CN101508510A - Process for treating waste water from leather rich in aldehyde with aldehyde tannage - Google Patents
Process for treating waste water from leather rich in aldehyde with aldehyde tannage Download PDFInfo
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- CN101508510A CN101508510A CNA2009100586074A CN200910058607A CN101508510A CN 101508510 A CN101508510 A CN 101508510A CN A2009100586074 A CNA2009100586074 A CN A2009100586074A CN 200910058607 A CN200910058607 A CN 200910058607A CN 101508510 A CN101508510 A CN 101508510A
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- aldehyde
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- tannage
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Abstract
The invention discloses an aldehyde tannage aldehyde enriched leather wastewater treatment technical process. The technical process is used to carry out the decontamination treatment on the aldehyde tannage leather wastewater with the formaldehyde content of 600 to 800 mg/L. The technical process comprises the following steps of grate filtration, aldehyde removal through addition, pH value regulation, ABR anaerobic treatment, aeration treatment, vertical flow sedimentation and sand filtration, wherein in the aldehyde removal stage, sodium bisulphite is adopted as an aldehyde removal agent and the mass quantity ratio of sodium bisulphite: aldehyde is 1-3: 1; the pH value is 6 to 6.8; and the reaction time is 10 to 60 minutes. The treatment of the aldehyde tannage leather wastewater can completely meet the state emission requirements; and in addition, the technical process has low operation cost and the price for the treatment of each cube of wastewater is 0.5 to 0.7 Yuan.
Description
Technical field
The present invention relates to wastewater treatment, the preconditioning technique of formaldehyde during especially the aldehyde tannage leather waste water is handled.
Prior art
Usually the process for tanning of leather has two kinds of chromic tanning and aldehyde tannages.Because chromium has color, concerning light or white leather, chromic tanning is also inapplicable.Therefore,, can select for use formaldehyde (or acetaldehyde) usually, eliminate the interference of color as tanning agent in order to satisfy industrial particular requirement to the leather color.The advantage of utilizing formaldehyde to carry out leather tanning is that raw material is obtained easily, uses more convenient.And the leather colour purity is white, and tanning with other combines, and does not have color interference, meets the light nondiscoloration, and characteristics such as sweat proof, washable, acid and alkali-resistance are arranged, and for oxygenant, reductive agent stronger resistibility is arranged also.Shortcoming is that feel is flat partially thin, not anti-ageing, and easy embrittlement, hydrothermal stability is less.Because use formaldehyde as tanning agent, operation is immersion, degreasing, pickling, tanning.The general formaldehyde content of its wastewater effluent water quality between 600～800mg/L, COD
CrBetween 10000～12000mg/L, pH is between 6.0～6.8.Because the waste water water yield of discharging, variation water quality are big and complicated component, comprise that (non-ionic type Fatty Alcohol(C12-C14 and C12-C18) polyoxy-alkene ether, molecular formula are RO (CH for formaldehyde, salt, sulfuric acid, JFC
2CH
2O) nH) etc.Wherein toxic substance such as formaldehyde, sulfuric acid is totally unfavorable to follow-up biological treatment, and NaCl content height in the water, can reach 2000mg/L sometimes, enter Aerobic Pond after, also can play restraining effect to aerobic bacteria.In order to reduce the difficulty of subsequent biological treatment, carry out pre-treatment earlier according to the water quality situation of waste water.Leather-making waste water is collected separately, after objectionable impuritiess such as pre-treatment removal formaldehyde, butchered with other again and the sanitary wastewater mixing, carry out follow-up biological treatment.
A lot of experimental studies has been carried out in the processing of researcher's PARA FORMALDEHYDE PRILLS(91,95) waste water.The main method of handling formaldehyde waste water at present has: senior oxidation technologies such as Fenton process, photocatalytic oxidation, wet oxidation processing, steam blow-off method, oxidation-absorption method, SBR technology etc.With regard to present progress, generally all be that advanced oxidation is handled, comprise oxidation, photochemical catalysis oxidation or the like preconditioning technique use as industrial formaldehyde-containing wastewater, again according to the advanced oxidation result, be aided with suitable method for subsequent processing.Though this class methods treatment effect is better, non-secondary pollution, this type of oxidation technology cost is very high, also has very big difficulty on the actual engineering so will apply to.Therefore, seek formaldehyde treated method a kind of simple to operate, efficient, cheap the development of China's leather industry is had positive meaning.
Summary of the invention
Process for treating waste water from leather rich in aldehyde with aldehyde tannage, PARA FORMALDEHYDE PRILLS(91,95) content carries out the decontamination processing at the aldehyde tannage leather waste water of 600～800mg/L, adopts following step: grid filtration-addition aldehydes removal-pH value adjusting-ABR anaerobic treatment-aeration is handled-precipitation-sand filtration of perpendicular stream; Wherein in the aldehydes removal stage, the employing sodium bisulfite is a de-aldehyde agent, and the ratio sodium bisulfite of amount of substance: aldehyde is 1～3:1; PH value 6～6.8; 10～60 minutes reaction times.
Adopt method as above, in actual aldehyde tannage leather-making waste water, NaHSO
3When being 2:1 with the ratio of HCHO amount of substance, the clearance of formaldehyde can reach more than 99% in the waste water, can satisfy the primary standard that formaldehyde content in the waste water of national regulation is no more than 1mg/L fully.Adopt processing method of the present invention, can reach national emission request fully to the aldehyde tannage treatment of Tannery Wastewater, and running cost is low, 1 cube of waste water price of every processing is between 0.5～0.7 yuan.Subsequent biological treatment technology is also had no adverse effects its practical process.
Description of drawings is as follows:
Fig. 1 is the process flow sheet of process for treating waste water from leather rich in aldehyde with aldehyde tannage of the present invention.
Embodiment
According to the engineering experiment to pure formaldehyde and formaldehyde-containing wastewater, we spy takes materialization and biological treatment combination process that Sichuan rabbit industry company limited's aldehyde tannage leather-making waste water and slaughterhouse wastewater are handled, and in conjunction with Fig. 1 narration, its technology is as follows:
(1) grating tank
Grating tank is the sewage disposal first road pre-treatment facility, and in order to thick materials such as object-catching, scurf, meat mincing, furs, the protection water pump prevents that it from stopping up, and guarantees the normal operation of subsequent disposal facility.Reduce Pollutant levels simultaneously, alleviated the load of subsequent disposal facility.
Butcher remove hair and wait the solid residue thing through grating tank with sanitary wastewater after, can directly waste water be entered equalizing tank, then to put into neutralization tank separately through the leather-making waste water of grating tank and handle.
(2) addition aldehydes removal pond
Leather-making waste water will be put into neutralization tank separately and handle after waiting the solid residue thing through grating tank removal hair.Since contain toxic materials such as formaldehyde in this part water, very big to the influence of subsequent biological treatment, therefore must remove formaldehyde earlier, just can enter subsequent technique.Formaldehyde content in the waste water is controlled at country to be allowed in the emission standards.
(3) equalizing tank
Owing to process hides, butcher and the water quality and the water yield of the mixed waste water of living alter a great deal in time, adopt equalizing tank, the fluctuation of the waste water water yield and water quality is controlled in the stable scope, and the pH value should be controlled at 6.5～7.5 and is advisable in equalizing tank, guarantees that subsequent treatment process normally carries out.
(4) ABR anaerobic pond
Anaerobic reactor can make the main pollution load in the waste water remove with low cost movement, and plays multiple effects such as digested sludge.The advantage of ABR is the reaction efficiency height, compact construction, and not only energy consumption is low, and can reclaim biogas.Sludge yield low (be aerobic 1/3～1/5), and can digest aerobic sludge, easily dehydration.The pollutants removal rate of this system is about 60%～80%.
(5) aeration tank
Aerator carries out the secondary aeration under the employing liquid.The pollutants removal rate of this system is about 80%～90%.
(6) vertical sedimentation tank
Waste water enters vertical sedimentation tank and carries out sedimentation after biological treatment, reach the effect of mud-water separation.Mud at the bottom of the settling tank pond is put into mud-collecting well and is drawn back the aeration tank, and the mud quantity of reflux is decided according to practical situation.
(7) sand filter
Waste water enters sand filter at last through after a series of biology-chemical treatments.Behind the sand filter clarification filtration, qualified discharge.
Under basic technology condition as above,, following embodiment is arranged at the aldehydes removal pre-treatment.
Embodiment 1
We experimentize the leather-making waste water that Sichuan factory contains formaldehyde, and its water-quality guideline is: formaldehyde content between 600～800mg/L, COD
CrBetween 10000～12000mg/L.PH is 6.6, at normal temperatures, earlier concentration of formaldehyde is diluted to 100mg/L, presses NaHSO again
3With the ratio of HCHO amount of substance be that 2:1 adds after sodium bisulfite carries out nucleophilic addition, reaction times continues 30min, the concentration of formaldehyde of waste water is reduced to 0.892mg/L, satisfy fully the primary standard that formaldehyde content in the waste water of national regulation is no more than 1mg/L (formaldehyde to the lethal concentration of bacterium 100～150mg/L).Add cultured mud in addition reaction liquid, leave standstill, measure the concentration of formaldehyde when 24h and 72h respectively, formaldehyde content is 0.728mg/L during 24h, and formaldehyde content is 0.532mg/L during 72h, and promptly formaldehyde content is in downward trend always, does not occur ging up.This is because the amount of the sodium bisulfite that adds is excessive, impels molecular balance to move right, and makes the formaldehyde reaction in the waste water more complete, helps the removal of formaldehyde.
Embodiment 2
Other condition is with embodiment 1, and pH is 6.3 by NaHSO
3With the ratio of HCHO amount of substance be that 3:1 adds after sodium bisulfite carries out nucleophilic addition, the reaction times continues 30min, the clearance of formaldehyde is similar to and reaches 100%.
Embodiment 3
Other condition is with embodiment 1, and pH is 6.8 by NaHSO
3With the ratio of HCHO amount of substance be that 1:1 adds after sodium bisulfite carries out nucleophilic addition, the reaction times continues 30min, the clearance of formaldehyde is similar to and reaches 85%.
Claims (2)
1, process for treating waste water from leather rich in aldehyde with aldehyde tannage, PARA FORMALDEHYDE PRILLS(91,95) content carries out the decontamination processing at the aldehyde tannage leather waste water of 600～800mg/L, adopts following step: grid filtration-addition aldehydes removal-pH value adjusting-ABR anaerobic treatment-aeration is handled-precipitation-sand filtration of perpendicular stream; In the aldehydes removal stage, the employing sodium bisulfite is a de-aldehyde agent, and the ratio sodium bisulfite of amount of substance: aldehyde is 1～3:1; PH value 6-6.8; 10～60 minutes reaction times.
2, the process for treating waste water from leather rich in aldehyde with aldehyde tannage according to claim is characterized in that described aldehydes removal processing condition are that the ratio sodium bisulfite of amount of substance: aldehyde is 2:1; PH value 6～6.8; 30 minutes reaction times.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100586074A CN101508510A (en) | 2009-03-16 | 2009-03-16 | Process for treating waste water from leather rich in aldehyde with aldehyde tannage |
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| CNA2009100586074A CN101508510A (en) | 2009-03-16 | 2009-03-16 | Process for treating waste water from leather rich in aldehyde with aldehyde tannage |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449677A (en) * | 2013-09-12 | 2013-12-18 | 安徽省绿巨人环境技术有限公司 | Treatment process for wastewater produced in production of PU (Poly Urethane) synthetic leather |
| CN104909523A (en) * | 2015-07-01 | 2015-09-16 | 百川化工(如皋)有限公司 | High-concentration formaldehyde sewage treatment system and treatment method |
-
2009
- 2009-03-16 CN CNA2009100586074A patent/CN101508510A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449677A (en) * | 2013-09-12 | 2013-12-18 | 安徽省绿巨人环境技术有限公司 | Treatment process for wastewater produced in production of PU (Poly Urethane) synthetic leather |
| CN103449677B (en) * | 2013-09-12 | 2014-12-17 | 安徽省绿巨人环境技术有限公司 | Treatment process for wastewater produced in production of PU (Poly Urethane) synthetic leather |
| CN104909523A (en) * | 2015-07-01 | 2015-09-16 | 百川化工(如皋)有限公司 | High-concentration formaldehyde sewage treatment system and treatment method |
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Open date: 20090819 |