CN1513771A - Electrolytic treatment method of azodicarbonamide foaming agent waste water - Google Patents
Electrolytic treatment method of azodicarbonamide foaming agent waste water Download PDFInfo
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Abstract
An electrolytic process for treating the sewage of azodimethylamide includes depositing, regulating pH=5-11, pumping it in electrolyzer with non-diaphragm electrolyzer reactor using RuIrTi coated Ti plate as anode and activated ultralow-carbon stainless steel place as cathode, applying constant-current DC, and electrolyzing for 30-120 min. Its advantage is high effect to remove COD, ammoniacal nitrogen and hydrazine hydrate.
Description
Technical field
The invention belongs to the organic industrial sewage process field, particularly relate to a kind of electrolytic processing method of azodicarbonamide foaming agent waste water.
Background technology
In AC whipping agent (Cellmic C 121) production process, contain the pollutents such as COD, ammonia nitrogen and hydrazine hydrate of higher concentration in the waste water of discharge.Wherein the content of COD about 500-900mg/L, ammonia nitrogen content about 3000-4000mg/L, the content of hydrazine hydrate is about 15-20mg/L.In addition, the muriate and the sulfate radical that also contain higher concentration in the waste water.Because above-mentioned water quality specially, bring certain difficulty for the processing of waste water.These many people were carried out research, proposed various treatment processs,, all do not obtain the ideal treatment effect as treatment processs such as bleaching powder seminal fluid facture, neutralization-distillation method or blow-off method, crystallization-method of enrichment, photocatalytic oxidations.
" AC whipping agent Wastewater Treatment and application " (pollution prevention technique, 1999 the 3rd phases) introduced, and adopts the bleaching powder seminal fluid of AC whipping agent factory to make this waste water of oxidizer treatment.Bleaching powder seminal fluid main component is a Losantin, and Losantin is unstable in water, easily emits nascent state oxygen, and chlorine and nascent oxygen have very strong oxidation capacity, make the oxidation operation in the waste water, thereby reduces the COD value.Carrying out engineering test in Jiangsu AC whipping agent factory proves, the clearance of the COD of this waste water is 78.1%, and ammonia-N removal rate is 35.4%.This method major advantage is: treatment process is simple, handles the approach that adopts " waste recycling ", and reduced investment is applicable to the processing of chlor-alkali plant AC whipping agent factory effluent.The main drawback of this method is: in wastewater treatment process, because chlorine discharges, easily cause secondary pollution and equipment corrosion.In addition, not good to the ammonia nitrogen treatment effect.
Industrial, electrolysis process mainly is used in chlor-alkali industry.Because electrolysis has, and is drawn attention by people, also begins to use it for the processing of waste water in recent years.According to " progress of electrolytic process water technology " (chemical industry environmental protection, 2001,1 phase, 11～5) report, the major advantage of brine electrolysis treatment technology is: 1. the OH that produces in the process does not have the organic pollutant reaction in selectively direct and the waste water, it is degraded to dioxide, water and simple organic, does not have or seldom produce secondary pollution; 2. the energy efficiency height just can carry out at normal temperatures and pressures; 3. both can be used as the separate unit individual curing, can combine with other treatment processs again; 4. equipment and operate fairly simple.Abroad, the brine electrolysis treatment technology is also referred to as " environmental friendliness " technology.
Because above several aspects, the brine electrolysis treatment process has been used to the processing of waste water from dyestuff, reducing COD, decolouring, improves BOD
5Aspects such as/COD ratio demonstrate good effect, and are therefore selected as a kind of pretreatment process before the waste water from dyestuff biochemical treatment.CN1201760A discloses the report about " utilizing the waste water containing dye and the treatment process that contains pigment wastewater of heat energy " of one piece of Korea S, is exactly the application of brine electrolysis treatment process in dye wastewater treatment.But this piece report only relates to waste water containing dye and contains the processing of pigment wastewater, and its main inventive point is the decoloring ability that utilizes heat energy to improve electrolysis process and reaches the purpose that increases treatment capacity.
Summary of the invention
Purpose of the present invention is exactly by adopting the brine electrolysis treatment process, solves problems such as secondary pollution problem, equipment corrosion problem and ammonia nitrogen treatment effect in the Cellmic C 121 wastewater treatment process be not good.
The method that electrolytic process of the present invention is handled azodicarbonamide foaming agent waste water is achieved in that
The step of the electrolytic processing method of azodicarbonamide foaming agent waste water of the present invention is:
(1) waste water after adjusting pH is 5～11, preferred 5.7～10.6, enters electrolyzer through post precipitation;
What (2) electrolyzer adopted is the undivided cell reactor, chooses ruthenium-iridium-tantalum coated titanium plate and does anode, and Ultra-low carbon activation stainless steel plate is done negative electrode, and pole plate is spaced apart 3～10mm, and preferred polar plate spacing is 3mm;
(3) the constant current direct current that is provided by silicon controlled rectifier direct supply housing is provided pole plate, and control current density is 2450～6440A/m2, and preferred current density is 5550A/m
2Minimum pulse is spaced apart 0.1s.
(4) the electrolysis residence time is 30～120min.
After electrolysis treatment of the present invention, the COD of pollutent, ammonia nitrogen and hydrazine hydrate etc. can reach state sewage emission standard in the azodicarbonamide foaming agent waste water, even handle the degree that can't check.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment.
In the electrolyzer of the present invention pole plate is housed because plate material and condition of surface have great effect to reaction, so choose corrosion-resistant, chlorine evolution potential is low, can bear the electrode of high current density.This research is chosen ruthenium-iridium-tantalum coated titanium plate and is done anode after screening, and Ultra-low carbon activation stainless steel plate is done negative electrode.
The constant current direct current that is provided by silicon controlled rectifier direct supply housing is provided pole plate.So-called constant current direct current is exactly to have rectification-alternating-current is become the current constant of direct current, constant current-maintenance output DC and the electric current of pulse-exportable pulsed current performance.Its minimum pulse is spaced apart 0.1s, and can be easily according to the different requirements of handling waste water, by regulating the size of electric current, the current density of conversion electrolytic pole board.
Principal pollutant analysis project: COD, ammonia nitrogen, hydrazine hydrate.
Embodiment 1-5
Embodiment 1-5 has illustrated the variation with electrolysis time of different current densities and COD clearance
Different current densities have bigger influence to the COD clearance, along with current density from 2450A/m
2To 6440A/m
2Increase, the reinforcement of electrolytic action, in the identical time, the COD clearance also increases thereupon, sees Table 1.
Different current densities of table 1 and COD clearance are with the variation of electrolysis time
| Embodiment | Current density, A/m 2 | ??COD | Electrolysis time, min | ||||
| ????0 | ????30 | ????60 | ????90 | ????120 | |||
| ????1 | ????2450 | Water outlet, mg/L | ????821 | ????808 | ????700 | ????592 | ????269 |
| Clearance, % | ????1.64 | ????14.75 | ????27.88 | ????67.2 | |||
| ????2 | ????3890 | Water outlet, mg/L | ????725 | ????430 | ????324 | ????213 | ????174 |
| Clearance, % | ????40.73 | ????55.25 | ????70.61 | ????75.92 | |||
| ????3 | ????4670 | Water outlet, mg/L | ????620 | ????384 | ????354 | ????177 | ????118 |
| Clearance, % | ????38.09 | ????42.08 | ????71.43 | ????80.95 | |||
| ????4 | ????5550 | Water outlet, mg/L | ????725 | ????483 | ????322 | ????188 | ????27 |
| Clearance, % | ????33.33 | ????55.55 | ????74.07 | ????96.32 | |||
| ????5 | ????6440 | Water outlet, mg/L | ????765 | ????490 | ????337 | ????165 | ????12 |
| Clearance, % | ????35.95 | ????55.95 | ????78.43 | ????98.43 |
Embodiment 6-8
Embodiment 6-8 represents different poles distance between plates and the COD clearance changing conditions with electrolysis time.
The more little electrolytic efficiency of spacing of theoretical electrolytic pole board is high more, but saliferous is higher in the waste water, and complicated component experiment showed, polar plate spacing when 3 ~ 10mm, and along with dwindling of polar plate spacing, in the identical time, the COD clearance also improves thereupon, sees Table 2.
Table 2 different poles distance between plates and COD clearance are with the variation of electrolysis time
| Embodiment | Polar plate spacing | Project | Electrolysis time, min | ||||||||
| ??0 | ??15 | ??30 | ??45 | ??60 | ??75 | ??90 | ??105 | ??120 | |||
| ??6 | ??10mm | Water outlet COD, mg/L | ??548 | ??434 | ??404 | ??350 | ??240 | ??204 | ??135 | ??30 | ??0 |
| The COD clearance, % | ??20. ??8 | ??26. ??3 | ??36. ??1 | ??56. ??2 | ??62. ??8 | ??75. ??4 | ??94. ??5 | ??100 ??.0 | |||
| ????7 | ????6mm | Water outlet COD, mg/L | ??556 | ??422 | ??412 | ??314 | ??220 | ??190 | ??95 | ??10 | ??0 |
| The COD clearance, % | ??24. ??1 | ??259 | ??43. ??5 | ??60. ??4 | ??65. ??8 | ??82. ??9 | ??98. ??2 | ??100 ??.0 | |||
| ????8 | ????3mm | Water outlet COD, mg/L | ??597 | ??433 | ??403 | ??284 | ??194 | ??149 | ??45 | ??0 | ??0 |
| The COD clearance, % | ??27. ??5 | ??32. ??5 | ??52. ??4 | ??67. ??5 | ??75. ??0 | ??92. ??5 | ??100 ??.0 | ??100 ??.0 | |||
Embodiment 9-11
Embodiment 9-11 explanation condition of different pH down with COD and ammonia nitrogen removal frank changing conditions with electrolysis time.See Table 3.
Table 3 condition of different pH down and COD and ammonia nitrogen removal frank over time
| Embodiment | ??pH | Project | Electrolysis time, min | ||||||||
| ??0 | ??15 | ??30 | ??45 | ??60 | ??75 | ??90 | ??105 | ??12 ??0 | |||
| ????9 | ??5.7 | Water outlet COD mg/L | ??597 | ??433 | ??403 | ??284 | ??194 | ??149 | ??45 | ??0 | ??0 |
| The COD clearance, % | ??27.5 | ??32.5 | ??52. ??4 | ??67. ??5 | ??75. ??0 | ??92. ??5 | ??100 | ??10 ??0 | |||
| The water outlet ammonia nitrogen, mg/L | ??339 ??8 | ??3265 | ??2839 | ??221 ??7 | ??159 ??4 | ??828 | ??48 | ??0 | ??0 | ||
| Ammonia nitrogen removal frank, % | ??3.9 | ??16.4 | ??34. ??8 | ??53. ??1 | ??75. ??6 | ??98. ??6 | ??100 | ??10 ??0 | |||
| ????10 | ??8.6 | Water outlet COD mg/L | ??537 | ??422 | ??375 | ??238 | ??186 | ??125 | ??34 | ??0 | ??0 |
| The COD clearance, % | ??21.4 | ??30.2 | ??55. ??7 | ??65. ??4 | ??76. ??7 | ??93. ??7 | ??100 | ??10 ??0 | |||
| The water outlet ammonia nitrogen, mg/L | ??354 ??5 | ??3509 | ??2972 | ??232 ??9 | ??159 ??4 | ??971 | ??166 | ??0 | ??0 | ||
| Ammonia nitrogen removal frank, % | ??1.0 | ??16.2 | ??34. ??3 | ??55. ??0 | ??72. ??6 | ??95. ??3 | ??100 | ??10 ??0 | |||
| ????11 | ??10.6 | Water outlet COD mg/L | ??567 | ??435 | ??388 | ??258 | ??199 | ??130 | ??41 | ??0 | ??0 |
| The COD clearance, % | ??23.3 | ??31.6 | ??54. ??5 | ??64. ??9 | ??77. ??1 | ??92. ??8 | ??100 | ??10 ??0 | |||
| The water outlet ammonia nitrogen, mg/L | ??324 ??3 | ??3198 | ??2792 | ??223 ??9 | ??124 ??4 | ??791 | ??110 | ??0 | ??0 | ||
| Ammonia nitrogen removal frank, % | ??1.4 | ??13.9 | ??31. ??0 | ??61. ??64 | ??75. ??6 | ??96. ??6 | ??100 | ??10 ??0 | |||
Embodiment 12
According to above result, under best electrolytic condition, current density is 5550A/m
2, polar plate spacing is 3mm, and pH is 5.7 o'clock, and the contaminant degradation rate sees Table 4 over time.
The best electrolytic condition contaminant degradation of table 4 rate over time
| Pollutent | Time, min | |||||||
| ??0 | ??15 | ????30 | ??45 | ??60 | ??75 | ??90 | ??105 | |
| ??COD，mg/L | ??597 | ??433 | ????403 | ??284 | ??194 | ??149 | ??45 | ??0 |
| The COD clearance, % | ??27.5 | ????32.5 | ??52. ??4 | ??67. ??5 | ??75. ??0 | ??92. ??5 | ??100 | |
| ??NH 3-N，mg/L | ??3398 | ??3265 | ????2839 | ??221 ??7 | ??159 ??4 | ??828 | ??48 | ??0 |
| ??NH 3-N clearance % | ??3.9 | ????16.4 | ??34. ??8 | ??53. ??1 | ??75. ??6 | ??98. ??6 | ??100 | |
| Hydrazine hydrate, mg/L | ??15.9 ??7 | ????0.16 | ??0 | |||||
| The hydrazine hydrate clearance, % | ????99.0 | ??100 ??.0 | ||||||
Claims (5)
1. the electrolytic processing method of an azodicarbonamide foaming agent waste water. the steps include:
(1) waste water after adjusting pH is 5～11, enters electrolyzer through post precipitation;
(2) the undivided cell reactor is adopted in electrolysis, chooses ruthenium-iridium-tantalum coated titanium plate and does anode, and Ultra-low carbon activation stainless steel plate is done negative electrode, and pole plate is spaced apart 3～10mm;
(3) the constant current direct current that is provided by silicon controlled rectifier direct supply housing is provided pole plate, and control current density is 2450～6440A/m2, and minimum pulse is spaced apart 0.1s;
(4) the electrolysis residence time is 30～120min.
2. method of wastewater treatment as claimed in claim 1 is characterized in that: described current density is 5550A/m
2
3. method of wastewater treatment as claimed in claim 1 is characterized in that: described polar plate spacing is 3mm.
4. method of wastewater treatment as claimed in claim 1 is characterized in that: described pH is 5.7～10.6.
5. method of wastewater treatment as claimed in claim 1 is characterized in that: described current density is 5550A/m
2Described polar plate spacing is 3mm; Described pH is 5.7～10.6.
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| CN 02160118 CN1212976C (en) | 2002-12-31 | 2002-12-31 | Electrolytic treatment method of azodicarbonamide foaming agent waste water |
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| CN 02160118 CN1212976C (en) | 2002-12-31 | 2002-12-31 | Electrolytic treatment method of azodicarbonamide foaming agent waste water |
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| CN1513771A true CN1513771A (en) | 2004-07-21 |
| CN1212976C CN1212976C (en) | 2005-08-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410193C (en) * | 2006-06-12 | 2008-08-13 | 江苏大学 | Method for treating wastewater from ADC vesicant, and integrated plant |
| CN108314263A (en) * | 2018-02-28 | 2018-07-24 | 江苏大学 | A kind of ADC foaming agent condensed mother liquors treatment process |
-
2002
- 2002-12-31 CN CN 02160118 patent/CN1212976C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410193C (en) * | 2006-06-12 | 2008-08-13 | 江苏大学 | Method for treating wastewater from ADC vesicant, and integrated plant |
| CN108314263A (en) * | 2018-02-28 | 2018-07-24 | 江苏大学 | A kind of ADC foaming agent condensed mother liquors treatment process |
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| CN1212976C (en) | 2005-08-03 |
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