CN103864196A - Treatment method for waste liquid produced by permanganate titration COD (chemical oxygen demand) online determination instrument - Google Patents

Treatment method for waste liquid produced by permanganate titration COD (chemical oxygen demand) online determination instrument Download PDF

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CN103864196A
CN103864196A CN201410101625.7A CN201410101625A CN103864196A CN 103864196 A CN103864196 A CN 103864196A CN 201410101625 A CN201410101625 A CN 201410101625A CN 103864196 A CN103864196 A CN 103864196A
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waste liquid
concentration
potassium permanganate
line determination
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CN103864196B (en
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丁明光
王恩强
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Molway Environmental Science & Technology Co Ltd
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Abstract

The invention provides a treatment method for waste liquid produced by a permanganate titration COD (chemical oxygen demand) online determination instrument. The treatment method for the waste liquid produced by the permanganate titration COD online determination instrument is characterized by comprising the following steps: firstly, preparing a transforming agent solution, wherein concentration of Na2C2O4 in the transforming agent solution is 1-50g/L, concentration of Na2S2O3.5H2O is 0-100g/L, concentration of FeSO4 is 0-27g/L, concentration of FeCl2 is 0-23g/L, concentration of ethyl alcohol is 0-24g/L and concentration of phenol is 0-24g/L; secondly, adding the transforming agent solution into the waste liquid which is produced by the permanganate titration COD online determination instrument, heating, stirring and performing reaction; thirdly, adding alkaline into the waste liquid after the reaction in the step two is finished, stirring and performing reaction, standing after the reaction is finished, separating supernate from sediment, and regulating pH value of the supernate to be 7.0-8.0, so that treated waste liquid is obtained. By adopting the treatment method for the waste liquid produced by the permanganate titration COD online determination instrument, the waste liquid produced by COD online determination by adopting a national standard method can be rapidly and comprehensively treated, and solution which is difficult to store and has high toxicity can be transformed into solid which is easy to store and transport and has low toxicity.

Description

The method for treating waste liquid that potassium permanganate process on-line determination COD instrument produces
Technical field
The present invention relates to the method for treating waste liquid that potassium permanganate process on-line determination COD instrument produces, the waste liquid producing for the treatment of potassium permanganate process on-line determination COD instrument.
Background technology
Potassium permanganate process measure COD be at present both at home and abroad consistent generally acknowledged mensuration COD standard method (State Bureau of Environmental Protection compiles, water and effluent monitoring analytical procedure [M]. the 4th edition. Beijing: environmental science press, 2002,10-213).The principle of measuring is: the mixed solution of water sample, potassium permanganate and the vitriol oil is heated to 100 DEG C in digestion pool, high manganese ion is reduced positive divalent and changes color from positive 7 valencys as oxygenant manganese, in reaction, the ORP value of solution becomes corresponding relation with the content of organic compound in sample, COD analytical instrument by ORP value and potassium permanganate consumption directly the COD in sample is shown.Part instrument Sulfuric acid disilver salt catalyzer, the interference of removing chlorion with Mercury bisulfate.Therefore, measure in the waste liquid of COD acidity high, and the content of toxic heavy metal manganese, silver is high.If not treated, directly enter water drain, can cause serious secondary pollution.Especially China is now in the high-speed developing period, the increasing of environment supervision, online water quality is all actively being installed by various places environmental administration, Online monitoring of pollution sources equipment, current most of import and domestic " COD on line analyzer " all adopt GB potassium permanganate process to measure COD, and these on line analyzers all do not design the treatment unit of waste liquid, these discharging of waste liquid that contain toxic heavy metal ion are in water drain or field environment, although each amount is little, but concentration is higher, accumulate over a long period, still can cause serious secondary pollution, seem day by day urgent so study the treatment process of this waste liquid.
Mainly under stirring at low speed to the treatment process of measuring COD waste liquid at present, extraction agent is dissolved in after solvent, slowly add promoting agent, high-speed stirring again, add isopyknic additive agent modified, make water-in-oil-type liquid, manganese concentration is processed at the waste water of 10~200m g/L, profit volume ratio is 1: 3~1: 50, outer water p H is 3.0~6.5, after stirring at low speed 10~40min, stratification, the oil phase obtaining after layering is through supercentrifuge breakdown of emulsion, isolate organic phase and interior water, interior water is for the recycling of manganese, organic phase is returned and is continued to use, water outlet manganese content reaches discharging standards.
Summary of the invention
The method for treating waste liquid that the object of this invention is to provide the generation of potassium permanganate process on-line determination COD instrument can make the toxic heavy metal ion waste liquid harmless treatment producing in national standard method (GB/11892-1989) on-line measurement COD process, prevents that secondary pollution from occurring.
In order to achieve the above object, the invention provides the method for treating waste liquid that a kind of potassium permanganate process on-line determination COD instrument produces, it is characterized in that, concrete steps comprise:
The first step: preparation transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 1-50g/L, Na 2s 2o 35H 2the concentration of O is 0-100g/L, FeSO 4concentration is 0-27g/L, FeCl 2concentration be that the concentration of 0-23g/L, ethanol is that the concentration of 0-24g/L, phenol is 0-24g/L;
Second step: add transforming agent solution in the waste liquid producing to potassium permanganate process on-line determination COD instrument, heated and stirred reaction;
The 3rd step: will add alkali in the reacted waste liquid of second step, stirring reaction, leaves standstill after reaction, separation of supernatant and settling, regulating the pH value of supernatant liquor is 7.0-8.0, obtains waste liquid after treatment.
Preferably, the metal ions in waste liquor concentration that described potassium permanganate process on-line determination COD instrument produces is, Mn 2+: 1-68g/L, MnO 4 -: 0-2.83g/L, Ag +: 0.1-2.22g/L, C 2o 4 2-: 0-2.5g/L.
Preferably, the transforming agent in described second step is 1-3.5 with the ratio of the volume of the waste liquid of potassium permanganate process on-line determination COD instrument generation :10.
Preferably, the temperature of reaction in described second step is 40-80 DEG C.
Preferably, the alkali in the 3rd described step is NaOH, Ca (OH) 2and Na 2cO 3in at least one, its quality adding with the ratio of the volume of waste liquid is: 10-600g: 1L.
Preferably, use hydrochloric acid soln or sulphuric acid soln to regulate the pH value of supernatant liquor in the 3rd described step, the concentration of volume percent of hydrochloric acid soln or sulphuric acid soln is 10%-30%.
Preferably, described waste liquid after treatment qualified discharge after the expanded graphite cleaner of load nano-titanium dioxide.
More preferably, in the expanded graphite cleaner of described load nano-titanium dioxide, the amount of the expanded graphite of load nano-titanium dioxide is the 10%-50% of cleaner volume.
Transforming agent solution of the present invention can be reduced into divalent mn ion by 7 valency mn ions in solution, has reduced MnO in waste liquid 4the concentration of-ion.Can dilute vitriol oil concentration in waste liquid, eliminate the interference of the vitriol oil to subsequent chemical reaction in waste liquid, avoid it in subsequent step, to affect Mn simultaneously 2+generation, accelerated the reaction in solution by adding alkali to make the stronger Mn2+ of remaining toxicity in waste liquid, Ag+ be converted into precipitation collect remove; Supernatant liquor just can qualified discharge after simple pH processes, realized waste liquid fast and effectively processing, and change easy storage and transport, solid that toxicity is lower into by being not easy storage and transport, solution that toxicity is higher.After testing, in supernatant liquor, only containing the ion to environment toxicological harmless, heavy metal Ag+, Mn2+ content are almost nil, well below the index request of national standard.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention can fast, comprehensively process the waste liquid that adopts national standard method on-line determination COD to produce, and has realized and has changed easy storage and transport, solid that toxicity is lower into by being not easy storage and transport, solution that toxicity is higher.
(2) the present invention, by preparing and adding transforming agent, effectively avoids the vitriol oil of waste liquid middle and high concentration to participate in chemical reaction generation SO2, and harm operator's is healthy, reaches the object of effective removal toxic heavy metal simultaneously;
(3) by adding transforming agent, can by have that positive 7 valency manganese are converted into remove positive divalent manganese;
(4) by adding alkali or alkaline solution, reacting the last throw out generating is the very low compound of nontoxic or toxicity that only contains heavy metal, and volume is little, only accounts for 1/10 of overall solution volume, recovery, simple to operate;
(5) speed of response is fast, and whole reaction process can complete in 15min, and reaction effect is easy to identify according to color.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
The waste liquid that adds 1L potassium permanganate process on-line determination COD instrument to produce in reactor, metal ions in waste liquor concentration is, Mn 2+: lg/L, MnO 4 -: 2.1g/L, Ag +: 0.2g/L.
Preparation transforming agent solution: by Na 2c 2o 4, Na 2s 2o 35H 2o, Fe 2(SO 3) 3, FeCl 2, ethanol and phenol is added to the water, stirring and dissolving, obtains transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 10g/L, Na 2s 2o 35H 2the concentration of O is 24.5g/L, FeSO 4concentration is 5.2g/L, FeCl 2concentration be that the concentration of 02g/L, ethanol is that the concentration of 15.1g/L, phenol is 15.1g/L, pH value of solution scope is between 6.5~8.5;
In reactor, add 5L transforming agent solution, be heated to 70 DEG C of stirring reactions 2 minutes, now, in waste liquid, do not contain MnO 4 -ion, only contains Mn 2+ion:
In reactor, add 5g NaOH again, stirring reaction 5 minutes; Static placement, the supernatant liquor of draining, separation of supernatant and settling, adding 15% dilute hydrochloric acid to regulate the pH value of supernatant liquor is 7.0, obtains waste liquid after treatment, collects settling simultaneously.Detect through (national standard method and elemental analyser), in waste liquid after treatment, only contain the ion to environment toxicological harmless, heavy metal Ag +, Hg 2+, Mn 2+, MnO 4 -content be respectively 0.01, do not detect, 0.01 and 0, well below the index request of national standard.
Embodiment 2:
The waste liquid that adds 1L potassium permanganate process on-line determination COD instrument to produce in reactor, metal ions in waste liquor concentration is, Mn 2+: 2g/L, MnO 4 -: 0.1g/L, Ag +: 0g/L.
Preparation transforming agent solution: by Na 2c 2o 4, Na 2s 2o 35H 2o, Fe 2(SO 3) 3, FeCl 2, ethanol is added to the water, stirring and dissolving, obtains transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 2g/L, Na 2s 2o 35H 2the concentration of O is 14.5g/L, FeSO 4concentration be 3.1g/L, FeCl 2concentration be that the concentration of 0.2g/L, ethanol is 10.1g/L, pH value of solution scope is between 6.5~8.5.
In reactor, add 5L transforming agent solution, be heated to 70 DEG C of stirring reactions 2 minutes, now, in waste liquid, do not contain MnO 4 -ion, only contains Mn 2+ion;
In reactor, add 6g Ca (OH) again 2, stirring reaction 5 minutes; Static placement, the supernatant liquor of draining, separation of supernatant and settling, adding 17% dilute hydrochloric acid to regulate the pH value of supernatant liquor is 8.0, obtains waste liquid after treatment, collects settling simultaneously.Detect through national standard method and elemental analyser, in waste liquid after treatment, only contain the ion to environment toxicological harmless, heavy metal Ag +, Hg 2+, Mn 2+, MnO 4 -content be respectively do not detect, do not detect, 0.01 and do not detect, well below the index request of national standard.
Embodiment 3:
The waste liquid that adds 1L potassium permanganate process on-line determination COD instrument to produce in reactor, metal ions in waste liquor concentration is, Mn 2+: 1.4g/L, MnO 4 -: 0.4g/L, Ag +: 1.5g/L.
Preparation transforming agent solution: by Na 2c 2o 4, FeCl 2, ethanol is added to the water, stirring and dissolving, obtains transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 3g/L, FeCl 2concentration be that the concentration of 1.9g/L, ethanol is 20.1g/L, pH value of solution scope is between 6.5~8.5.
In reactor, add 5L transforming agent solution, be heated to 75 DEG C of stirring reactions 2 minutes, now, in waste liquid, do not contain MnO 4 -ion, only contains Mn 2+ion:
In reactor, add 10g Na again 2cO 3, stirring reaction 5 minutes; Static placement, the supernatant liquor of draining, separation of supernatant and settling, adding 25% dilute hydrochloric acid to regulate the pH value of supernatant liquor is 7.5, obtains waste liquid after treatment, collects settling simultaneously.Detect through national standard method and elemental analyser, in waste liquid after treatment, only contain the ion to environment toxicological harmless, heavy metal Ag +, Hg 2+, Mn 2+, MnO 4 -content be respectively 0.01,0.01, do not detect and do not detect, well below the index request of national standard.
Embodiment 4
The waste liquid that adds 1L potassium permanganate process on-line determination COD instrument to produce in reactor, metal ions in waste liquor concentration is, Mn 2+: 6.8g/L, MnO 4 -: 1.2g/L, Ag +: 1.5g/L.
Preparation transforming agent solution: by Na 2c 2o 4, Na 2s 2o 35H 2o, Fe 2(SO 3) 3, FeCl 2, ethanol, phenol is added to the water, stirring and dissolving, obtains transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 8.8g/L, Na 2s 2o 35H 2the concentration of O is 12.5g/L, FeSO 4concentration is 4.1g/L, FeCl 2concentration be that the concentration of 0.5g/L, ethanol is 14.1g/L, phenol: 1.1g/L, pH value of solution scope is between 6.5~8.5.
In reactor, add 5L transforming agent solution, be heated to 80 DEG C of stirring reactions 2 minutes, now, in waste liquid, do not contain MnO 4 -ion, only contains Mn 2+ion;
In reactor, add 19g Na again 2cO 3, stirring reaction 5 minutes; Static placement, the supernatant liquor of draining, separation of supernatant and settling, adding 25% dilute hydrochloric acid to regulate the pH value of supernatant liquor is 7.5, obtains waste liquid after treatment, collects settling simultaneously.Detect through national standard method and elemental analyser, in waste liquid after treatment, only contain the ion to environment toxicological harmless, heavy metal Ag +, Hg 2+, Mn 2+, MnO 4 -content be respectively 0.01, do not detect, 0.01 and do not detect, well below the index request of national standard.
Above-mentioned waste liquid after the processing again of the expanded graphite cleaner of load nano-titanium dioxide, Ag +, Hg 2+, Mn 2+, MnO 4 -all do not detect.When in the expanded graphite cleaner of load nano-titanium dioxide, the amount of the expanded graphite of load nano-titanium dioxide is cleaner volume 10%-50%, all do not detect.Far below GB8978-1996 defined standard.

Claims (8)

1. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument produces, is characterized in that, concrete steps comprise:
The first step: preparation transforming agent solution, Na in described transforming agent solution 2c 2o 4concentration be 1-50g/L, Na 2s 2o 35H 2the concentration of O is 0-100g/L, FeSO 4concentration be 0-27g/L, FeCl 2concentration be that the concentration of 0-23g/L, ethanol is that the concentration of 0-24g/L, phenol is 0-24g/L;
Second step: add transforming agent solution in the waste liquid producing to potassium permanganate process on-line determination COD instrument, heated and stirred reaction;
The 3rd step: will add alkali in the reacted waste liquid of second step, stirring reaction, leaves standstill after reaction, separation of supernatant and settling, regulating the pH value of supernatant liquor is 7.0-8.0, obtains waste liquid after treatment.
2. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, is characterized in that, the metal ions in waste liquor concentration that described potassium permanganate process on-line determination COD instrument produces is: Mn 2+: 1-6.8g/L, MnO 4 -: 0-2.83g/L, Ag +: 0.1-2.22g/L, C 2o 4 2-: 0-2.5g/L.
3. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, is characterized in that, the transforming agent in described second step is 1-3.5 with the ratio of the volume of the waste liquid of potassium permanganate process on-line determination COD instrument generation: 10.
4. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, is characterized in that, the temperature of reaction in described second step is 40-80 DEG C.
5. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, is characterized in that, the alkali in the 3rd described step is NaOH, Ca (OH) 2and Na 2cO 3in at least one, its quality adding with the ratio of the volume of waste liquid is: 10-600g: 1L.
6. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, it is characterized in that, in the 3rd described step, use hydrochloric acid soln or sulphuric acid soln to regulate the pH value of supernatant liquor, the concentration of volume percent of hydrochloric acid soln or sulphuric acid soln is 10%-30%.
7. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 1 produces, is characterized in that, described waste liquid after treatment is qualified discharge after the expanded graphite cleaner of load nano-titanium dioxide.
8. the method for treating waste liquid that potassium permanganate process on-line determination COD instrument as claimed in claim 7 produces, it is characterized in that, in the expanded graphite cleaner of described load nano-titanium dioxide, the amount of the expanded graphite of load nano-titanium dioxide is the 10%-50% of cleaner volume.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105588927A (en) * 2014-11-14 2016-05-18 株式会社岛津制作所 Treatment method for waste liquid in COD measurement apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52104354A (en) * 1976-02-27 1977-09-01 Shimadzu Corp Method and apparatus for treating water containing permanganic acid io ns
JPS5367676A (en) * 1976-11-30 1978-06-16 Nippon Soda Co Ltd Detoxifying method for waste solution
DE10029146A1 (en) * 1999-06-26 2000-12-28 Merck Patent Gmbh Recycling sulfuric acid solution containing metals, preferably test solutions from determination of chemical oxygen demand, involves redox-controlled separation of silver amalgam with iron and precipitation as hydroxide
CN102464399A (en) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 Composite agent for removing manganese in wastewater and application method thereof
CN102583815A (en) * 2012-01-28 2012-07-18 马鞍山市桓泰环保设备有限公司 Method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with potassium dichromate method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52104354A (en) * 1976-02-27 1977-09-01 Shimadzu Corp Method and apparatus for treating water containing permanganic acid io ns
JPS5367676A (en) * 1976-11-30 1978-06-16 Nippon Soda Co Ltd Detoxifying method for waste solution
DE10029146A1 (en) * 1999-06-26 2000-12-28 Merck Patent Gmbh Recycling sulfuric acid solution containing metals, preferably test solutions from determination of chemical oxygen demand, involves redox-controlled separation of silver amalgam with iron and precipitation as hydroxide
CN102464399A (en) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 Composite agent for removing manganese in wastewater and application method thereof
CN102583815A (en) * 2012-01-28 2012-07-18 马鞍山市桓泰环保设备有限公司 Method for treating waste liquid produced during on-line chemical oxygen demand (COD) determination with potassium dichromate method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105588927A (en) * 2014-11-14 2016-05-18 株式会社岛津制作所 Treatment method for waste liquid in COD measurement apparatus

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