CN101357794A - Ion-exchange process technique of hexavalent chrome-containing waste water - Google Patents
Ion-exchange process technique of hexavalent chrome-containing waste water Download PDFInfo
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- CN101357794A CN101357794A CNA2008101569103A CN200810156910A CN101357794A CN 101357794 A CN101357794 A CN 101357794A CN A2008101569103 A CNA2008101569103 A CN A2008101569103A CN 200810156910 A CN200810156910 A CN 200810156910A CN 101357794 A CN101357794 A CN 101357794A
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Abstract
The invention discloses an ion exchange treatment technology of wastewater containing hexavalent chromium, the ion exchange treatment technology combines the regulation of pH value of the wastewater, the absorption, the regeneration, the maintenance and the recovery of Cr<6+> ions, thereby realizing the automatic treatment of the Cr<6+> ions in the wastewater containing the chromium; the technology of the invention has high degree of automation and good treatment effect and can be applied in the large-scale water treatment; chromium removing columns are designed to three columns or multiple columns, intermediate tanks which can regulate the pH value are arranged among various ion exchange columns, when two columns or multiple columns are connected in series for working, the pH value can be regulated during the intermediate process, thereby ensuring the wastewater treatment effect to be better and being capable of overcoming the problem that the pH is changed due to the change of the concentration of the ions during the conventional ion exchange process, thereby causing the decrease of the absorption ability of the ions by the resin; the outlet water quality can stably maintain the Cr<6+> to be less than 0.5mg/L; ion exchange resin can be effectively maintained and stably work for a long time; regenerated liquid can be recovered, thereby saving resources.
Description
Technical field
The present invention relates to a kind of treatment process of waste water, be specifically related to a kind of ion exchange treatment process that contains hexavalent chromium wastewater.
Background technology
Contain hexavalent chromium wastewater and extensively be present in plating, production field of metallurgy, not only cause the loss of resource, and cause serious environmental to pollute.Therefore the discharging that contains hexavalent chromium wastewater is strictly controlled.Ion exchange method is one of effective ways of processing waste water containing chrome, comparing other treatment processs, to have processing cost low, recyclable chromic advantage, but present treatment system and technology exist level of automation low, regeneration of resin and attended operation complexity, be not suitable for existing simultaneously in the large-scale wastewater treatment, particularly waste water trivalent chromium, the with serious pollution problem of resin is never had effective solution.Therefore can't realize at present extensively and large-scale application with the ion exchange method processing waste water containing chrome.
Summary of the invention
Technical problem to be solved by this invention provides a kind of can carrying out and extensively handles the technology that contains hexavalent chromium wastewater with the extensive ion exchange method of using, to realize containing the Cr in the hexavalent chromium wastewater
6+The ionic automatization is handled.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of ion exchange treatment process that contains hexavalent chromium wastewater comprises the steps:
(1) will contain hexavalent chromium wastewater and after the physical cleaning processing is qualified, send into the pH regulator pond, adjust pH to 1～6, pH value preferred 2～5;
(2) waste water is sent into the placed in-line ion exchange column absorption of n-1 root Cr
6+Ion, n gets the natural number in 3～10, be provided with the medial launder that to regulate the pH value between the adjacent two radical ion exchange columns, keep the pH value 1～6, the pH value is preferred 2～5, can make water treatment effect better like this, can overcome in the conventional ion exchange process, because the pH that the variation of ionic concn produces changes, thus the problem that causes resin that the ionic adsorptive power is descended; The water outlet of n-1 radical ion exchange column detects Cr
6+Ionic concentration, the effusive liquid of water outlet of n-1 radical ion exchange column is Cr
6+Ion reaches the waste water of emission standard;
(3) as the Cr of the water outlet of n-1 radical ion exchange column
6+When ionic concn reaches 0.5mg/L,
The 1st radical ion exchange column and other n-2 radical ion exchange column are disconnected;
N radical ion exchange column connect with other n-2 radical ion exchange column (other n-2 radical ion exchange column is other ion exchange column except the 1st radical ion exchange column), the 2nd radical ion exchange column becomes the 1st radical ion exchange column, the 3rd radical ion exchange column becomes the 2nd radical ion exchange column, by that analogy, become n-1 radical ion exchange column until n radical ion exchange column, return step (2);
Simultaneously, it is saturated to improve the resin utilization ratio to guarantee that resin adsorbs as far as possible that original the 1st radical ion exchange column carries out the circulation absorption in pH regulator pond-dechromisation post-pH regulator pond, and the largest loop adsorption time is calculated as follows: cycle time T=η * resin leakage time T
1-resin regeneration time T
2, η gets 0.6～1; After circulation absorption finishes, original the 1st radical ion exchange column is regenerated by following program: water to pH regulator pond-alkali lye is washed and is entered in regeneration liquid bath-post residue alkali lye back suction behind the post and clean post-rinse water to diluted alkaline groove-water and enter pH regulator pond-acid solution and circulate and wash post in the emptying post, and it is stand-by that original completely the 1st radical ion exchange column of regenerating becomes n radical ion exchange column.
In addition, because of long term operation causes resin stain, when the operating capacity of the resin in the ion exchange column drop to initial value 0.8 the time, start following resin maintenance program: the circulation of single ion exchange column reproducer-safeguard liquid is squeezed into 2～12 hours-water of single ion exchange column and is cleaned post-rinse water and enter pH regulator pond-acid solution circulation and washed post 1～2 hour, and safeguarded every radical ion exchange column successively according to this program.Wherein, when the resin slight pollution, the described liquid of safeguarding comprises following components in weight percentage: 8～16% hydrochloric acid, and all the other are deionized water; During the resin serious pollution, promptly adopt hydrochloric acid to safeguard when liquid can't make resin return to initial exchange capacity, then be serious pollution, need this moment with the liquid of safeguarding that contains oxygenant, promptly comprise following components in weight percentage: sodium-chlor 10～25%, hydrogen peroxide 3～10%, sodium hydroxide 1～5%, all the other are water.
Said n radical ion exchange column is equipped with macroporous strong basic anionite-exchange resin, and post hollow volume is 1/3 of a column volume, and each cylinder is provided with the resin thief hole, is used to take a sample detect the operating capacity of resin.
In the step (3), the used alkali lye of resin regeneration is the sodium hydroxide of 4～10% (w/w), and described acid solution is the hydrochloric acid of 1～10% (w/w).
In the step (3), alkali lye is washed the post process and is washed post with the speed of 1 times of bed volume/h.
In the step (3), the Na in the regenerated liquid
2CrO
4, after Zeo-karb is handled, become H
2CrO
4Utilize or further process recovery solid Na again
2Cr
2O
7
The circulation adsorption time is calculated as follows: the longest cycle time T=η * resin leakage time T
1-resin regeneration time T
2, η gets 0.6～1.
Wherein resin regeneration time T
2=post water emptying time+recovery time+scavenging period+pickling cycling time=post water emptying time+N
1* resin volume ÷ regeneration velocity+post water emptying time+N
2* resin volume ÷ cleans flow velocity+N
3* resin volume ÷ pickling flow velocity, N usually
1Get 2～4, N
2Get 3～12, N
3Get 3～6.Usually regeneration velocity is got 1～4 times of bed volume/h, cleans flow velocity and gets 3～6 bed volumes/h, and pickling resin flow velocity is got 3～6 times of bed volume/h.Can be according to Cr in the waste water
6+The exchange capacity of concentration, circular flow, amount of resin and resin, determine actual cycling time, in principle as long as guarantee that as far as possible resin can be fully saturated, if consideration will be reclaimed Cr
6+, in order to guarantee to reclaim Cr
6+Concentration and purity, then the saturation ratio of resin is high as far as possible, in this case, the saturation ratio of actual measurement resin and the cycling time that needs are necessary, but which kind of situation no matter, can not surpass the longest cycle time T cycling time
2The saturation ratio of resin is determined as follows, identical time point, Cr in the exchange column water outlet
6+Measured concentration and the water inlet in measured concentration Cr
6+Concentration when identical, saturation ratio is 100%, if water inlet Cr
6+Measured concentration be A, and Cr in the water outlet
6+Measured concentration be 0.9A, then saturation ratio is 90%, by that analogy.
Wherein, leakage time T
1Measure: Cr in waste water
6+When concentration is maximum, picking up counting when exchange column is intake, is T the time when leakage occurring
1
The ion exchange treatment process that contains hexavalent chromium wastewater of the present invention adopts online Cr
6+The automatic mode that detector and programmable logic controller (PLC) are controlled all valves, pressure and flow guarantees the processing quality of waste water and the security of operation.
Beneficial effect: the ion exchange treatment process that contains hexavalent chromium wastewater of the present invention has following advantage:
1, level of automation height, treatment effect is good, can be applicable to extensive water treatment.
2, the dechromisation post is designed to three posts or multicolumn, be provided with the medial launder that to regulate the pH value between each ion exchange column, when two posts or multicolumn tandem working, pilot process can be regulated pH value, make water treatment effect better, can overcome in the conventional ion exchange process, because the PH that the variation of ionic concn produces variation, thereby the problem that causes resin that the ionic adsorptive power is descended.
3, effluent quality can be stablized maintenance Cr
6+＜0.5mg/L.
4, ion exchange resin can effectively be safeguarded, but long-term stable operation.
5, regenerated liquid is recyclable, economizes on resources.
6, handle cyanide containing wastewater with present common chemical method and compare, also having does not need to add chemical agent in waste water, and processed waste water saliferous rate is low, helps the advantage that waste water reclamation utilizes.
Description of drawings
Fig. 1 is the device synoptic diagram that contains the ion exchange treatment process of hexavalent chromium wastewater of the present invention.
Embodiment:
Embodiment 1:
Certain Electroplate Factory's chromate waste water water quality sees Table 1:
The high-content mg/L of table 1 chromate waste water pollutent
| Kind of waste water | The water yield (m 3/d) | pH | Cr 6+ | Cr 3+ | Cu 2+ | Ni 2+ | Zn 2+ | CN - |
| Chromate waste water | 100 | 0.5-0.7 | 150 | 30 | 10 | 8 | 6 | 5 |
Water outlet after art breading of the present invention requires to reach Cr
6+Concentration＜0.5mg/L, concrete equipment and operate as follows:
One, equipment:
The dechromisation post: by the design of three posts, single-column resin volume is 2m
3, resin is D301/D301T, and the exchange column material is a glass reinforced plastic, and resin height accounts for 2/3 of full post height.Total water outlet is established a cyanogen on-line monitoring instrument.The absorption of exchange column, regeneration are by the automated operation design.
Wash post tank: useful volume 20m
3, have fluid level controller to keep water level automatically, pump 3 working flow rate Q 〉=8m
3/ time.
Diluted alkaline groove: useful volume 6m
3, volume pump working flow rate Q 〉=2m
3In/time, diluted alkaline is 4%NaOH, the band fluid level controller.
Sour water groove: useful volume 4m
3, the band fluid level controller.
Regeneration liquid bath: useful volume 4m
3, pump 5 working flow rate Q 〉=4m
3/ time, the band fluid level controller.
Circulation groove 1 volume 6m
3, the control of band liquid level, pump 2 working flow rate Q 〉=4m
3/ time.
Pump a, b, the effective working flow 〉=5m of c, d
3/ h.
Groove 1,2,3 useful volumes 〉=4m
3, the band fluid level controller, and the pH monitor is housed.
Two, workflow explanation:
Waste water is sent into the dechromisation post with pump 1, the working flow Q 〉=5m of transferpump
3/ h.The dechromisation post is designed to three posts, and resin adopts macroporous strong basic anionite-exchange resin, single-column resin volume 2m
3, resin top void volume is 1/3 of a resin volume, each cylinder is established the resin thief hole.Between transferpump water outlet and dechromisation post water-in tensimeter and under meter are set, the control pressure gauge pressure is no more than 0.2MPA, installs the automatically unloading loop in case of necessity additional.Dechromisation post water outlet is provided with thief hole.Native system adopts the automatic red-tape operati mode of PLC, at system's water outlet chromic content in the online automatic colorimetric analysis instrument control water outlet is set, (Cr when chromic content overproof appears in sexavalent chrome leakage and the water outlet in the dechromisation post
6+＜0.5mg/L), to the pH regulator pond, the water intaking valve outlet valve of opening another dechromisation post simultaneously continues to keep water outlet to the subsequent disposal operation to on-line automatic colorimetric analysis instrument by PLC control pneumavalve automatic switchover water outlet.Saturated as far as possible it is definite press following formula cycling time to improve the resin utilization ratio to guarantee the dechromisation resin in the circulation that the dechromisation post that leakage occurs continues to carry out waste water by pH regulator pond-dechromisation post-pH regulator pond, cycling time=resin leakage time-resin regeneration time.Resin regeneration time=post water emptying time+N
1* resin volume ÷ regeneration velocity+regenerator emptying time+N
2* resin volume ÷ cleans flow velocity+N
3* resin volume ÷ pickling flow velocity=0.3+3 * 2 ÷ 2+0.3+3 * 2 ÷ 8+2 * 2 ÷ 4=5.35 hours.N
1＝3，N
2＝3，N
3＝2。Regeneration velocity 2m
3In/time, clean flow velocity 8m
3/ time, pickling resin flow velocity 4m
3/ time.The leakage time T
1Measure: Cr in waste water
6+During concentration maximum (150mg/L), pick up counting when exchange column is intake, the time actual measurement is T when leakage occurring
1=58 hours, therefore the longest cycle time T=0.8 * 58-5.35=41.05 hour, this example actual cycle time set was 36 hours.The cycling time of setting, display alarm started the autoregeneration program when reaching.Regenerator adopts 4～10% sodium hydroxide, and the regenerator transferpump adopts volume pump, volume pump 1 flow velocity Q=2m
3/ h.Reproducer is: resin is saturated-post in the water back suction to pH regulator pond (0.3h)-volume pump open-alkali lye enter in regeneration liquid bath (3h)-post the alkali lye back suction to diluted alkaline groove (0.3h)-volume pump pass-pump 3 open-clear water washes post (1.5h)-pump 3 pass-pumps 2 and opens-sour water circulates and wash post (1h)-finish regeneration.Regenerative process becomes auto-programming by this flow scheme design.Sour water adopts the hydrochloric acid of pH1～6, and use acid washing post is when advancing waste water next time, prevents that the pH value rising of water termination in initial stage waste water and the post from causing initial stage water part Cr
6+With CrO
4 2-Form exists, and makes resin absorption Cr
6+Ability drop, thus water outlet Cr caused
6+Exceed standard.Wash water storage tank, diluted alkaline groove and sour water groove are installed the automatic level controller self-feeding and are kept liquid level.When the operating capacity of resin drop to initial value 0.8 the time (sampling and measuring), start the resin maintenance program.Maintenance program is: after the resin regeneration-safeguard that liquid pump 2 leaves-safeguard that liquid returns circulation groove and 6 hours-pump, the 2 pass-pumps 3 that circulate are opened (6m
3Rinse water)-and rinse water enters pH regulator/mixing pit-pump 3 pass-pumps 2 and opens-and the sour water circulation washes 1 hour-pump of post 2 and closes-finish maintenance.Maintenance process becomes auto-programming by this flow scheme design.Safeguard during the resin slight pollution that liquid adopts 1～10% hydrochloric acid, adopts the liquid of safeguarding of following proportioning: sodium-chlor 10～25%, hydrogen peroxide 3～10%, sodium hydroxide 1～5% during serious pollution.Regenerated liquid after resin is saturated contains 10～13% Na
2CrO
4, reusable edible.Waste water in the medial launder 1,2,3 is controlled in the scope of pH1～3 by the pH monitoring device.
Three, dechromisation post automatically working process description:
Post 1, post 2, post 3 are respectively dechromisation post 1, dechromisation post 2, dechromisation post 3.Chromate waste water from the chromate waste water water collecting basin enters the pH regulator pond after solid impurity is removed in pre-treatment, as follows and routine processes:
1, absorption: pump 1 leaves, and valve 2 leaves, and valve 28 leaves, and chromate waste water enters post 1 from the pH regulator pond through pump 1, valve 2, enters groove 2 through valve 28 then.Flow control valve 52 leaves, and makes wastewater flow remain on 5m
3/ h also can adopt frequency transformer to replace motor valve 63 control pumps 1, keeps the influent waste water flow.After waste water flowed into, groove 2 liquid levels rose, when groove 2 liquid levels to the upper limit, pump b leaves (by the control of the liquidometer in the groove 2), valve 5 leaves, valve 32 leaves, waste water enters post 2 from groove 2 through pump b, valve 5, passes through valve 32 then, through Cr
6+Reach controlling index (Cr in the thread detector detection
6+After the concentration≤0.5mg/L), enter pond, i.e. post 1 and post 2 series operations in the middle of the waste water behind the dechromisation.
2,2 water inlets of post 1 post are switched: after after a while, along with the increase of ion exchange column adsorptive capacity, Cr will appear in post 2
6+The ion leakage is as the Cr that is located at water outlet
6+Detect Cr in the water at thread detector
6+(Cr when ionic concn exceeds standard
6+Concentration 〉=0.5mg/L), valve 2 closes, and valve 6 leaves, and valve 29 leaves, and influent waste water switches to post 2 by post 1, promptly enters post 2 by pump 1 through valve 6, enters groove 3 through valve 29 again.Valve 5 closes simultaneously, and valve 32 closes, and post 2 stops efflux wastewater, and pump b stops, and valve 28 closes, and post 1 stops to groove 2 drainings.After waste water entered groove 3, groove 3 liquid levels rose, when groove 3 liquid levels to the upper limit, valve 9 leaves, valve 33 leaves, pump c leaves (by the control of the liquidometer in the groove 3), waste water enters post 3 from groove 3 through pump c, valve 9, passes through valve 33 then, through Cr
6+Reach controlling index (Cr in the thread detector detection
6+After the concentration≤0.5mg/L), enter pond, i.e. post 2 and post 3 series operations in the middle of the waste water behind the dechromisation.
3, post 1 waste water circulation: when influent waste water is switched to post 2 by post 1 when, valve 55 leaves, pump 1-1 leaves, valve 47 leaves, valve 25 leaves, and valve 54 leaves, and waste water returns the pH regulator pond from the pH regulator pond through valve 55, pump 1-1, valve 47, post 1, valve 25, valve 54, circulate, in the circulation time limit of regulation, make post 1 continue absorption Cr
6+Ion is to improve the utilization ratio of resin.Arrive the circulation time limit T of regulation, valve 53 leaves, and valve 55 closes, and valve 51 leaves, and valve 54 closes, and valve 47 closes, and valve 34 leaves (emptying), the waste water in the post 1 from post 1 through valve 25, valve 53, pump 1-1, valve 51, back suction to the pH regulator pond.When post 1 liquid level drops to lower limit (in the post 1 fluid level controller being housed), promptly in the post after the water emptying, pump 1-1 stops, and valve 34 closes, and valve 53 closes, and valve 51 closes, and valve 25 closes, and post 1 waste water loop ends enters post 1 regeneration step.
4, post 1 regeneration: valve 44 leaves, and valve 14 leaves, and valve 34 leaves, and volume pump is opened, and 5% liquid caustic soda enters post 1 from the diluted alkaline groove through volume pump, valve 44, valve 14, flows into the regeneration liquid bath through valve 34 then.Volume pump is spacing to be arrived, and valve 44 closes, and valve 14 closes, and stops to carry 5% liquid caustic soda to post 1.Valve 19 leaves, and pump d leaves, and alkali lye is arrived the diluted alkaline groove through valve 19, pump d by back suction in the post 1, and after the alkali lye emptying, pump d closes (by fluid level controller control in the post 1) in the post, and valve 19 cuts out, and valve 34 cuts out.Valve 43 leaves, and valve 3 leaves, and valve 22 leaves, and pump 3 leaves (timing 90 minutes), washes post water and enters post 1 from washing the post tank through pump 3, valve 43, valve 3, and enter the PH equalizing tank through valve 22.Pump 3 timing were arrived in 90 minutes, and pump 3 closes, and valve 3 closes, and valve 22 cuts out, and valve 43 closes, and post 1 washing is finished.After post 1 washing was finished, valve 57 left, valve 41 leaves, and valve 42 leaves, valve 13 leaves, and valve 4 leaves, and pump 2 leaves, the sour water of pH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 13, post 1, valve 4, valve 42, circulates, and the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 13 closes, valve 4 closes, and valve 57 closes, and post 1 regeneration is finished.
5,3 water inlets of post 2 posts are switched: after after a while, along with the increase of ion exchange column adsorptive capacity, ion Cr will appear in post 3 water outlets
6+Leakage is as the Cr that is located at water outlet
6+Detect Cr in the water at thread detector
6+(Cr when ionic concn exceeds standard
6+Concentration 〉=0.5mg/L), valve 6 closes, and valve 10 leaves, and valve 30 leaves, and influent waste water switches to post 3 by post 2, promptly enters post 3 by pump 1 through valve 10, enters groove 1 through valve 30 again.Valve 9 closes simultaneously, and valve 33 closes, and post 3 stops efflux wastewater, and pump c stops, and valve 29 closes, and post 2 stops to groove 3 drainings.After waste water entered groove 1, groove 1 liquid level rose, when groove 1 liquid level to the upper limit, valve 1 leaves, valve 31 leaves, pump a leaves (by the control of the liquidometer in the groove 1), waste water enters post 1 from groove 1 through pump a, valve 1, passes through valve 31 then, through Cr
6+Reach controlling index (Cr in the thread detector detection
6+After the concentration≤0.5mg/L), enter pond, i.e. post 3 and post 1 series operation in the middle of the waste water behind the dechromisation.
6, post 2 waste water circulation: when influent waste water is switched to post 3 by post 2 when, valve 55 leaves, pump 1-1 leaves, valve 46 leaves, valve 26 leaves, and valve 54 leaves, and waste water returns the pH regulator pond from the pH regulator pond through valve 55, pump 1-1, valve 46, post 2, valve 26, valve 54, circulate, in the circulation time limit of regulation, make post 2 continue absorption Cr
6+Ion.Arrive the circulation time limit T of regulation, valve 53 leaves, and valve 55 closes, and valve 51 leaves, and valve 54 closes, and valve 46 closes, and valve 35 leaves (emptying), the waste water in the post 2 from post 2 through valve 26, valve 53, pump 1-1, valve 51, back suction to the pH regulator pond.When post 2 liquid levels drop to lower limit (in the post 2 fluid level controller being housed), promptly in the post after the water emptying, pump 1-1 stops, and valve 35 closes, and valve 53 closes, and valve 51 closes, and valve 26 closes, and post 2 waste water loop ends enter post 2 regeneration step.
7, post 2 regeneration: valve 44 leaves, and valve 16 leaves, and valve 35 leaves, and volume pump is opened, and 5% liquid caustic soda enters post 2 from the diluted alkaline groove through volume pump, valve 44, valve 16, flows into the regeneration liquid bath through valve 35 then.Volume pump is spacing to be arrived, and valve 44 closes, and valve 16 closes, and stops to carry 5% liquid caustic soda to post 2.Valve 20 leaves, and pump d leaves, and alkali lye is arrived the diluted alkaline groove through valve 20, pump d by back suction in the post 2, and after the alkali lye emptying, pump d closes (by fluid level controller control in the post 2) in the post, and valve 20 cuts out, and valve 35 cuts out.Valve 43 leaves, and valve 7 leaves, and valve 23 leaves, and pump 3 leaves (timing 90 minutes), washes post water and enters post 2 from washing the post tank through pump 3, valve 43, valve 7, and enter the PH equalizing tank through valve 23.Pump 3 timing were arrived in 90 minutes, and pump 3 closes, and valve 7 closes, and valve 23 cuts out, and valve 43 closes, and post 2 washings are finished.After post 2 washings were finished, valve 57 left, valve 41 leaves, and valve 42 leaves, valve 15 leaves, and valve 8 leaves, and pump 2 leaves, the sour water of PH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 15, post 2, valve 8, valve 42, circulates, and the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 15 closes, valve 8 closes, and valve 57 closes, and post 2 regeneration are finished.
8,1 water inlet of post 3 posts is switched: after after a while, along with the increase of ion exchange column adsorptive capacity, ion Cr will appear in post 1 water outlet
6+Leakage is as the Cr that is located at water outlet
6+Detect Cr in the water at thread detector
6+(Cr when ionic concn exceeds standard
6+Concentration 〉=0.5mg/L), valve 10 closes, and valve 1 leaves, and valve 28 leaves, and influent waste water switches to post 1 by post 3, promptly enters post 1 by pump 1 through valve 2, enters groove 2 through valve 28 again.Valve 1 closes simultaneously, and valve 31 closes, and post 1 stops efflux wastewater, and pump a stops, and valve 30 closes, and post 3 stops to groove 1 draining.After waste water entered groove 2, groove 2 liquid levels rose, when groove 2 liquid levels to the upper limit, valve 5 leaves, valve 32 leaves, pump b leaves (by the control of the liquidometer in the groove 2), waste water enters post 2 from groove 2 through pump b, valve 5, passes through valve 32 then, through Cr
6+Reach controlling index (Cr in the thread detector detection
6+After the concentration≤0.5mg/L), enter pond, i.e. post 1 and post 2 series operations in the middle of the waste water behind the dechromisation.
9, post 3 waste water circulation: when influent waste water is switched to post 1 by post 3 when, valve 55 leaves, pump 1-1 leaves, valve 45 leaves, valve 27 leaves, and valve 54 leaves, and waste water returns the pH regulator pond from the pH regulator pond through valve 55, pump 1-1, valve 45, post 3, valve 27, valve 54, circulate, in the circulation time limit of regulation, make post 3 continue absorption Cr
6+Ion.Arrive the circulation time limit T of regulation, valve 53 leaves, and valve 55 closes, and valve 51 leaves, and valve 54 closes, and valve 45 closes, and valve 36 leaves (emptying), the waste water in the post 3 from post 3 through valve 27, valve 53, pump 1-1, valve 51, back suction to the pH regulator pond.When post 3 liquid levels drop to lower limit (in the post 3 fluid level controller being housed), promptly in the post after the water emptying, pump 1-1 stops, and valve 36 closes, and valve 53 closes, and valve 51 closes, and valve 27 closes, and post 3 waste water loop ends enter post 3 regeneration step.
10, post 3 regeneration: valve 44 leaves, and valve 18 leaves, and valve 36 leaves, and volume pump is opened, and 5% liquid caustic soda enters post 3 from the diluted alkaline groove through volume pump, valve 44, valve 18, flows into the regeneration liquid bath through valve 36 then.Volume pump is spacing to be arrived, and valve 44 closes, and valve 18 closes, and stops to carry 5% liquid caustic soda to post 3.Valve 21 leaves, and pump d leaves, and alkali lye is arrived the diluted alkaline groove through valve 21, pump d by back suction in the post 3, and after the alkali lye emptying, pump d closes (by fluid level controller control in the post 3) in the post, and valve 21 cuts out, and valve 36 cuts out.Valve 43 leaves, and valve 11 leaves, and valve 24 leaves, and pump 3 leaves (timing 90 minutes), washes post water and enters post 3 from washing the post tank through pump 3, valve 43, valve 11, and enter the PH equalizing tank through valve 24.Pump 3 timing were arrived in 90 minutes, and pump 3 closes, and valve 11 closes, and valve 24 cuts out, and valve 43 closes, and post 3 washings are finished.After post 3 washings were finished, valve 57 left, valve 41 leaves, and valve 42 leaves, valve 17 leaves, and valve 12 leaves, and pump 2 leaves, the sour water of PH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 17, post 3, valve 12, valve 42, circulates, and the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 17 closes, valve 12 closes, and valve 57 closes, and post 3 regeneration are finished.
11, continue to repeat the step of 2-10.
12, discharging of sour water groove sour water and replacing: after acid waste water used for several times, the pH value can raise, and contains some foreign ions, and generally using needs replacing for 3-6 time.At this moment, adopt manual command.Valve 41 closes, and valve 47 leaves, and valve 38 leaves, and pump 2 starts, and useless sour water enters the PH equalizing tank from the sour water groove through valve 47, pump 2, valve 38, and when sour water tank liquor position drops to lower limit, pump 2 cuts out, and valve 38 closes.After the useless sour water emptying, begin to replenish fresh sour water, this moment, purge valve was opened, sour water tank liquor position rises to the upper limit, purge valve closes, and agitator motor is opened, and valve 37 leaves, pump 4 leaves, 8% hydrochloric acid adds the sour water grooves from the dilute hydrochloric acid storage tank through pump 4, valve 37, and the pH value that monitors sour water when PH monitor (control pump 4) is at 1-2, and pump 4 closes, valve 37 closes, discharging of groove sour water and replacing
13, shut down step: when equipment need not or keep in repair (overhaul) for a long time for a long time, follow these steps to carry out shutdown procedure.(1) medial launder empties: manual command, and valve 48,49,50 open simultaneously, pump a, b, c starts, and waste water is from groove 1,2,3, through valve 48,49,50, pump a, b, c enter the chromate waste water water collecting basin.Behind the discharge of wastewater, groove 1,2,3 liquid levels arrive down respectively in limited time, pump a, b, c closes, valve 48,49,50 close.(2) water empties in the post: manual command, and valve 53 leaves, and valve 51 leaves, and valve 34,35,36 leaves (air inlet).Valve 25,26,27 leaves, and pump 1-1 starts, in the post waste water respectively through valve 25,26,27, valve 53, pump 1-1, valve 51 returns the PH equalizing tank.When post 1, post 2, post 3 liquid levels arrival lower limit, valve 25,26,27 closes, and pump 1-1 closes, and valve 51 closes, and valve 53 closes, valve 34,35,36 passes.(3) column regeneration: manual command, 4,7,10 programs are carried out respectively set by step, according to shutting down practical situation two pillars of working are regenerated.(4) system makes zero: system's return to primitive age state.
14, resin maintenance service: after operation after a while, resin has pollution to a certain degree, therefore must safeguard resin, to recover the exchange capacity of resin.Before safeguarding beginning, resin will be regenerated earlier.Adopt manual command, the mode that program automatically performs.Program is: 1. post 1 safeguards that valve 56 leaves, and pump 2 leaves, and valve 41 leaves, valve 13 leaves, and valve 4 leaves, and valve 58 leaves, and safeguards that liquid returns circulation groove from circulation groove through valve 56, pump 2, valve 41, valve 13, post 1, valve 4, valve 58, circulate, circulate after 6 hours, valve 56, pump 2, valve 41, valve 58 are closed.After safeguarding the liquid loop ends, valve 40 leaves, and valve 43 leaves, and pump 3 leaves, wash post water and enter post 1 through pump 3, valve 43, valve 13 from washing the post tank, coupled columns 1 cleans, and Cleaning Wastewater enters the chromate waste water water collecting basin through post 1, valve 4, valve 40, cleans after 2 hours, pump 3 stops, valve 43 closes, and valve 40 closes, and post 1 washing is finished.After post 1 washing was finished, valve 57 left, valve 41 leaves, and valve 42 leaves, pump 2 leaves, and the sour water of PH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 13, post 1, valve 4, valve 42, circulates, the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 13 closes, valve 4 closes, and valve 57 closes, and post 1 is safeguarded and finished.2. post 2 safeguards that valve 56 leaves, and pump 2 leaves, and valve 41 leaves, valve 15 leaves, and valve 8 leaves, and valve 58 leaves, and safeguards that liquid returns circulation groove from circulation groove through valve 56, pump 2, valve 41, valve 15, post 2, valve 8, valve 58, circulate, circulate after 6 hours, valve 56, pump 2, valve 41, valve 58 are closed.After safeguarding the liquid loop ends, valve 40 leaves, and valve 43 leaves, and pump 3 leaves, wash post water and enter post 2 through pump 3, valve 43, valve 15 from washing the post tank, coupled columns 2 cleans, and Cleaning Wastewater enters the chromate waste water water collecting basin through post 2, valve 8, valve 40, cleans after 2 hours, pump 3 stops, valve 43 closes, and valve 40 closes, and post 2 washings are finished.After post 2 washings were finished, valve 57 left, valve 41 leaves, and valve 42 leaves, pump 2 leaves, and the sour water of PH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 15, post 2, valve 8, valve 42, circulates, the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 15 closes, valve 8 closes, and valve 57 closes, and post 2 is safeguarded and finished.3. post 3 safeguards that valve 56 leaves, and pump 2 leaves, and valve 41 leaves, valve 17 leaves, and valve 12 leaves, and valve 58 leaves, and safeguards that liquid returns circulation groove from circulation groove through valve 56, pump 2, valve 41, valve 17, post 3, valve 12, valve 58, circulate, circulate after 6 hours, valve 56, pump 2, valve 41, valve 58 are closed.After safeguarding the liquid loop ends, valve 40 leaves, and valve 43 leaves, and pump 3 leaves, wash post water and enter post 3 through pump 3, valve 43, valve 17 from washing the post tank, coupled columns 3 cleans, and Cleaning Wastewater enters the chromate waste water water collecting basin through post 3, valve 12, valve 40, cleans after 2 hours, pump 3 stops, valve 43 closes, and valve 40 closes, and post 3 washings are finished.After post 3 washings were finished, valve 57 left, valve 41 leaves, and valve 42 leaves, pump 2 leaves, and the sour water of PH2-4 returns the sour water groove from the sour water groove through valve 57, valve 41, pump 2, valve 17, post 3, valve 12, valve 42, circulates, the sour water circulation is after 1 hour, pump 2 closes, and valve 41 closes, and valve 42 closes, valve 17 closes, valve 12 closes, and valve 57 closes, and post 3 is safeguarded and finished.
15, the useless liquid of safeguarding of circulation groove discharges: manual command, valve 56 leaves, valve 38 leaves, pump 2 leaves, and gives up and safeguards that liquid enters the chromate waste water water collecting basin from circulation groove through valve 56, pump 2, valve 38.Useless safeguard the liquid discharging after, circulation groove 1 liquid level drops to lower limit, pump 2 closes, valve 38 closes, valve 56 closes.
16, the processing of regenerated liquid in the regeneration liquid bath: regenerated liquid is for containing Cr
6+The Na of 30～40g/L
2CrO
4Alkaline aqueous solution, the regenerated liquid liquid level is sent into the recovery process processing automatically by pump 5 after arriving the upper limit in the regeneration liquid bath, reclaims chromic acid.
Claims (8)
1, a kind of ion exchange treatment process that contains hexavalent chromium wastewater is characterized in that this method comprises the steps:
(1) will contain hexavalent chromium wastewater and send into the pH regulator pond, adjust pH to 1～6;
(2) waste water is sent into the placed in-line ion exchange column absorption of n-1 root Cr
6+Ion, n are got the natural number in 3～10, are provided with the medial launder that can regulate the pH value between the adjacent two radical ion exchange columns, keep the pH value 1～6, and the water outlet of n-1 radical ion exchange column detects Cr
6+Ionic concentration, the effusive liquid of water outlet of n-1 radical ion exchange column is Cr
6+Ion reaches the waste water of emission standard;
(3) as the Cr of the water outlet of n-1 radical ion exchange column
6+When ionic concn reaches 0.5mg/L,
The 1st radical ion exchange column and other n-2 radical ion exchange column are disconnected;
N radical ion exchange column is connected with other n-2 radical ion exchange column, the 2nd radical ion exchange column becomes the 1st radical ion exchange column, and the 3rd radical ion exchange column becomes the 2nd radical ion exchange column, by that analogy, become n-1 radical ion exchange column until n radical ion exchange column, return step (2);
Simultaneously, original the 1st radical ion exchange column carries out the circulation absorption in pH regulator pond-dechromisation post-pH regulator pond, and the largest loop adsorption time is calculated as follows: cycle time T=η * resin leakage time T
1-resin regeneration time T
2, η gets 0.6～1; After circulation absorption finishes, original the 1st radical ion exchange column is regenerated by following program: water to pH regulator pond-alkali lye is washed and is entered in regeneration liquid bath-post residue alkali lye back suction behind the post and clean post-rinse water to diluted alkaline groove-water and enter pH regulator pond-acid solution and circulate and wash post in the emptying post, and it is stand-by that original completely the 1st radical ion exchange column of regenerating becomes n radical ion exchange column.
2, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1 is characterized in that said n radical ion exchange column is equipped with macroporous strong basic anionite-exchange resin.
3, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1 is characterized in that the used alkali lye of resin regeneration is the sodium hydroxide of 4～10% (w/w) in the step (3), and described acid solution is the hydrochloric acid of 0.3～10% (w/w).
4, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1 is characterized in that alkali lye is washed the post process in the step (3) to wash post with the speed of 1 times of bed volume/h.
5, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1 is characterized in that the Na in the regenerated liquid in the step (3)
2CrO
4, after Zeo-karb is handled, become H
2CrO
4Utilize or further process recovery solid Na again
2Cr
2O
7
6, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1, the operating capacity that it is characterized in that the resin in the ion exchange column drops to 0.8 o'clock of initial value, start following resin maintenance program: the circulation of single ion exchange column reproducer-safeguard liquid is squeezed into 2～12 hours-water of single ion exchange column and is cleaned post-rinse water and enter pH regulator pond-acid solution circulation and washed post 1～2 hour, and safeguarded every radical ion exchange column successively according to this program.
7, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 6, when it is characterized in that the resin slight pollution, the described liquid of safeguarding comprises following components in weight percentage: 8～16% hydrochloric acid, all the other are deionized water; During the resin serious pollution, the described liquid of safeguarding comprises following components in weight percentage: sodium-chlor 10～25%, and hydrogen peroxide 3～10%, sodium hydroxide 1～5%, all the other are deionized water.
8, the ion exchange treatment process that contains hexavalent chromium wastewater according to claim 1 is characterized in that the online Cr of this process using
6+The automatic mode of all valves of detector and Controlled by Programmable Controller, pressure and flow.
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| CN103938259A (en) * | 2014-05-13 | 2014-07-23 | 洛阳伟信电子科技有限公司 | Regeneration method of trivalent-chromium electroplating solution |
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| CN105130064A (en) * | 2015-09-25 | 2015-12-09 | 深圳前海中盛环保科技有限公司 | Novel method for treating chrome-containing wastewater and recycling chrome of chrome pigments |
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| CN115571948A (en) * | 2022-10-09 | 2023-01-06 | 泉州中节能水处理科技有限公司 | Method for treating and recycling electroplating chromium-containing wastewater through ion exchange |
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| CN109852995B (en) * | 2019-01-23 | 2021-03-05 | 郑宏 | Process for producing electrolytic nickel by ion exchange-electrolysis combined method |
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| KR102475076B1 (en) | 2019-11-29 | 2022-12-07 | 고려대학교 산학협력단 | Methode for iron chromate using ion-exchnage resin |
| CN114751486A (en) * | 2021-12-28 | 2022-07-15 | 中国启源工程设计研究院有限公司 | Device and method for recovering chromic acid from high-concentration chromium-containing wastewater in electroplating centralized control area through resin adsorption |
| CN115571948A (en) * | 2022-10-09 | 2023-01-06 | 泉州中节能水处理科技有限公司 | Method for treating and recycling electroplating chromium-containing wastewater through ion exchange |
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