CN105753132A - High-concentration high-chroma chromium-containing waste water pretreatment method - Google Patents
High-concentration high-chroma chromium-containing waste water pretreatment method Download PDFInfo
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- CN105753132A CN105753132A CN201610197100.7A CN201610197100A CN105753132A CN 105753132 A CN105753132 A CN 105753132A CN 201610197100 A CN201610197100 A CN 201610197100A CN 105753132 A CN105753132 A CN 105753132A
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- reaction
- chromium
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- waste water
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
- C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
- C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
Abstract
The invention discloses a high-concentration high-chroma chromium-containing waste water pretreatment method.The method comprises the steps that waste water is collected to an acid-base regulation tank, dilute sulphuric acid of which the volume ratio is 1:9 is used for regulating the pH to be 3-5, the treated waste water is pumped into a reaction tank through a sewage lift pump, a certain amount of copperas (FeSO4.7H2O) solution is added, and mechanical stirring is conducted for 1 h.A certain volume of hydrogen peroxide (H2O2) with the mass fraction of 30% is slowly added, an aerated stirring reaction is conducted for 1-2 h, and the temperature of a reaction tank system is controlled to range from 40 DEG C to 50 DEG C; after the reaction is finished, mixed liquid automatically flows to a neutralization tank, the pH of the mixed liquid is regulated back to be 7-8, the mixed liquid then automatically flows to a settling tank, natural settling is conducted for 30 min, settling sludge is pumped into a sediment concentration tank through a sludge lift pump, a concentrated solution flows back to the acid-base regulation tank, and centrifugal dewatering is continuously conducted on concentrated chromium-containing sludge; chromium-containing slag cakes subjected to centrifugation can be recycled, and centrifugal slag liquid flows back to the acid-base regulation tank.According to the high-concentration high-chroma chromium-containing waste water pretreatment method, COD, chroma, CR<6+> and total chromium in waste tanning liquor can be treated synchronously.
Description
One, technical field
The invention belongs to the disposal of waste gas, water and industrial residue technical field of leather industry, be specifically related to a kind of high concentration, high chroma chromate waste water preprocess method.
Two, background technology
Process hides processing mainly has preparation, tanning, 3 workshop sections of arrangement, and the waste liquid after leather tanning workshop section has that colourity is big, COD and Cr6+The feature that concentration is high.Cr therein6+There is very strong toxicity, water body and soil can be caused extremely serious pollution.Additionally, COD, colourity in waste liquid are also very big to the harm of water environment.
The method processing waste tanning liquor both at home and abroad has: absorption method, membrane separation process, Coagulation Method, oxidizing process and electrolysis etc..The selection of dye property and adsorbent is had certain requirement by absorption method.Membrane separation process operation and maintenance cost is all higher, and operation management is complicated.The sludge quantity that Coagulation Method produces is many and difficult.Electrolysis need to consume mass energy, is not promoted.Widely used at present is oxidizing process, namely utilizes ozone, ultraviolet etc. that the Organic substance in dyeing waste liquid is degraded.But above-mentioned several method is only capable of removing the colourity in waste liquid and COD, for the Cr that leather tanning waste liquid toxic is stronger6+, it is impossible to realize synchronizing to remove.
The patent No. is the patent of CN103848520A, and Zhang Zhanxu etc. utilizes Fenton reagent to carrying out advanced treating through the leather waste water of materialization and biochemical treatment, in acid condition, and Fe2+With H2O2Adding mol ratio is 1:3, and when reaction temperature is 40 DEG C, COD clearance can reach more than 78.7%.The patent No. is (i.e. the present inventor) such as the patent of CN101921028A, Zhang Wenyi, utilizes Fe2+Reproducibility, by the Cr in silicon steel passivation solution6+Change into Cr3+, iron ion, hydrogen peroxide, chromium ion three mol ratio be n (Fe2+)∶n(H2O2)∶n(Cr6+During)=5.2: 10.4: 1, Cr6+Clearance can reach 99.98%.
On December 27th, 2013, Chinese Ministry of Environmental Protection issues " process hides and fur manufacturing industrial water pollution thing discharge standard " (GB30486-2013), it is stipulated that existing enterprise no longer performed the relevant regulations in " integrated wastewater discharge standard " (GB8978-1996) from 1 day July in 2014.Wherein to colourity, Cr6+And always all more former discharge standard of chromium concn is strictly a lot.The present invention is based on this, it is proposed to substep adds FeSO4·7H2O、H2O2Method pretreatment leather tanning waste stream process, utilizes one first to add Melanteritum (FeSO4·7H2O) solution reduction Cr6+, mechanic whirl-nett reaction is after 1 hour, then adds hydrogen peroxide (H2O2) form Fenton reagent, and utilize the mixed method of aeration agitation oxygenation to process leather tanning waste liquid, it is achieved colourity, Cr6+, COD and total chromium synchronization remove.
Three, summary of the invention
In view of above-mentioned process leather tanning liquid waste processing difficulty is big, efficiency is low, high in cost of production problem, the present invention provides one to add FeSO at times4·7H2O and H2O2And the method for aeration aerating stirring, it is achieved efficient, the synchronization of pollutant in leather tanning waste liquid are removed.
The cardinal principle of the present invention: Cr in acid condition6+With Cr2O7 2-Form exist, it is possible to by Fe2+It is reduced into the Cr that toxicity is relatively low3+.Reactive chemistry formula is:
Cr2O7 2-+6Fe2++14H+→2Cr3++6Fe3++7H2O
Cr2O7 2-There is very strong oxidisability, at acid condition H+With O2、H2O2Combined effect under, can Organic substance in oxidation Decomposition solution.Reactive chemistry formula is:
What leather tanning waste liquid colourity was high is primarily due to sulfonic group (R-SO3H) existence, it can increase the water solublity of dyestuff, has higher electron density.In acid condition, Fe2+Meeting and H2O2Reaction generates the easy attack high electron density point of OH, OH that oxidisability is extremely strong, thus the sulfonic group aoxidized in waste liquid and hardly degraded organic substance, reduces colourity and the COD of waste liquid.Meanwhile, Fe is utilized2+、Fe3+、Cr3+、H2O2、OH-, OH plasma and O2Cooxidation and the characteristic of co-precipitation, reduce the Cr in waste liquid further6+And COD concentration.Reactive chemistry formula is:
H2O2+Fe2+→Fe3++OH-+·OH
OH+R-SO3H→R1-SO2O-R2+H2O
Fe2++·OH→Fe3++OH-
Fe3++H2O2→FeOOH2++H+
Cr3++3OH-→Cr(OH)3↓
Fe3++3OH-→Fe(OH)3↓
Fe2++2OH-→Fe(OH)2↓
C (macromole)+OH+O2+H+→ C (little molecule)+H2O
Traditional F enton oxidation technology is usually when pH is 2～4, adds FeSO simultaneously4With H2O2, form OH, the Organic substance in catalytic oxidation waste water.
The present invention and this traditional F enton oxidation technology are different in that the following aspects:
(1) present invention first adds FeSO4·7H2O, adds H again after aerated reaction a period of time2O2。
(2) FeSO in the present invention4Main Function be remove the chromium in waste liquid, and as the catalyst of subsequent reactions, also there is certain coagulation simultaneously, reduce the float in waste liquid.
(3) H is added2O2Afterwards, H2O2With Fe2+、Fe3+、Cr3+、Cr6+、OH-, OH plasma and O2Form the reaction system of cooxidation, co-precipitation, remove the COD in waste liquid, reduce the colourity of waste liquid.
(4) simultaneously, Cr6+Also there is strong oxidizing property in an acidic solution, at acid condition H+With H2O2、O2Combined effect under, the larger molecular organics in oxidation Decomposition solution, become small organic molecule, other Direct Resolution is CO2And H2O。
The invention have the advantages that
(1) cost of the present invention is low, know-why simple, agents useful for same is easy to get, use procedure risk is little, easy and simple to handle, maintenance cost is low.
(2) present invention have that reaction rate is fast, good decolorizing effect, the Cr that can synchronize in removal waste liquid6+And COD, do not produce the features such as secondary pollution, it is achieved that the colourity in existing enterprise's waste tanning liquor, Cr6+With total chromium in workshop or production facility discharge of wastewater mouth qualified discharge.
(3) larger molecular organics decomposition and inversion can be small organic molecule by the present invention, is conducive to microorganism to organic biochemical degradation, can improve the stability of later stage biochemical treatment.
(4) mud that the present invention settles down, containing heavy metal chromium, recoverable.
Four, specific embodiments
The present invention is with FeSO4·7H2O and H2O2Specific embodiments for Feedstock treating leather tanning waste liquid is as follows:
First by leather tanning waste collection to acid-alkali accommodation pond, adding volume ratio is the dilute sulfuric acid of 1:9, and regulating pH is 3～5.Secondly the waste liquid in regulating reservoir is pumped in aeration agitation reaction tank by sewage lifting, adds a certain amount of Melanteritum (FeSO4·7H2O) solution, mechanic whirl-nett reaction 1h.It is slow added into the hydrogen peroxide (H that mass fraction is 30% of certain volume2O2), aeration agitation reaction 1～2h, keep Fe2+And H2O2Mol ratio be 1:10, temperature of reaction system maintains 40～50 DEG C.Question response terminates to open afterwards valve, makes mixed liquor from flowing into mechanical agitation neutralization pond, adjusts back pH to 7～8 with lime water, then open valve, makes mixed liquor from flowing to sedimentation tank, natural subsidence 30min.Precipitating sludge in sedimentation tank is by sludge pump suction sediment concentration basin, and concentrated solution is back in acid-alkali accommodation pond, and the chromium-bearing sludge after concentration enters centrifuge dehydration in centrifugal separator.The rotating speed of centrifugal separator is 3000～3500r/min, and the centrifugation time is 5～8min, the containing chromium slag cake recoverable after centrifugal, and centrifugal slag liquid is back in acid-alkali accommodation pond.Whole reaction time is 3.5h.
5 embodiments of the present invention are provided with the waste tanning liquor of certain Leather Factory for processing object below:
Embodiment 1
That the present embodiment processes is 5m3Containing chrome tanning waste liquid 1: water sample pH is 7.5～8, Cr6+Concentration is 19mg/L, COD concentration is 2700mg/L, and colourity is 40000 times.Specific embodiment step is as follows: first by leather tanning waste collection to acid-alkali accommodation pond, adding volume ratio is the dilute sulfuric acid of 1:9, and regulating pH is 5.It is pumped into machine aeration again through sewage lifting and mixes in reaction tank, add containing the Melanteritum solution that Melanteritum quality is 6.95kg, mechanic whirl-nett reaction 1h.It is then slowly added into the hydrogen peroxide 25L that mass fraction is 30%, opens roots blower, aeration agitation reaction 1～2h.Maintenance system temperature is 50 DEG C.Reaction opens valve after terminating, and makes mixed liquor from flowing in mechanical agitation neutralization pond, adjusts back the pH to 8 of mixed liquor with lime water, then open valve again, makes mixed liquor from flowing to sedimentation tank, natural subsidence 30min.Supernatant C r in sedimentation tank 46+Concentration is 0.15mg/L, and colourity reduces to 10 times, and COD concentration is 426.7mg/L, Cr6+99.56% and 84.20% has been respectively reached with the average removal rate of COD.
Embodiment 2 is that the amount of disposing waste liquid is different, raw material dosage is different, reaction condition is different with 5 from the difference of embodiment 1, and processing method is identical.Table 1 is collecting of the former medicine dosage of 5 embodiments, technological parameter and treatment effect.
The former medicine dosage of table 1 present invention, technological parameter and treatment effect
Claims (2)
1. high concentration, a high chroma chromate waste water preprocess method, its feature successively as follows:
1) by wastewater collection to acid-alkali accommodation pond, adding the dilute sulfuric acid adjustment pH that volume ratio is 1:9 is 3～5, is pumped in aeration agitation reaction tank again through sewage lifting；
2) in aeration agitation reaction tank, a certain amount of Melanteritum (FeSO is added4·7H2O) solution, mechanic whirl-nett reaction 1h, it is slow added into the hydrogen peroxide (H that mass fraction is 30% of certain volume2O2), open roots blower, aeration agitation reaction 1～2h, keep Fe2+And H2O2Mol ratio be 1:10, temperature of reaction system maintains 40～50 DEG C；
3) after reaction terminates, opening valve, mixed liquor, from flowing to mechanical agitation neutralization pond, adds lime water readjustment pH to 7～8, then opens valve, and mixed liquor is from flowing in sedimentation tank natural subsidence, and the time of staying is 30min；
4) gravity flow of the supernatant in sedimentation tank penetration depth treatment facility, precipitating sludge is pumped into sediment concentration basin by sludge lifting.Chromium-bearing sludge after concentration enters centrifuge dehydration in centrifugal separator, the containing chromium slag cake recoverable after centrifugal.Concentrated solution is concentrated with centrifugal slag liquid and is back in acid-alkali accommodation pond.
2. a kind of high concentration according to claims 1, high chroma chromate waste water preprocess method, it is characterized in that: step 2) dosing method of Chinese medicine is for first adding a certain amount of Melanteritum (FeSO4·7H2O) solution, mechanic whirl-nett reaction is after 1 hour, then adds the hydrogen peroxide (H that mass fraction is 30% of certain volume2O2), aeration agitation reaction 1～2h.
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| CN201610197100.7A CN105753132A (en) | 2016-03-31 | 2016-03-31 | High-concentration high-chroma chromium-containing waste water pretreatment method |
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| CN201610197100.7A CN105753132A (en) | 2016-03-31 | 2016-03-31 | High-concentration high-chroma chromium-containing waste water pretreatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793505A (en) * | 2018-07-11 | 2018-11-13 | 常州大学 | The method for handling floating cupric sulfide waste water and acidic organic wastewater simultaneously |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186402A (en) * | 2007-11-27 | 2008-05-28 | 华泰集团有限公司 | Fenton two-stage method oxidation processing technique for paper-making pulping waste water |
| CN101921028A (en) * | 2010-08-25 | 2010-12-22 | 常州大学 | Method for treating liquid waste of silicon steel passivation solution |
-
2016
- 2016-03-31 CN CN201610197100.7A patent/CN105753132A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186402A (en) * | 2007-11-27 | 2008-05-28 | 华泰集团有限公司 | Fenton two-stage method oxidation processing technique for paper-making pulping waste water |
| CN101921028A (en) * | 2010-08-25 | 2010-12-22 | 常州大学 | Method for treating liquid waste of silicon steel passivation solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793505A (en) * | 2018-07-11 | 2018-11-13 | 常州大学 | The method for handling floating cupric sulfide waste water and acidic organic wastewater simultaneously |
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