CN102381781A - Process for recovering chromium in chrome tanned leather waste water - Google Patents
Process for recovering chromium in chrome tanned leather waste water Download PDFInfo
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- CN102381781A CN102381781A CN2011102827053A CN201110282705A CN102381781A CN 102381781 A CN102381781 A CN 102381781A CN 2011102827053 A CN2011102827053 A CN 2011102827053A CN 201110282705 A CN201110282705 A CN 201110282705A CN 102381781 A CN102381781 A CN 102381781A
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Abstract
The invention relates to a process for recovering chromium in chrome tanned leather waste water. The invention is characterized in that the process for recovering chromium in chrome tanned leather waste water is in favor of subsequent reutilization of chromium mud and realization of standard discharge of total chromium content in waste water after recovering chromium, the chrome tanned leather waste water is effectively split and individually collected. The method comprises a first filtration by using 1-3mm grid, a secondary filtration by using a filter press, a third filtration by employing a reaction for controlling the pH value of temperature and reusing the filter press for press filtration. The content of the obtained filter residue which is chromium oxide of the chromium mud is great than 8wt%, and the content of filtrate which is the total chromium content of the discharged waste water is less than or equal to 1.5mg/L by referring Cr.
Description
Technical field
The invention belongs to the clearer production technology in the tanning industry, particularly relate to the recovery method of chromium in a kind of process hides Chrome Tanning Wastewater.
Background technology
Present stage, it generally is to adopt simple alkaline chemical precipitation that tannery handles Chrome Tanning Wastewater, and the deposition of gained is exactly a chromium-bearing sludge, is called for short in " chromium mud ".This chromium mud impurity is many, and chromium content is low, and recycle value is low.The method of disposal that enterprise taked is to burn or landfill basically, but the hidden danger that these two kinds of methods had not only been wasted resource but also had secondary pollution.On the other hand, the difficult qualified discharge of realizing of total chrome content surpasses 50mg/L usually in the waste water that Chrome Tanning Wastewater is discharged after treatment, has influenced the biochemical treatment of follow-up comprehensive wastewater.
Consider that from the angle of environment protection and Sustainable development innoxious, minimizing, the recycling treatment of chromium mud are trends of the times.The middle tannery of new " the national Hazardous wastes register " of on August 1st, 2008 issuing and implementation chromium mud be listed (HW21,193-001-21*).Country's first " 12 special topic planning "---in heavy metal contamination integrated control " the 12 " planning, chromium is included in first kind plan objects, and leather and goods thereof already are put into emphasis prevention and control industry.This just requires each leather-making enterprises with chromate waste water and contain the most important thing of the improvement of chromium refuse as environmental protection of enterprise improvement work.
Summary of the invention
The objective of the invention is to the problem that chromium mud recycle value is low and the waste discharge total chrome content is higher after the general Chrome Tanning Wastewater processing, a kind of follow-up chromium recovery technology of utilizing and realizing total chrome content qualified discharge in the waste water of chromium recovery back of chromium mud that helps is provided.
To achieve these goals, the technical scheme of taking of the present invention is following:
The recovery technology of chromium in a kind of process hides Chrome Tanning Wastewater comprises once filtration, secondary filtration, reaction and three filtrations, and it is characterized in that: the process hides Chrome Tanning Wastewater is carried out effectively shunting and single collection, and wherein,
⑴ once filter: through effectively shunting and single collection Chrome Tanning Wastewater get into collecting tank after the grid crack is 1 ~ 3mm grid filtration;
⑵ secondary filtration: be collected in through once filtering that Chrome Tanning Wastewater is metered into reaction tank again in the collecting tank after pressure filter filters;
⑶ reaction: the temperature of waste water in the control reaction tank, under whipped state, add alkali lye, regulate Chrome Tanning Wastewater pH value to 8.5 ~ 9.5, reacted 1 ~ 3 hour, make chromium fully be converted into chromium hydroxide precipitation; Under whipped state, add the anionic polyacrylamide of Chrome Tanning Wastewater quality 2 ~ 8ppm then, continue to stir 5 ~ 30 minutes, stop to stir afterreaction more than 3.5 hours;
⑷ three times filters: again through the pressure filter press filtration, the gained filter residue was the chromium sesquioxide content＞8wt% of chromium mud after reaction was accomplished, and filtrating is that the total chrome content of waste discharge is in Cr≤1.5mg/L.
As a kind of preferred, described process hides Chrome Tanning Wastewater is carried out effectively shunting and single collection is through different conduit systems, and waste water such as washing in the tanning operation, deliming, softening, degreasing are separated the single collection of realization Chrome Tanning Wastewater with Chrome Tanning Wastewater.
As a kind of preferred, in described secondary filtration step ⑵, canvas press cloth specification >=200 orders.
As a kind of preferred, in described reactions step ⑶, described adding alkali lye is that wastewater temperature is 20 ~ 40 ℃ in the control reaction tank, and slow adding mass concentration is 30% ~ 50% aqueous sodium hydroxide solution under whipped state.
As a kind of preferred, in described reactions step ⑶, the anionic polyacrylamide of described adding Chrome Tanning Wastewater is that mass concentration is 1 ‰ the aqueous solution.
As a kind of preferred, in described three filtration step ⑷, canvas press cloth specification >=250 orders.
As a kind of preferred, in described reactions step ⑶, described stirring is mechanical stirring or pneumatic blending.
The present invention through effluent segregation with the Chrome Tanning Wastewater single collection after, through the multi-filtering device, remove most of scurf, impurity such as hair slag etc., the chromium sesquioxide content that guarantees to reclaim chromium mud is greater than 8wt%, so that the utilization again of chromium mud.Chrome Tanning Wastewater is reacted under certain temperature condition, to guarantee reaction effect.After adding alkali reaction, add anionic polyacrylamide and accelerate settling velocity, also reduce precipitation volume simultaneously.Waste water through chromium recycling back discharging can reach chromium drain requirement up to standard in the workshop among the national sewage comprehensive emission standard GB8978-1996.
Description of drawings
Fig. 1 is one embodiment of the present invention technological process synoptic diagram.1 mechanical grille wherein, 2 collecting tanks, 3 surge pump A, 4 chamber-type press filters, 5 reaction tanks, 6 surge pump B, 7 barrier film chamber-type press filters.
Fig. 2 is an another embodiment of the present invention technological process synoptic diagram.1 mechanical grille wherein, 2 collecting tanks, 3 surge pump A, 4 chamber-type press filters, 5 reaction tank pre-mixing districts, 6 reaction tank main reaction region, 7 anionic polyacrylamides preparation bucket, 8 surge pump B, 9 settling tanks, 10 surge pump C, 11 barrier film chamber-type press filters.
Embodiment
Through embodiment further introduction is done in invention below in conjunction with accompanying drawing.
Embodiment 1:
At tan(ning)drum place, tanning workshop, part flow arrangement is set, Chrome Tanning Wastewater single collection and process grid crack are that the mechanical grille 1 of 1mm is removed bulk scurf and other large granular impurities, get into Chrome Tanning Wastewater collecting tank 2; Waste water such as washing, deliming, softening, degreasing get into the comprehensive wastewater collecting tank.Chrome Tanning Wastewater in the collecting tank 2 is squeezed into the chamber-type press filter 4 that adopts 200 order terylene filter clothes through surge pump A3 and is filtered, further remove fine particle impurity such as the hair slag in the Chrome Tanning Wastewater, thin scurf, wood chip after, get into reaction tank 5.Liquid level arrives the regulation liquid level in reaction tank 5, opens mechanical stirring, and the Chrome Tanning Wastewater temperature slowly adds 30% aqueous sodium hydroxide solution then at 25 ℃ in the control reaction tank 5, and the pH value is adjusted to 9.5, continues to stir 30 minutes, stops to stir afterreaction after 2 hours; Open once more and stir; The anionic polyacrylamide of disposable adding Chrome Tanning Wastewater quality 7ppm (using clear water that anionic polyacrylamide is mixed with mass concentration before adding earlier is 1 ‰ the aqueous solution); Continue to stir 10 minutes; Stopped to stir the back standing and reacting 3.5 hours, and reaction mixture was squeezed into barrier film chamber-type press filter 7 press filtrations of adopting 300 order polypropylene fibre filter clothes with pneumatic diaphragm pump B6.Getting filter residue is chromium mud, its chromium sesquioxide content＞8wt%; Filtrating is waste discharge, and its total chrome content gets into the composite wastewater equalizing tank in Cr≤1.5mg/L.
Embodiment 2:
At tan(ning)drum place, tanning workshop, part flow arrangement is set, Chrome Tanning Wastewater single collection and process grid crack are that the mechanical grille 1 of 1mm is removed bulk scurf and other large granular impurities, get into Chrome Tanning Wastewater collecting tank 2; Waste water such as washing, deliming, softening, degreasing get into the comprehensive wastewater collecting tank.Chrome Tanning Wastewater in the collecting tank 2 is squeezed into the chamber-type press filter 4 that adopts 200 order terylene filter clothes through surge pump A3 and is filtered, further remove fine particle impurity such as the hair slag in the Chrome Tanning Wastewater, thin scurf, wood chip after, get into reaction tank 5.Liquid level arrives the regulation liquid level in reaction tank 5, opens mechanical stirring, and the Chrome Tanning Wastewater temperature is at 40 ℃ in the control reaction tank 5; Slowly add 30% aqueous sodium hydroxide solution then; The pH value is adjusted to 9.5, continue to stir 20 minutes, stop to stir afterreaction after 1.5 hours; Open once more and stir; The anionic polyacrylamide of disposable adding Chrome Tanning Wastewater quality 7ppm (using clear water that anionic polyacrylamide is mixed with mass concentration before adding earlier is 1 ‰ the aqueous solution); Continue to stir 10 minutes; Stopped to stir the back standing and reacting 3 hours, and reaction mixture was squeezed into barrier film chamber-type press filter 7 press filtrations of adopting 300 order polypropylene fibre filter clothes with pneumatic diaphragm pump B6.Getting filter residue is chromium mud, its chromium sesquioxide content＞8wt%; Filtrating is waste discharge, and its total chrome content gets into the composite wastewater equalizing tank in Cr≤1.5mg/L.
Embodiment 3:
At tan(ning)drum place, tanning workshop, part flow arrangement is set, Chrome Tanning Wastewater single collection and process grid crack are that the mechanical grille 1 of 1mm is removed bulk scurf and other large granular impurities, get into Chrome Tanning Wastewater collecting tank 2; Waste water such as washing, deliming, softening, degreasing get into the comprehensive wastewater collecting tank.Chrome Tanning Wastewater in the collecting tank 2 is squeezed into the chamber-type press filter 4 that adopts 200 order terylene filter clothes through surge pump A3 and is filtered, further remove fine particle impurity such as the hair slag in the Chrome Tanning Wastewater, thin scurf, wood chip after, get into reaction tank pre-mixing district 5.Open the mechanical stirring in reaction tank pre-mixing district 5; Control Chrome Tanning Wastewater temperature slowly adds 30% aqueous sodium hydroxide solution then at 25 ℃ in reaction pre-mixing district 5, the pH value is controlled at 9.5; The reaction mixture overflow gets into reaction tank main reaction region 6, and the reaction times was at 2 hours.Through pneumatic diaphragm pump B8 the reaction mixture in the reaction tank main reaction region 6 is pumped in the settling tank 9; When pumping into, being 1 ‰ the anionic polyacrylamide aqueous solution with the mass concentration of using clear water to prepare in advance in the anionic polyacrylamide preparation bucket 7 adds wherein by the 7ppm of Chrome Tanning Wastewater quality.Reaction mixture is 3.5 hours in 9 residence time of settling tank, and supernatant directly gets into the composite wastewater equalizing tank, and deposition is squeezed into barrier film chamber-type press filter 11 press filtrations of adopting 300 order polypropylene fibre filter clothes through pneumatic diaphragm pump C10.Getting filter residue is chromium mud, its chromium sesquioxide content＞8wt%; Filtrating is waste discharge, and its total chrome content gets into the composite wastewater equalizing tank in Cr≤1.5mg/L.
Embodiment 4:
At tan(ning)drum place, tanning workshop, part flow arrangement is set, Chrome Tanning Wastewater single collection and process grid crack are that the mechanical grille 1 of 1mm is removed bulk scurf and other large granular impurities, get into Chrome Tanning Wastewater collecting tank 2; Waste water such as washing, deliming, softening, degreasing get into the comprehensive wastewater collecting tank.Chrome Tanning Wastewater in the collecting tank 2 is squeezed into the chamber-type press filter 4 that adopts 200 order terylene filter clothes through surge pump A3 and is filtered, further remove fine particle impurity such as the hair slag in the Chrome Tanning Wastewater, thin scurf, wood chip after, get into reaction tank pre-mixing district 5.Open the mechanical stirring in reaction tank pre-mixing district 5; Control Chrome Tanning Wastewater temperature slowly adds 30% aqueous sodium hydroxide solution then at 40 ℃ in reaction pre-mixing district 5, the pH value is controlled at 9.5; The reaction mixture overflow gets into reaction tank main reaction region 6, and the reaction times was at 1.5 hours.Through pneumatic diaphragm pump B8 the reaction mixture in the reaction tank main reaction region 6 is pumped in the settling tank 9; When pumping into, being 1 ‰ the anionic polyacrylamide aqueous solution with the mass concentration of using clear water to prepare in advance in the anionic polyacrylamide preparation bucket 7 adds wherein by the 7ppm of Chrome Tanning Wastewater quality.Reaction mixture is 3.5 hours in 9 residence time of settling tank, and supernatant directly gets into the composite wastewater equalizing tank, and deposition is squeezed into barrier film chamber-type press filter 11 press filtrations of adopting 300 order polypropylene fibre filter clothes through pneumatic diaphragm pump C10.Getting filter residue is chromium mud, its chromium sesquioxide content＞8wt%; Filtrating is waste discharge, and its total chrome content gets into the composite wastewater equalizing tank in Cr≤1.5mg/L.
Claims (7)
1. the recovery technology of chromium in the process hides Chrome Tanning Wastewater comprises once filtration, secondary filtration, reaction and filters for three times that it is characterized in that: the process hides Chrome Tanning Wastewater is carried out effectively shunting and single collection, and wherein,
⑴ once filter: through effectively shunting and single collection Chrome Tanning Wastewater get into collecting tank after the grid crack is 1 ~ 3mm grid filtration;
⑵ secondary filtration: be collected in through once filtering that Chrome Tanning Wastewater is metered into reaction tank again in the collecting tank after pressure filter filters;
⑶ reaction: the temperature of waste water in the control reaction tank, under whipped state, add alkali lye, regulate Chrome Tanning Wastewater pH value to 8.5 ~ 9.5, reacted 1 ~ 3 hour, make chromium fully be converted into chromium hydroxide precipitation; Under whipped state, add the anionic polyacrylamide of Chrome Tanning Wastewater quality 2 ~ 8ppm then, continue to stir 5 ~ 30 minutes, stop to stir afterreaction more than 3.5 hours;
⑷ three times filters: again through the pressure filter press filtration, the gained filter residue was the chromium sesquioxide content＞8wt% of chromium mud after reaction was accomplished, and filtrating is that the total chrome content of waste discharge is in Cr≤1.5mg/L.
2. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1; It is characterized in that: described process hides Chrome Tanning Wastewater is carried out effectively shunting and single collection is through different conduit systems; Waste water such as washing in the tanning operation, deliming, softening, degreasing are separated the single collection of realization Chrome Tanning Wastewater with Chrome Tanning Wastewater.
3. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1 is characterized in that: in described secondary filtration step ⑵, and canvas press cloth specification >=200 orders.
4. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1; It is characterized in that: in described reactions step ⑶; Described adding alkali lye is that wastewater temperature is 20 ~ 40 ℃ in the control reaction tank, and slow adding mass concentration is 30% ~ 50% aqueous sodium hydroxide solution under whipped state.
5. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1 is characterized in that: in described reactions step ⑶, the anionic polyacrylamide of said adding Chrome Tanning Wastewater is that mass concentration is 1 ‰ the aqueous solution.
6. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1 is characterized in that: in described three filtration step ⑷, and canvas press cloth specification >=250 orders.
7. the recovery technology of chromium in the process hides Chrome Tanning Wastewater according to claim 1 is characterized in that: in described reactions step ⑶, described stirring is mechanical stirring or pneumatic blending.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002478A (en) * | 2016-11-01 | 2018-05-08 | 昆山循清环保工程有限公司 | Handle extractant of trivalent chromic ion and preparation method thereof, extracting process in chroming waste liquor |
| CN111587227A (en) * | 2017-11-14 | 2020-08-25 | 科学与工业研究会 | Method for achieving zero water discharge in post-tanning operations |
| CN115465968A (en) * | 2022-09-16 | 2022-12-13 | 嘉兴学院 | Method for separating and recovering chromium in chrome tanning waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239769A (en) * | 2008-02-01 | 2008-08-13 | 浙江大学 | Leather-making waste water reusing treatment method |
| CN101407366A (en) * | 2008-10-28 | 2009-04-15 | 温州大学 | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation |
| CN102145961A (en) * | 2011-02-22 | 2011-08-10 | 波鹰(厦门)科技有限公司 | Tanning wastewater recycling device and method based on electrochemistry and ultrafiltration |
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- 2011-09-22 CN CN 201110282705 patent/CN102381781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239769A (en) * | 2008-02-01 | 2008-08-13 | 浙江大学 | Leather-making waste water reusing treatment method |
| CN101407366A (en) * | 2008-10-28 | 2009-04-15 | 温州大学 | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation |
| CN102145961A (en) * | 2011-02-22 | 2011-08-10 | 波鹰(厦门)科技有限公司 | Tanning wastewater recycling device and method based on electrochemistry and ultrafiltration |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002478A (en) * | 2016-11-01 | 2018-05-08 | 昆山循清环保工程有限公司 | Handle extractant of trivalent chromic ion and preparation method thereof, extracting process in chroming waste liquor |
| CN108002478B (en) * | 2016-11-01 | 2021-06-29 | 昆山循清环保工程有限公司 | Extraction agent for treating trivalent chromium ions in chrome tanning waste liquid, preparation method and extraction method thereof |
| CN111587227A (en) * | 2017-11-14 | 2020-08-25 | 科学与工业研究会 | Method for achieving zero water discharge in post-tanning operations |
| CN115465968A (en) * | 2022-09-16 | 2022-12-13 | 嘉兴学院 | Method for separating and recovering chromium in chrome tanning waste liquid |
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