CN102718342A - Deep recycling system and technology for chrome sludge acid leachate - Google Patents
Deep recycling system and technology for chrome sludge acid leachate Download PDFInfo
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- CN102718342A CN102718342A CN2012102163466A CN201210216346A CN102718342A CN 102718342 A CN102718342 A CN 102718342A CN 2012102163466 A CN2012102163466 A CN 2012102163466A CN 201210216346 A CN201210216346 A CN 201210216346A CN 102718342 A CN102718342 A CN 102718342A
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Abstract
The invention relates to a treatment method for chrome-containing sludge, and provides a deep recycling system and a deep recycling technology for chrome sludge acid leachate, which efficiently improve the recycling effect and are efficient and low in consumption. The system comprises a pressure filter, a chemical reaction purification tank, an ion exchange treatment system, a liquid collecting tank, a coagulation sedimentation tank, a sludge storage tank and a discharge hole; the output port of the pressure filter is connected with the input port of the chemical reaction purification tank; the output port of the chemical reaction purification tank is connected with the input port of the ion exchange treatment system; the output port of the ion exchange treatment system is connected with the liquid collecting tank and the coagulation sedimentation tank; the output port of the coagulation sedimentation tank is connected with the sludge storage tank and the discharge hole; a pH monitoring and regulating device is arranged in each of the chemical reaction purification tank and the coagulation sedimentation tank; and an elution device is arranged in the ion exchange treatment system.
Description
Technical field
The present invention relates to the treatment process of chromium-bearing sludge, particularly a kind of degree of depth reclaiming system and technology of chromium mud acid immersion.
Background technology
Leather processing is to be raw material with animal skin such as ox, pigs, through the manufacture a finished product process of skin of chemical treatment and mechanical workout.Generally comprise preparation, tanning and ornamenting three big workshop sections.Because chrome tanning is the main process for tanning of at present domestic and international process hides, these workshop section's principal pollutant are inorganic salt and heavy metal chromium, produce chromate waste water.Wastewater discharge accounts for more than 8% of process hides Total Water, and the discharging of High Content Chromium waste liquid not only causes great pollution to environment, and causes the significant wastage of resource.The treatment process of chromate waste water is a lot, comprises distillation under vacuum, reverse osmosis method, ion exchange method, solution extraction, alkaline precipitation and direct recycle method etc.And present domestic application more be alkaline precipitation, produce a large amount of chromium-bearing sludges.
The reasonable treatment and disposal of chromium-bearing sludge is current more scabrous problem always, and the treatment process of chromium-bearing sludge has roasting method (publication number: CN1940097, CN1696064), pickling process (publication number: CN102363820A, CN101041500), bioleaching method (publication number: CN101830616A, CN102424509A) etc.Present most widely used treatment process is a pickling process; Especially lower concentration pickling process (publication number: CN102381783A); Yet, no matter adopting which kind of reuse technology, effect is not very desirable after the chromium mud acid immersion reuse of generation; Through the in-depth analysis of seminar, we learn that organic composition and the salinity impurity in the immersion of chromium mud acid is the key factor of restriction chrome tanning performance.
Therefore press for a kind of effective reuse effect, efficient treatment process improved of exploitation, and realize the recovery and the resource utilization of chromium.
Summary of the invention
Therefore, to above-mentioned problem, the present invention proposes a kind of effective degree of depth reclaiming system and technology of improving reuse effect, the immersion of efficient chromium mud acid.
For solving this technical problem; The present invention takes following scheme: a kind of degree of depth reclaiming system of chromium mud acid immersion; Comprise pressure filter, chemical reaction treating pond, ion exchange treatment system, collecting tank, coagulative precipitation tank, storage basin and drain; Said pressure filter delivery port is connected with chemical reaction treating pond input aperture; Said chemical reaction treating pond delivery port is connected with ion exchange treatment system input aperture, and said ion exchange treatment System Outlet is connected with coagulative precipitation tank with collecting tank, and said coagulative precipitation tank delivery port is connected with storage basin and drain; Said chemical reaction treating pond and coagulative precipitation tank are provided with pH monitoring setting device, and said ion exchange treatment system is provided with the wash-out device.
Further, also be provided with whipping appts on the said chemical reaction treating pond.
Further, also be provided with whipping appts on the said coagulative precipitation tank.
Further, said wash-out device can be following current flushing or back flushing any.
A kind of degree of depth reuse treatment process of chromium mud acid immersion comprises the steps,
(1), immersion is held back solid particulate and impurity through pressure filter to the chromium mud acid, obtains containing the chromium filtered liq;
(2), will go up the chromium filtered liq that contains that a step obtains and feed the chemical reaction treating pond; Add oxygenant to the chemical reaction treating pond again and carry out chemical reaction; The pH value of regulating mixed solution in the chemical reaction treating pond with pH monitoring setting device maintains in the 2-4 scope it; It is green that the mixed solution color is, wherein oxygenant (v/v)=2.5% ~ 7.5%;
(3), will go up the mixed solution that a step obtains is the ion exchange treatment system of carrier through the dilution back through the IRN77 resin with flow velocity 5-15ml/min; Carrying out wash-out with flow velocity 5-15ml/min handles; Obtain the water outlet of ion exchange treatment system with absorption saturated column, wherein the eluant strength scope 5-15% (
V/v) between, eluent volume (L): IRN77 amount of resin (g)=5:8 ~ 5:4, mixeding liquid volume (L): IRN77 amount of resin (g)=1:2 ~ 3:4;
(4), will go up the ion exchange treatment system water outlet feeding coagulative precipitation tank that a step obtains; Adopt alkaline mix reagent to carry out coagulating; Adopt the stirring measure that it is fully reacted simultaneously; Obtain chromium metal mud and carry out acidleach processing, wherein ion exchange treatment system water outlet (L): alkaline mix reagent (g)=1:4 ~ 1:6;
(5), absorption saturated column that step (3) is obtained carries out wash-out, obtains elutriant, deposits collecting tank in.
Further, the pH regulator liquid in the said pH monitoring setting device be 1mol/L NaOH or 1mol/L HCL any.
Further, oxygenant can be 2.5%～3.5% NaCLO or 3.5%～7.5% H in the said step (2)
2O
2In any.
Further, eluent can be 5%～15% H in the said step (3)
2SO
4Or binary mixing acid (2.5%～7.5%) H
2SO
4Among+(2.5%～7.5%) HCl any.
Further, said step (4) neutral and alkali confection is formulated with the mass ratio of 2.5:1:0.5～5.5:1:0.5 by NaOH, MgO and CaO.
Through adopting the aforementioned techniques scheme, the invention has the beneficial effects as follows: through to adding oxygenant in the immersion of chromium mud acid, make the chromium mud acid soak the removal that the organism in the waste water obtains to a certain degree and do not change simultaneously Cr
3+Valence state, again through trivalent chromium there being the ion exchange treatment system than high absorption capacity trivalent chromium is effectively adsorbed, the water outlet of ion exchange treatment system is carried out coagulating sedimentation through alkaline mix reagent and is handled; Guarantee that water outlet chromium content is lower than 1.5mg/l; A little chromium mud returns acidleach workshop section, and saturated adsorbing carried out following current or adverse current wash-out, obtains the high chrome tanning liquid of purity; Realize the efficient reuse of the degree of depth of chromium mud acid immersion, greatly reduced system skin cost.
Description of drawings
Fig. 1 is the system architecture diagram of the embodiment of the invention;
Fig. 2 is the structural representation of chemical reaction treating pond in the embodiment of the invention;
Fig. 3 is the structural representation of embodiment of the invention intermediate ion exchange treatment system;
Fig. 4 is the structural representation of coagulative precipitation tank in the embodiment of the invention.
Embodiment
Combine accompanying drawing and embodiment that the present invention is further specified at present.
With reference to figure 1, Fig. 2, Fig. 3 and Fig. 4; The degree of depth reclaiming system of a kind of chromium mud acid immersion of the present invention; Comprise pressure filter 1, chemical reaction treating pond 2, ion exchange treatment system 3, collecting tank 4, coagulative precipitation tank 5, storage basin 6 and drain 7; Said pressure filter 1 delivery port is connected with chemical reaction treating pond 2 fluid inlets; Said chemical reaction treating pond 2 delivery ports are connected with ion exchange treatment system 3 input apertures, and said ion exchange treatment system 3 delivery ports are connected with coagulative precipitation tank 5 input apertures with collecting tank 4, and said coagulative precipitation tank 5 delivery ports are connected with storage basin 6 and drain 7.Said chemical reaction treating pond 2 is made up of PH monitoring setting device 21, first whipping appts 22 and reaction kettle 23; This reaction kettle 23 is provided with fluid inlet 231, dispensing mouth 232 and delivery port 233; Wherein fluid inlet 231 is connected with pressure filter 1 delivery port; Dispensing mouthfuls 232 is used to throw in oxygenant, and delivery port 233 then is connected with ion exchange treatment system 3 imports.Ion exchange treatment system 3 is made up of filler 31 and cylinder 32, and this cylinder is provided with fluid inlet 321, feeding opening 322 and delivery port 323, and wherein, feeding opening 322 is used to throw in eluent, and delivery port 323 then links to each other with collecting tank 4 and coagulative precipitation tank 5 imports.Said coagulative precipitation tank 5 is made up of PH monitoring setting device 51, second whipping appts 52 and reactor drum 53; Reactor drum 53 is provided with input aperture 531, feeding opening 532 and delivery port 533; This input aperture 531 is connected with the outlet of ion exchange treatment system 3; This feeding opening 532 is used to add alkaline mix reagent, and 533 of delivery ports are connected with storage basin 6 and drain 7.The model that said pressure filter 1 employing Jiangsu Qian Yuan Environmental Protection Technology Co., Ltd produces is the plate-and-frame filter press of XMYZB 12/1000.
Treatment process in conjunction with the recycling treatment system of Chrome Tanning Wastewater of the present invention comprises the steps,
(1), immersion is held back solid particulate and impurity through pressure filter 1 to the chromium mud acid, obtains containing the chromium filtered liq;
(2), will go up the chromium filtered liq that contains that a step obtains and feed chemical reaction treating pond 2; Add NaCLO to chemical reaction treating pond 2 again and carry out chemical reaction, use first whipping appts 22 to stir simultaneously, stir 30min at a slow speed; Be the pH value of the HCL adjusting chemical reaction treating pond 2 interior mixed solutions of 1mol/L simultaneously through 21 monitorings of the monitoring of the pH on the chemical reaction sedimentation tank 2 setting device and employing pH regulator liquid; Its pH value is maintained in the 2-4 scope, and it is green that the mixed solution color is, wherein NaCLO (
V/v)=3%;
(3), will go up the mixed solution that a step obtains is the ion exchange treatment system 3 of carrier through the dilution back through the IRN77 resin with flow velocity 10ml/min; Carrying out wash-out with flow velocity 10ml/min handles; Obtain water outlet of ion exchange treatment system and absorption saturated column, wherein eluent is 12% H
2SO
4(
V/v), eluent volume (L): IRN77 amount of resin (g)=7:8, mixeding liquid volume (L): amount of resin (g)=3:5;
(4), will go up the ion exchange treatment system water outlet feeding coagulative precipitation tank 5 that a step obtains; Coagulative precipitation tank 5 confection that adds NaOH, MgO and CaO carries out chemical reaction again; Use second whipping appts 52 to stir simultaneously; Stir earlier fast 1min, after stir 30min slowly, simultaneously through 51 monitorings of the monitoring of the pH on the coagulative precipitation tank 5 setting device and to adopt pH regulator liquid be the pH value that the HCL of 1mol/L regulates mixed solutions in the coagulative precipitation tank 5; Its pH value is maintained in the 8.5-10.5 scope, make the Cr in the waste water
3+Fully form Cr (OH)
3Precipitate; Obtain solidliquid mixture; Solidliquid mixture precipitated solid is fed in the storage basin 6, liquid is discharged through drain 7, wherein; NaOH (g): MgO (g): CaO (g)=4:1:0.5 in the alkalescence confection, ion exchange treatment system water outlet (L): alkaline mix reagent (g)=1:4 ~ 1:6;
(5), absorption saturated column that step (3) is obtained carries out the following current wash-out, obtains elutriant, deposits collecting tank 4 in.
The oxygenant that adds in the chemical reaction treating pond in the degree of depth recycling treatment system of chromium mud acid immersion of the present invention can be 2.5%～3.5% NaCLO or 3.5%～7.5% H
2O
2In any; PH regulator liquid on the pH regulator device be 1mol/L NaOH or 1mol/L HCl any; The wash-out device can be any of following current flushing or back flushing in the ion exchange treatment system; In the ion exchange treatment system eluant strength scope 5-15% (
V/v) between, eluent can be 5%～15% H
2SO
4Or binary mixing acid (2.5%～7.5%) H
2SO
4Among+(2.5%～7.5%) HCl any; Flow rate of liquid is good with 5-15ml/min in the ion exchange treatment system.In the ion exchange system with eluent volume (L): IRN77 amount of resin (g)=5:8 ~ 5:4, mixeding liquid volume (L): amount of resin (g)=1:2 ~ 3:4 is good; And the ratio of NaOH, MgO and CaO mass ratio is good with 2.5:1:0.5～5.5:1:0.5 in the confection that drops in the coagulative precipitation tank.
The present invention is through adding oxygenant in the chromium mud acid immersion, makes the chromium mud acid soak the removal that the organism in the waste water obtains to a certain degree and do not change simultaneously Cr
3+Valence state, again through trivalent chromium there being the IRN77 ion exchange treatment system than high absorption capacity trivalent chromium is effectively adsorbed, the water outlet of ion exchange treatment system is carried out coagulating sedimentation through alkaline mix reagent and is handled; Guarantee that water outlet chromium content is lower than 1.5mg/l; A little chromium mud returns acidleach workshop section, and saturated adsorbing carried out following current or adverse current wash-out, obtains the high chrome tanning liquid of purity; Realize the efficient reuse of the degree of depth of chromium mud acid immersion, greatly reduced system skin cost.
Although specifically show and introduced the present invention in conjunction with preferred embodiment; But the those skilled in the art should be understood that; In the spirit and scope of the present invention that do not break away from appended claims and limited; Can make various variations to the present invention in form with on the details, be protection scope of the present invention.
Claims (9)
1. the degree of depth reclaiming system of chromium mud acid immersion; It is characterized in that: comprise pressure filter, chemical reaction treating pond, ion exchange treatment system, collecting tank, coagulative precipitation tank, storage basin and drain; Said pressure filter delivery port is connected with chemical reaction treating pond input aperture; Said chemical reaction treating pond delivery port is connected with ion exchange treatment system input aperture; Said ion exchange treatment System Outlet is connected with coagulative precipitation tank with collecting tank; Said coagulative precipitation tank delivery port is connected with storage basin and drain, and said chemical reaction treating pond and coagulative precipitation tank are provided with pH monitoring setting device, and said ion exchange treatment system is provided with the wash-out device.
2. the degree of depth reclaiming system of chromium mud acid immersion according to claim 1 is characterized in that: also be provided with whipping appts on the said chemical reaction treating pond.
3. the degree of depth reclaiming system of chromium mud acid immersion according to claim 1 is characterized in that: also be provided with whipping appts on the said coagulative precipitation tank.
4. the degree of depth reclaiming system of chromium mud acid immersion according to claim 1, it is characterized in that: said wash-out device can be any of following current flushing or back flushing.
5. the degree of depth reuse treatment process of chromium mud acid immersion is characterized in that: comprises the steps,
(1), immersion is held back solid particulate and impurity through pressure filter to the chromium mud acid, obtains containing the chromium filtered liq;
(2), will go up the chromium filtered liq that contains that a step obtains and feed the chemical reaction treating pond; Add oxygenant to the chemical reaction treating pond again and carry out chemical reaction; The pH value of regulating mixed solution in the chemical reaction treating pond with pH monitoring setting device maintains in the 2-4 scope it; It is green that the mixed solution color is, wherein oxygenant (v/v)=2.5% ~ 7.5%;
(3), will go up the mixed solution that a step obtains is the ion exchange treatment system of carrier through the dilution back through the IRN77 resin with flow velocity 5-15ml/min; Carrying out wash-out with flow velocity 5-15ml/min handles; Obtain the water outlet of ion exchange treatment system with absorption saturated column, wherein the eluant strength scope 5-15% (
V/v) between, eluent volume (L): IRN77 amount of resin (g)=5:8 ~ 5:4, mixeding liquid volume (L): IRN77 amount of resin (g)=1:2 ~ 3:4;
(4), will go up the ion exchange treatment system water outlet feeding coagulative precipitation tank that a step obtains; Adopt alkaline mix reagent to carry out coagulating; Adopt the stirring measure that it is fully reacted simultaneously; Obtain chromium metal mud and carry out acidleach processing, wherein ion exchange treatment system water outlet (L): alkaline mix reagent (g)=1:4 ~ 1:6;
(5), absorption saturated column that step (3) is obtained carries out wash-out, obtains elutriant, deposits collecting tank in.
6. the degree of depth reuse treatment process of chromium mud acid according to claim 5 immersion is characterized in that: the pH regulator liquid in the said pH monitoring setting device be 1mol/L NaOH or 1mol/L HCL any.
7. the degree of depth reuse treatment process of chromium mud acid immersion according to claim 5 is characterized in that: oxygenant can be 2.5%～3.5% NaCLO or 3.5%～7.5% H in the said step (2)
2O
2In any.
8. the degree of depth reuse treatment process of chromium mud acid immersion according to claim 5 is characterized in that: eluent can be 5%～15% H in the said step (3)
2SO
4Or binary mixing acid (2.5%～7.5%) H
2SO
4Among+(2.5%～7.5%) HCl any.
9. the degree of depth reuse treatment process of chromium mud acid immersion according to claim 5, it is characterized in that: said step (4) neutral and alkali confection is formulated with the mass ratio of 2.5:1:0.5～5.5:1:0.5 by NaOH, MgO and CaO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210216346.6A CN102718342B (en) | 2012-06-28 | The degree of depth reclaiming system of a kind of chromium mud acid immersion and technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210216346.6A CN102718342B (en) | 2012-06-28 | The degree of depth reclaiming system of a kind of chromium mud acid immersion and technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102718342A true CN102718342A (en) | 2012-10-10 |
| CN102718342B CN102718342B (en) | 2016-11-30 |
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ID=
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609683A (en) * | 2014-12-12 | 2015-05-13 | 浙江工商大学 | Chrome tanning sludge heavy metal chromium regeneration method |
| CN104961277A (en) * | 2015-07-09 | 2015-10-07 | 常州大学 | Method for recycling and utilizing chromium in tannery waste water |
| CN109626662A (en) * | 2019-01-29 | 2019-04-16 | 浙江中金格派锂电产业股份有限公司 | Sodium chlorate-ion exchange resin treatment metallurgical waste water technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982433A (en) * | 2010-11-09 | 2011-03-02 | 南京大学 | Method for harmless and recycling treatment of stainless steel acid washing waste water neutralization sludge |
| CN102381783A (en) * | 2011-09-30 | 2012-03-21 | 哈尔滨工业大学 | Processing system for changing chrome tanning wastewater into resource and processing technique thereof |
| CN202744401U (en) * | 2012-06-28 | 2013-02-20 | 哈尔滨工业大学 | Deep recycling system for chromium-bearing sludge leached water |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982433A (en) * | 2010-11-09 | 2011-03-02 | 南京大学 | Method for harmless and recycling treatment of stainless steel acid washing waste water neutralization sludge |
| CN102381783A (en) * | 2011-09-30 | 2012-03-21 | 哈尔滨工业大学 | Processing system for changing chrome tanning wastewater into resource and processing technique thereof |
| CN202744401U (en) * | 2012-06-28 | 2013-02-20 | 哈尔滨工业大学 | Deep recycling system for chromium-bearing sludge leached water |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609683A (en) * | 2014-12-12 | 2015-05-13 | 浙江工商大学 | Chrome tanning sludge heavy metal chromium regeneration method |
| CN104609683B (en) * | 2014-12-12 | 2016-10-05 | 浙江工商大学 | A kind of renovation process of chrome tanning Heavy Metals in Sludge chromium |
| CN104961277A (en) * | 2015-07-09 | 2015-10-07 | 常州大学 | Method for recycling and utilizing chromium in tannery waste water |
| CN109626662A (en) * | 2019-01-29 | 2019-04-16 | 浙江中金格派锂电产业股份有限公司 | Sodium chlorate-ion exchange resin treatment metallurgical waste water technique |
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Granted publication date: 20161130 Termination date: 20170628 |