗田工業株式会社 | Method for measuring concentration of dithiocarbamic acid heavy metal scavenger and reagent for concentration measurement |
| CN106032294A (en) * | 2015-03-19 | 2016-10-19 | 厦门蔚扬药业有限公司 | Method for treating residual heavy metal ions in organic reaction with dithiocarbamate |
| JP6765200B2 (en) * | 2015-03-25 | 2020-10-07 | 住友重機械エンバイロメント株式会社 | Chelating agent quantification method and chelating agent quantification system |
| JP6969076B2 (en) * | 2015-08-07 | 2021-11-24 | 東ソー株式会社 | Purifying agent for heavy metal-containing aqueous solution, and method for purifying heavy metal-containing aqueous solution |
| CN106915812A (en) * | 2015-12-28 | 2017-07-04 | 沈阳中科环境工程科技开发有限公司 | A kind of chemical nickle-plating wastewater inorganic agent and preparation method thereof |
| JP6862659B2 (en) * | 2016-03-01 | 2021-04-21 | 東ソー株式会社 | How to purify nickel-containing aqueous solution |
| JP6862660B2 (en) * | 2016-03-01 | 2021-04-21 | 東ソー株式会社 | Purifying agent for nickel-containing aqueous solution and purification method for nickel-containing aqueous solution |
| JP7031176B2 (en) * | 2016-09-08 | 2022-03-08 | 東ソー株式会社 | Purifying agent for nickel-containing aqueous solution and purification method for nickel-containing aqueous solution |
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| CN108508114A (en) * | 2018-05-25 | 2018-09-07 | 中科广化（重庆）新材料研究院有限公司 | The high performance liquid chromatograph assay method of sodium dimethyl dithiocarbamate content in a kind of solution |
| CN108414467A (en) * | 2018-05-25 | 2018-08-17 | 中科广化（重庆）新材料研究院有限公司 | The ultraviolet specrophotometer assay method of sodium dimethyl dithiocarbamate content in a kind of solution |
| CN109988438B (en) * | 2019-04-12 | 2020-11-13 | 浙江纳美新材料股份有限公司 | Organic pigment micronization pretreatment method |
| CN112756372A (en) * | 2020-12-19 | 2021-05-07 | 宁波明州环境能源有限公司 | Method for judging addition of chelating agent in fly ash stabilization process |
| CN115684144A (en) * | 2023-01-03 | 2023-02-03 | 广东环凯生物技术有限公司 | Method for rapidly detecting arsenic content in water |
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| JPS5745633B2 (en) * | 1973-12-08 | 1982-09-29 | ||
| CA2078648A1 (en) * | 1991-09-30 | 1993-03-31 | David C. Yeaw | Test kit and method for the determination of metal ion concentration in solution |
| US5328599A (en) * | 1993-03-08 | 1994-07-12 | Nalco Chemical Company | System using sulfide ion-selective electrodes for control of chemical feed of organic sulfide products for metal ion precipitation from waste water |
| US5435969A (en) * | 1994-03-29 | 1995-07-25 | Nalco Chemical Company | Monitoring water treatment agent in-system concentration and regulating dosage |
| JP3460570B2 (en) * | 1997-04-07 | 2003-10-27 | Ｊｆｅスチール株式会社 | Method for determining proper amount of heavy metal stabilizer and method for treating chemicals in waste |
| JP4543502B2 (en) * | 2000-06-01 | 2010-09-15 | 栗田工業株式会社 | Determination method of required addition amount of chelating heavy metal scavenger, chemical injection control method and chemical injection control device |
| JP3911541B2 (en) * | 2003-01-09 | 2007-05-09 | Ｄｏｗａエコシステム株式会社 | Fly ash treatment |
| JP5150853B2 (en) * | 2008-03-19 | 2013-02-27 | オリエンタル技研工業株式会社 | Method and apparatus for determining the appropriate amount of fixative for immobilizing heavy metals in incineration fly ash |
| JP5378873B2 (en) * | 2009-05-08 | 2013-12-25 | Ｄｏｗａエコシステム株式会社 | Method for determining required amount of chelating agent and method for treating fly ash |
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